CN101838363B - Method for producing propylene series copolymer - Google Patents

Method for producing propylene series copolymer Download PDF

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CN101838363B
CN101838363B CN2010101755231A CN201010175523A CN101838363B CN 101838363 B CN101838363 B CN 101838363B CN 2010101755231 A CN2010101755231 A CN 2010101755231A CN 201010175523 A CN201010175523 A CN 201010175523A CN 101838363 B CN101838363 B CN 101838363B
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zirconium dichloride
methylene radical
cyclopentadienyl moiety
fluorenyl
propylene
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CN101838363A (en
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土肥靖
冈本胜彦
森亮二
中村达也
雪田崇史
中川贵
绀野美幸
山村雄一
池永成伸
桧原真弓
广田成俊
丸林博雅
长桥幸治
绪续士郎
山口智弘
樋口匡史
一木康夫
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Mitsui Chemicals Inc
Mitsui Chemical Industry Co Ltd
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Mitsui Chemical Industry Co Ltd
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Abstract

The present invention relates to a method for producing propylene series copolymer, wherein the propylene is polymerized with at least one monometer selected from alpha-olefin and polyene except for propylene at the presence of catalyst. The catalyst comprises the following components: (a-2) crosslinked metallocene compound represented by a general formula [1-2]; and (b) at least more than one compound selected from the following components: (b-1) organic aluminium oxide, (b-2) a compound which forms ion pairs and (b-3) organic aluminium compound, wherein, R1, R2, R3 and R4 are hydrogen atoms; R5, R8, R9 and R12 are atoms or groups selected from hydrogen atom, alkyl and silicon-containing group; R6 and R11 are same atoms or same groups selected from hydrogen atom, alkyl and silicon-containing group; R7 and R10 are same atoms or same groups selected from hydrogen atom, alkyl and silicon-containing group; R6, R7, R10 and R11 are not all hydrogen atoms simultaneously; the adjacent groups in R5-R12 can combine with one another for forming a ring; R13 and R14 are aryl chlorides, etc., M is Ti, etc., Y is carbon atom, etc., Q is halogen, etc., and j is an integer selected from 1-4.

Description

The method of manufacture of propylene series copolymer
This case is On May 18th, 2006, application number does 200680017089.6 (PCT/JP2006/309972), denomination of invention is the dividing an application of patented claim of the method for manufacture, propene polymer, propylene polymer composition and uses thereof of method of manufacture, the propylene series copolymer of catalyst for olefines polymerizing, olefin polymer.
Technical field
The present invention (1) relates to the catalyst for olefines polymerizing that contains the crosslinked metallocene compound with ad hoc structure and uses the method for manufacture of the olefin polymer of this catalyst for olefines polymerizing.
The present invention (2) relates to the method for manufacture of propylene series copolymer.
The molding that the present invention (3) relates to propene polymer and obtained by this polymkeric substance, more specifically, the molding that relates to the syndiotactic propene polymer and obtain by this polymkeric substance.
The molding that the present invention (4) relates to propylene polymer composition, be made up of said composition, the pellet that is made up of propylene polymer composition, the thermoplastic polymer that is made up of this pellet is with properties-correcting agent, thermoplastic resin composition's method of manufacture.
The molding that the present invention (5) relates to propylene polymer composition, is made up of said composition.
The present invention (6) relates to the molding that propylene polymer composition forms with using said composition.
Background technology
As for olefines polymerization homogeneous phase series catalysts; So-called metallocene compound has been widely known by the people; The method of use the method for metallocene compound olefin polymerization, particularly terminal olefin being carried out Ziegler-Natta type polymerization since having disclosed the isotactic polymerization by people such as W.Kaminsky, from further raising polymerization activity with improve stereospecific property equal angles and carried out a large amount of improvement research (non-patent literature 1).
Ring as this research; Disclose the result who in the presence of the catalyzer that contains as the metallocene compound of transition-metal catalyst and aikyiaiurnirsoxan beta, carries out propylene polymerization by people such as J.A.Ewen and can access the Vestolen PP 7052 that syndiotactic five unit composition ratio surpass 0.7 high tacticity; Wherein, above-mentioned metallocene compound is dentate (non-patent literature 2) to utilize isopropylidene (isopropylidene) to make cyclopentadienyl moiety and the crosslinked dentate synthetic isopropylidene (cyclopentadienyl moiety) (9-fluorenes) that forms of fluorenyl.
As the improvement of this metallocene, have through making fluorenyl be converted into 2,7-di-t-butyl fluorenyl is attempted the research (patent documentation 1) of raising stereospecific property.
In addition, also have report to disclose and make fluorenyl be converted into 3, thus 6-di-t-butyl fluorenyl improve stereospecific property trial (patent documentation 2), change the trial (patent documentation 3,4) of crosslinked of cyclopentadienyl moiety and fluorenyl bonded.In addition; 5 dimethylated methylene base (the 3-tertiary butyl-5-methyl cyclopentadienyl) (fluorenyl) zirconium dichlorides of also having introduced methyl of cyclopentadiene ring are compared with dimethylated methylene base (3-tertiary butyl cyclopentadienyl moiety) (fluorenyl) zirconium dichloride, more can obtain high-molecular weight isotactic Vestolen PP 7052 (patent documentation 5).
But the polymerization of these metallocene compounds is still insufficient.And, utilize existing catalyzer, though can access the alpha-olefinic polymer that the fusing point as stereospecific property index reach a certain height, can not obtain carrying out high molecular weight polymers.The manufacturing of the polymkeric substance that for this reason, people hope to have certain HMP, molecular weight is high.And hope to obtain than the high polymkeric substance of existing goods fusing point.And, in order to realize industriallization, also hope under the temperature more than the normal temperature, preferably, can make alpha-olefinic polymer, but the catalyzer that does not also have up to now to realize such purpose exists with above-mentioned characteristic surpassing under the high temperature of normal temperature.
In addition; Even the existing catalyzer that has improved specific alpha-olefine polymerizing performance also may not be suitable to other terminal olefin, for example vinyl polymerization, along with the difference of the kind of the polymkeric substance that will make the more catalyst changeout of having to; Therefore, very inconvenient on making.
The inventor etc. are after furtheing investigate in view of above-mentioned condition; The result finds, uses the catalyst for olefines polymerizing that contains specific transition-metal catalyst, for example under the situation of alpha-olefine polymerizings such as propylene; Not only in polymerized at normal temperature but also the polymerization under can the high temperature of suitability for industrialized production; Also can obtain dystectic alpha-olefinic polymer, and be also can obtain having excellent activity and high-molecular weight ethylene-based polymer under the situation of alpha-olefine polymerizing of staple with ethene under the high temperature polymerization condition, promptly; Can demonstrate high-performance to far-ranging polymerization, thereby accomplish the present invention (1).
On the other hand, propylene series copolymer is used for various uses as the properties-correcting agent of thermoplastic resin material or thermoplastic resin.As the polymerizing catalyst that when making propylene series copolymer, uses, known have Titanium series catalyst, a metallocene series catalysts.But, using under the situation of Titanium series catalyst problem such as the composition that exists the propylene that can make is limited, and MWD is wide, and consistency is inhomogeneous.Although and the copolymerization property of metallocene series catalysts and terminal olefin is excellent, can realize the polymerization of far-ranging composition, but then, the molecular weight when existing polymerization under the high temperature does not increase, because polymerization activity is low, can not realize the problem of cost degradation and so on.
On the other hand; Find by people such as J.A.Ewen; Use and contain, can obtain syndiotactic five unit composition ratio and surpass 0.7 the high Vestolen PP 7052 (non-patent literature 2) of tacticity to utilize isopropylidene to make cyclopentadienyl moiety and the crosslinked isopropylidene that forms of fluorenes (cyclopentadienyl moiety) (9-fluorenes) be the transition-metal catalyst of dentate and the catalyzer of aikyiaiurnirsoxan beta.
In addition, there is report to disclose: to use and the above-mentioned similar catalyzer of the active transition-metal catalyst of syndiotactic polypropylenes that demonstrates, can obtain the multipolymer (patent documentation 6) of high propylene of molecular weight and ethene.But this transition-metal catalyst polymerization at high temperature is low, especially aspect molecular weight, still has further room for improvement.
Reports such as the inventor:, can obtain the high propylene series copolymer of molecular weight (patent documentation 7) through using specific transition-metal catalyst.But people also further hope under hot conditions, also can make high molecular weight polymers.
Therefore, the inventor etc. are seeing that after the above-mentioned condition further investigation, the result finds: through using specific transition-metal catalyst, the molecular weight of the propylene series copolymer of gained is high, polymerization manufacturing at high temperature, thus accomplish the present invention (2).
On the other hand, Vestolen PP 7052 comprises isotactic Vestolen PP 7052, syndiotactic polypropylenes etc., and wherein, the isotactic Vestolen PP 7052 is widely used in various uses because of cheap and rigidity, thermotolerance and surface luster property are excellent.
Comparatively speaking, syndiotactic polypropylenes is known to be in the presence of the catalyzer that contains vanadium compound and ether and organoaluminum, obtains through low temperature polymerization.The polymkeric substance that adopts this method to obtain, low with tacticity therebetween, shown the syndiotactic character of inherent hardly.
In recent years; Contain the transition-metal catalyst with asymmetric dentate and the catalyzer of aikyiaiurnirsoxan beta since at first finding to utilize, can obtain Vestolen PP 7052 (J.Am.Chem.Soc., 1988 that syndiotactic five unit composition ratio surpass 0.7 high tacticity by people such as J.A.Ewen; 110; 6255-6256, non-patent literature 2) since, a large amount of achievements about syndiotactic polypropylenes are disclosed.For example; In japanese kokai publication hei 8-67713 communique (patent documentation 8); Disclosed and used the racemize-2 that contains titanium, zirconium, hafnium and vanadium, the method for manufacture of the syndiotactic polypropylenes of the catalyzer of 2-dimethyl-propylidene (1-η 5-cyclopentadienyl moiety) (1-η 5-fluorenyl) dichloro metallocene and catalyst aid.In addition; Disclosed to use by the application's applicant and contained 1, the content (japanese kokai publication hei 4-802147 communique (patent documentation 9)) of the syndiotactic polypropylenes of specific trait is satisfied in the polymerizing catalyst manufacturing of 4-hexamethylene two subunits two [(cyclopentadienyl moiety-9-fluorenyl) zirconium dichloride].
Syndiotactic polypropylenes is compared with existing isotactic Vestolen PP 7052; The transparency is fabulous, surface gloss is high; And flexibility is excellent; Therefore, except as the known film of the polyacrylic purposes of existing isotactic, sheet material, fiber, be injected into body and be blow molded into body etc. the purposes, expect that also it can be used for the new purposes that isotactic Vestolen PP 7052 up to now can not be suitable for.But, to compare with the isotactic Vestolen PP 7052 according to the syndiotactic polypropylenes that the above-mentioned open described method of communique obtains, crystallization velocity is slow, Tc is low, therefore exists the problem of shaping processability difference.For example, even the granulation stage of syndiotactic polypropylenes in continuous operation all is difficult to crystallization, and Tc is also very low, compares with the isotactic Vestolen PP 7052, injection-molded article or extrude film processed or time that sheet cools is required longer.This character is slowed down the production rate of molding, and the result has just caused the increase of energy expenditure.In addition, plasticity not only, and, also still have further room for improvement aspect thermotolerance, the transparency, rigidity and the intensity etc. of molding balanced.
In addition, the applicant once proposed the technical scheme that is described below.
In japanese kokai publication hei 3-12439 communique (patent documentation 10), employing has been proposed 13The peak intensity of the syndiotactic five unit group keys of the methyl spectrogram that C-NMR measures is in the technical scheme of the syndiotactic polypropylenes resin combination that contains alfon and ethene and propylene copolymer in fact more than 0.7 of the peak intensity of all methyl.Said composition is to have high syndiotactic property, and shock resistance, compsn that the transparency is excellent.
In addition; In japanese kokai publication hei 7-247387 communique (patent documentation 11); Proposed to contain the technical scheme of the syndiotactic polypropylenes based resin composition of resinous principle 50～99.9 weight parts that constitute by syndiotactic polypropylenes 50～99 weight parts and isotactic Vestolen PP 7052 1～50 weight part and softening agent 0.1～50 weight part.Said composition can obtain having excellent shaping processability, and the molding transparent, that flexibility is excellent, and crystallization velocity is fast, shaping processability is excellent.
In addition, in japanese kokai publication hei 8-59916 communique (patent documentation 12), employing has been proposed 13The syndiotactic five unit composition ratio that C-NMR measures are the technical scheme of the syndiotactic polypropylenes resin combination that contains syndiotactic polypropylenes 97～99.99 weight % and Vilaterm 0.01～3 weight % more than 0.7.The crystallization velocity of said composition is fast, shaping processability is excellent.
In TOHKEMY 2000-191852 communique (patent documentation 13), proposed to contain the technical scheme of the soft transparent property syndiotactic polypropylenes compsn of syndiotactic polypropylenes and amorphism propylene-alpha-olefin based copolymer.The transparency of said composition, flexibility, anti-impaired property, excellent heat resistance.
In addition, in TOHKEMY 2000-191858 communique (patent documentation 14), disclosed the soft transparent property syndiotactic polypropylenes compsn that contains syndiotactic polypropylenes and be essentially the propylene-ethylene copolymers of syndiotactic structure.According to record, the transparency of said composition, flexibility, anti-impaired property, excellent heat resistance.
But the described compsn of these above-mentioned arbitrary communiques aspect plasticity, thermotolerance, the transparency, shock resistance, flexibility, anti-impaired property etc. harmonious, all still has further room for improvement.
In addition, the described compsn of these above-mentioned arbitrary communiques aspect plasticity, thermotolerance, the transparency, low-temperature impact resistance and flexibility etc. harmonious, all still has further room for improvement.
In addition, the described compsn of these above-mentioned arbitrary communiques aspect plasticity, thermotolerance, flexibility, anti-impaired property, wearability and vibration damping property etc. harmonious, all still has further room for improvement.
Patent documentation 1: japanese kokai publication hei 4-69394 communique
Patent documentation 2: TOHKEMY 2000-212194 communique
Patent documentation 3: TOHKEMY 2004-189666 communique
Patent documentation 4: TOHKEMY 2004-189667 communique
Patent documentation 5: Japan special table 2001-526730 communique
Patent documentation 6: japanese kokai publication hei 2-274703 communique
Patent documentation 7: TOHKEMY 2004-161957 communique
Patent documentation 8: japanese kokai publication hei 8-67713 communique
Patent documentation 9: japanese kokai publication hei 4-802147 communique
Patent documentation 10: japanese kokai publication hei 3-12439 communique
Patent documentation 11: japanese kokai publication hei 7-247387 communique
Patent documentation 12: japanese kokai publication hei 8-59916 communique
Patent documentation 13: TOHKEMY 2000-191852 communique
Patent documentation 14: TOHKEMY 2000-191858 communique
Non-patent literature 1:Angew.Chem.Int.Ed.Engl., 24,507 (1985)
Non-patent literature 2:J.Am.Chem.Soc., 1988,110,6255-6256
Summary of the invention
The technical problem that the present invention (1) will solve is; Be provided under the situation of alpha-olefine polymerizings such as propylene; Under normal temperature condition, be exactly under hot conditions not only, also can obtain the fusing point height, have the alpha-olefinic polymer of enough big molecular weight; And under hot conditions is that the alpha-olefines polymerization of staple is fashionable with ethene; Also can obtain having the catalyst for olefines polymerizing of excellent activity and high-molecular weight ethylene-based polymer, that is, the manufacturing of far-ranging olefin polymer demonstrated high performance catalyst for olefines polymerizing.And, the method for manufacture of the olefin polymer that uses such catalyst for olefines polymerizing also is provided.
The technical problem that the present invention (2) will solve is, relates to the method for manufacture of propylene series copolymer, provides to be characterised in that and can to obtain polymerization activity excellence, propylene series copolymer that molecular weight is high, the at high temperature method of manufacture of polymeric propylene series copolymer.
The technical problem that the present invention (3) will solve is that the syndiotactic propylene copolymer and the molding therefrom that have improved the problems referred to above are provided.Particularly,, the syndiotactic that has excellent formability propene polymer is provided, and thermotolerance, the transparency, rigidity, the excellent molding of tensile break strength are provided through improving crystallization velocity and Tc.
The technical problem that the present invention (3) will solve is that the propylene polymer composition of plasticity, excellent heat resistance is provided.
The technical problem that the present invention (4) will solve is to solve aforesaid problem, and plasticity, excellent heat resistance are provided, flexibility, the transparency, the compsn that anti-impaired property is also excellent, and the molding that is obtained by said composition.And; The technical problem that the present invention (4) will solve is; Through using said composition can access plasticity, excellent heat resistance, flexibility, the transparency, anti-impaired property be the thermoplastic polymer composition of excellence also, and the pellet that contains propylene polymer composition is provided thus; The thermoplastic polymer that contains this pellet is used properties-correcting agent, thermoplastic resin composition's method of manufacture.
The technical problem that the present invention (5) will solve is to solve aforesaid problem, and plasticity, excellent heat resistance are provided, and flexibility, the transparency, the also excellent compsn of low-temperature impact resistance, and the molding that is obtained by said composition.
The technical problem that the present invention (6) will solve is to solve aforesaid problem; The propylene polymer composition of plasticity, excellent heat resistance is provided; And plasticity, thermotolerance, anti-impaired property, wearability, propylene polymer composition that vibration damping property is excellent be provided; And plasticity, thermotolerance, anti-impaired property, wearability, vibration damping property be provided not only; The propylene polymer composition that flexibility is also excellent provides not only plasticity, thermotolerance in addition, the propylene polymer composition that anti-impaired property, wearability, flexibility, low-temperature impact resistance are also excellent.
The present invention's (1) catalyst for olefines polymerizing (1) is characterised in that, contains:
(a-1) the crosslinked metallocene compound of formula [1-1] expression and
(b) be selected from (b-1) Organoaluminoxy compound,
(b-2) with the right compound of above-mentioned crosslinked metallocene compound (a-1) reacting forming ion and
(b-3) at least a kind of compound in the organo-aluminium compound.
Figure GSA00000105371100071
In the formula [1-1], R 1, R 2, R 3, R 4, R 5, R 8, R 9And R 12Be selected from hydrogen, alkyl, contain silica-based, separately can be identical also can be different;
R 6, R 7, R 10And R 11These four bases are not Wasserstoffatomss, and be selected from alkyl or contain silica-based, separately can be identical also can be different;
R 2And R 3Can interosculate and form ring;
Be selected from R 5And R 6, R 7And R 8, R 8And R 9, R 9And R 10, and R 11And R 12In more than one adjacent base combination in, this adjacent base can interosculate and form ring;
R 13And R 14For being selected from Wasserstoffatoms, alkyl and the atom or the substituting group of silicon atoms base except methyl, each other can be identical also can be different, this substituting group can interosculate and form ring;
M is Ti, Zr or Hf;
Y is carbon or silicon;
Q is selected from halogen, alkyl, anion binding base and can be with lone-pair electron coordinate neutral dentate, separately can be identical also can be different,
J is 1～4 integer.
In addition, the R in the above-mentioned general formula [1-1] 1, R 2, R 3And R 4Be preferably hydrogen.
The present invention's (1) catalyst for olefines polymerizing (1) preferably also contains carrier (c).
The method of manufacture of the present invention's (1) olefin polymer is in the presence of above-mentioned catalyst for olefines polymerizing (1), makes more than one the monomer polymerization that is selected from the terminal olefin of carbonatoms more than 2.
The present invention (2) relates to the method for manufacture of propylene series copolymer (B1); It is characterized in that; In the presence of catalyst for olefines polymerizing (2), make propylene and the terminal olefin and at least a monomer polymerization in the polyenoid that are selected from except propylene, said catalyst for olefines polymerizing (2) contains:
(a-2) the crosslinked metallocene compound shown in the formula [1-2] and
(b) be selected from (b-1) Organoaluminoxy compound,
(b-2) with the right compound of above-mentioned crosslinked metallocene compound (a-2) reacting forming ion and
(b-3) at least a kind of compound in the organo-aluminium compound.Below, in the present invention (2), when only mentioning terminal olefin, this terminal olefin does not comprise propylene.
Figure GSA00000105371100081
In the formula [1-2], R 1, R 2, R 3, R 4, R 5, R 8, R 9And R 12For being selected from hydrogen, alkyl, containing atom or base in silica-based, separately each other can be identical also can be different;
R 6And R 11For being selected from Wasserstoffatoms, alkyl and containing identical atom or the identical base in silica-based;
R 7And R 10For being selected from Wasserstoffatoms, alkyl and containing identical atom or the identical group in silica-based;
R 6, R 7, R 10And R 11All be not Wasserstoffatoms simultaneously;
R 2And R 3Can interosculate and form ring;
R 5～R 12In can interosculate between the adjacent base and form ring;
R 13And R 14Be selected from the aryl of carbonatoms 6～18, the alkyl of carbonatoms 1～40, the alkylaryl of carbonatoms 6～40, the fluoro aryl of carbonatoms 6～20, the fluoroalkyl aryl of carbonatoms 7～40, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20 and the iodine alkylaryl of carbonatoms 7～40; Separately can be identical also can be different
R 13And R 14In at least one be the aryl that is selected from carbonatoms 7～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40;
M is Ti, Zr or Hf;
Y is carbon or silicon;
Q is selected from neutrality, conjugation or non-conjugated diene below 10 of halogen, alkyl, carbonatoms, anion binding base and can be with the identical or different combination in the lone-pair electron coordinate neutral dentate,
J is 1～4 integer.
In the present invention's (2) the preferred implementation, in above-mentioned formula [1-2], R 13And R 14Be selected from the aryl of carbonatoms 11～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40, separately can be identical also can be different.
In the present invention's (2) the preferred implementation, in above-mentioned formula [1-2], R 6And R 11For being selected from alkyl and the identical base that contains in silica-based, and R 7And R 10For being selected from alkyl and the identical base that contains in silica-based, R 6And R 7Can interosculate and form ring, R 10And R 11Can interosculate and form ring.
In the preferred implementation of the present invention (2), the R in the above-mentioned formula [1-2] 1, R 2, R 3, R 4Be hydrogen.
In the preferred implementation of the present invention (2); The content of the propylene composition of the propylene series copolymer of making (B1) is 95～51 moles of %; The terminal olefin composition is to be selected from least a in ethene, 1-butylene, 4-methyl-amylene-1,1-hexene, 1-octene, the 1-decene; Its content is 5～49 moles of %; The polyenoid composition is to be selected from least a in conjugated diolefine, non-conjugated diene and the non-conjugated triolefin, and its content is 0～20 mole of % (wherein, terminal olefin composition and polyenoid composition add up to 5～49 moles of %).
In the preferred implementation of the present invention (2), the content of the propylene composition of the propylene series copolymer of manufacturing (B1) is 95～51 moles of %, and the terminal olefin composition is to be selected from least a in ethene, 1-butylene, the 1-octene; Its content is 5～49 moles of %; The polyenoid composition is to be selected from the diene and 4 with norbornylene skeleton, 8-dimethyl--1,4; 8-triolefin in the last of the ten Heavenly stems, 4-ethylidene-8-methyl isophthalic acid; At least a in the 7-nonadiene (EMND), its content is 0～20 mole of % (wherein, terminal olefin composition and polyenoid composition add up to 5～49 moles of %).
In above-mentioned method of manufacture, being P from the unitary mole fraction of the formation of ethene E, be P with mole fraction from the terminal olefin of carbonatoms more than 4 HAOSituation under, the P of the propylene series copolymer of manufacturing (B1) E/ P HAOValue be preferably 0～0.80.
In the preferred implementation of the present invention (2), be that 40 ℃～200 ℃, polymerization pressure are to make aforesaid propylene based copolymer (B1) under the condition of 0.5Mpa～10Mpa at polymerization temperature.
The present invention's (3) acrylic polymer is to contain to be higher than 90mol% (wherein; The unitary total amount of formation with in this polymkeric substance (A) is 100mol%) the formation unit that is derived from propylene (wherein; Constituting unitary total amount is 100mol%) propene polymer; It is the syndiotactic propene polymer that satisfies following condition [1] and [2-1]; Preferably contain and be higher than 90mol%, the formation unit that is derived from propylene below 100mol% and be lower than more than one the formation unit (wherein, constituting unitary total amount is 100mol%) in the terminal olefin that being derived from of 10mol% be selected from ethene and carbonatoms 4～20 more than the 0mol%; The syndiotactic propene polymer that satisfies following condition [1], [2-2] and [3] (wherein; In following explanation, " propene polymer " not only comprises alfon, sometimes also as the term that comprises with the multipolymer of above-mentioned terminal olefin.In addition, sometimes acrylic polymer of the present invention is also referred to as " syndiotactic propene polymer (A) ").
[1] adopts 13The syndiotactic five unit composition ratio (rrrr divides rate) that C-NMR measures are more than 85%.
The fusing point (Tm) that [2-1] use differential scanning calorimeter (DSC) is tried to achieve is more than 145 ℃.
[2-2] uses fusing point (Tm) that differential scanning calorimeter (below be called DSC) tries to achieve more than 145 ℃, and melting heat (Δ H) is more than the 40mJ/mg.
[3] be made as T in the isothermal crystal temperature that will use differential scanning calorimeter to try to achieve Iso, with the isothermal crystal temperature T IsoIn the hypocrystalline time be made as t 1/2Situation under, at 110≤T Iso≤150 (℃) scope in, satisfy following formula (Eq-1).
1.67×10 -4exp(0.10×T iso)≤t 1/2≤5.56×10 -4exp(0.12×T iso) (Eq-1)
Syndiotactic propene polymer of the present invention (A) preferably except above-mentioned condition, also satisfies following condition [4],
[4] amount that dissolves in the n-decane part is below 1 weight % (wt%).
In addition, in following explanation, except above-mentioned condition [1]～[3], also satisfy the syndiotactic propene polymer (A) of following condition [4], be called as syndiotactic propene polymer (A ') sometimes especially.
Syndiotactic propene polymer of the present invention (A) is except above-mentioned condition [1]～[4], preferably also satisfy following condition [a]～[d] simultaneously.
[a] modulus in tension is the scope of 500～2000MPa;
[b] tensile break strength is more than the 20MPa;
The inside turbidity value of the compacting sheet material of [c] thickness 1mm is below 50%;
[d] pin is gone into temperature more than 145 ℃.
Wherein, in following explanation, except condition [1]～[4], the syndiotactic propene polymer of also satisfy condition [α]～[δ] is called as syndiotactic propene polymer (A ") sometimes especially.
In addition, the present invention (3) comprises by above-mentioned syndiotactic propene polymer (A), (A ') and (molding that A ") obtains.
And propylene polymer composition of the present invention contains above-mentioned syndiotactic propene polymer (A).The present invention's (3) molding is obtained by above-mentioned compsn.
The present invention's (4) propylene polymer composition (X1) contains:
Syndiotactic propene polymer (AA) 10～95 weight parts; With
Propylene-alpha-olefin copolymers (B2) 90～5 weight parts (wherein, with (AA) and (B2) add up to 100 weight parts),
In this propylene polymer composition (X1), this polymkeric substance (AA) fully satisfies following condition (a), and this multipolymer (B2) fully satisfies following condition (b).
(a): adopt 13The syndiotactic five unit composition ratio (rrrr divides rate) that C-NMR measures are more than 85%; And utilize fusing point (Tm) that DSC tries to achieve more than 145 ℃; The unitary content of formation that is derived from propylene surpasses 90 moles of % (being 100 moles of % with the unitary total amount of formation in this polymkeric substance (AA) wherein)
(b): the unitary content of formation that is derived from propylene is 55～90 moles of %; The unitary content of formation that is derived from least a alkene in the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20 be 10～45 moles of % (wherein; Add up to 100 moles of % so that the formation unit that is derived from propylene and the formation of the terminal olefin (wherein not comprising propylene) that is derived from carbonatoms 2～20 are unitary); According to JIS K-6721; The MFR that measures down at 230 ℃, 2.16kg load is 0.01～100g/10 minute a scope, and satisfies the propylene-alpha-olefin copolymers more than following condition (b-1) or (b-2) any;
(b-1): adopt 13The syndiotactic triad branch rate (rr divides rate) that the C-NMR method is measured is more than 60%;
(b-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] (dL/g) satisfies following relational expression with above-mentioned MFR (g/10 minute, 230 ℃, 2.16kg load):
1.50×MFR (-0.20)≤[η]≤2.65×MFR (-0.20)。
Preferred implementation as the propylene polymer composition (X1) of the present invention (4) has:
Contain more than (AA) syndiotactic propene polymer 50 weight parts, below 95 weight parts; (B2) propylene-alpha-olefin copolymers 5 weight parts are above, 50 weight parts are following (wherein; With (AA) and (B2) add up to 100 weight parts) propylene polymer composition (after this, sometimes said composition being called " compsn (X1i) "); With
Contain (AA) syndiotactic propene polymer 10 weight parts above, be lower than 50 weight parts; (B2) propylene-alpha-olefin copolymers surpasses 50 weight parts, 90 weight parts are following (wherein; With (AA) and (B2) add up to 100 weight parts) propylene polymer composition (after this, sometimes said composition is called " compsn (X1ii).
Above-mentioned compsn (X1), (X1i) and (X1ii) be preferably (1) and use the hypocrystalline time (t in 110 ℃ the isothermal crystal that differential scanning calorimeter tries to achieve 1/2) scope below 1000sec.
Above-mentioned compsn (X1), (X1i) and (X1ii) be preferably (2) pin to go into temperature be more than 145 degree.
It is more than 145 ℃ that (2) pin that is preferably aforesaid propylene based polymer composition (X1i) is especially gone into temperature; And (3) 0 ℃ Izod shock strength is more than the 50J/m; (4) modulus in tension is in the scope of 100MPa～2000MPa, and the inside turbidity value of the compacting sheet material of (5) thickness 1mm is below 50%.
Aforesaid propylene based polymer composition (X1ii) is preferably (2) pin especially, and to go into temperature be more than 145 ℃, and (4) modulus in tension is in the scope of 1MPa～400MPa, and the inside turbidity value of the compacting sheet material of (5) thickness 1mm is below 30%.
At aforesaid propylene based polymer composition (X1), compsn (X1i) with (X1ii); Be preferably limiting viscosity [η] that above-mentioned syndiotactic propene polymer (AA) measures scope in 135 ℃ of naphthane, use melting heat (Δ H) that differential scanning calorimeter (DSC) measures as more than the 40mJ/mg at 0.1～10dL/g.
At aforesaid propylene based polymer composition (X1), compsn (X1i) or (X1ii), be preferably MWD (Mw/Mn, Mn: number-average molecular weight, Mw: that aforesaid propylene-alpha-olefinic polymer (B2) uses GPC to try to achieve weight-average molecular weight) below 3.5.
The propylene polymer composition (Y) of the present invention's (4) alternate manner contains:
Be derived from 99.7～70.0 moles of % in formation unit of propylene; With
Be derived from 0.3～30.0 mole of % in formation unit (wherein, being 100 moles of %) of the terminal olefin (not comprising propylene) of carbonatoms 2～20 with the formation unit of the terminal olefin (comprising propylene) that is derived from carbonatoms 2～20,
(2) pin is gone into temperature more than 145 ℃,
(3) the Izod shock strength is more than 50J/m,
(4) modulus in tension is the scope of 100MPa～2000MPa,
(5) the inside turbidity value of the compacting sheet material of thickness 1mm is below 50%.
And the propylene polymer composition (Z) of another embodiment of the present invention (4) contains: 95.0～55.0 moles of % in formation unit that are derived from propylene; With 5.0～45.0 moles of % in formation unit of the terminal olefin that is derived from carbonatoms 2～20 (but not comprising propylene) (wherein, adding up to 100 moles of %) so that the formation of the terminal olefin (comprising propylene) that is derived from carbonatoms 2～20 is unitary,
(2) pin is gone into temperature more than 145 ℃,
(3) modulus in tension is below 1MPa～400MPa,
(5) the inside turbidity value of the compacting sheet material of thickness 1mm is below 30%.
In addition, the present invention's (4) molding uses the aforesaid propylene based polymer composition to obtain.
The present invention's (4) pellet is the pellet that is made up of acrylic polymer (W), and this acrylic polymer (W) contains:
Syndiotactic propene polymer (AA1) 1～65 weight part;
Propylene-alpha-olefin copolymers (B21) 99～35 weight parts (wherein, with (AA1) and (B21) add up to 100 weight parts),
And this polymkeric substance (AA1) fully satisfies following condition (a1), and this multipolymer (B21) fully satisfies following condition (b1),
(a1): adopt 13The syndiotactic five unit composition ratio (rrrr divides rate) that C-NMR measures are more than 85%; And utilize fusing point (Tm) that DSC tries to achieve more than 145 ℃; The unitary content of formation that is derived from propylene surpasses 90 moles of % (being 100 moles of % with the unitary total amount of formation in this polymkeric substance (AA1) wherein)
(b1): the unitary content of formation that is derived from propylene is 55～90 moles of %; The unitary content of formation that is derived from least a alkene in the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20 be 10～45 moles of % (wherein; Add up to 100 moles of % so that the formation unit that is derived from propylene and the formation of the terminal olefin (but not comprising propylene) that is derived from carbonatoms 2～20 are unitary); According to JIS K-6721; 230 ℃, 2.16kg load down the MFR of mensuration be 0.01～100g/10 minute scope, and satisfy more than following condition (b1-1) or (b1-2) any;
(b1-1): adopt 13The syndiotactic triad branch rate (rr divides rate) that the C-NMR method is measured is more than 60%;
(b1-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] (dL/g) satisfies following relational expression with above-mentioned MFR (g/10 minute, 230 ℃, 2.16kg load):
1.50×MFR (-0.20)≤[η]≤2.65×MFR (-0.20)。
The present invention's (4) thermoplastic polymer is processed by above-mentioned pellet with properties-correcting agent.
The method of manufacture of the present invention's (4) thermoplastic polymer composition is characterised in that, above-mentioned thermoplastic polymer is mixing with properties-correcting agent and thermoplastic polymer.
The present invention's (5) propylene polymer composition (X2) is characterised in that, contains:
Syndiotactic propene polymer (AA) 100～25 weight parts;
Propylene-alpha-olefin copolymers (B2) 0～75 weight part (wherein, with (AA) and (B2) add up to 100 weight parts); With
With respect to (AA) and 100 weight parts of total (B2), be the ethene-alpha-olefin copolymer (C0) of 1～100 weight part,
And this polymkeric substance (AA) fully satisfies following condition (a), and this multipolymer (B2) fully satisfies following condition (b), and this multipolymer (C0) fully satisfies following condition (c),
(a1): adopt 13The syndiotactic five unit composition ratio (rrrr divides rate) that C-NMR measures are more than 85%; And utilize fusing point (Tm) that DSC tries to achieve more than 145 ℃; The unitary content of formation that is derived from propylene surpasses 90 moles of % (being 100 moles of % with the unitary total amount of formation in this polymkeric substance (AA) wherein)
(b): the unitary content of formation that is derived from propylene is 55～90 moles of %; The unitary content of formation that is derived from least a alkene in the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20 be 10～45 moles of % (wherein; Add up to 100 moles of % so that the formation unit that is derived from propylene and the formation of the terminal olefin (but not comprising propylene) that is derived from carbonatoms 2～20 are unitary); According to JIS K-6721; 230 ℃, 2.16kg load down the MFR of mensuration be 0.01～100g/10 minute scope, and satisfy more than following condition (b-1) or (b-2) any:
(b-1): adopt 13The syndiotactic triad branch rate (rr divides rate) that the C-NMR method is measured is more than 60%,
(b-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] (dL/g) satisfies following relational expression with above-mentioned MFR (g/10 minute, 230 ℃, 2.16kg load):
1.50×MF?R (-0.20)≤[η]≤2.65×MFR (-0.20)。
(c) be derived from 50～99 moles of % in formation unit of propylene; 1～50 mole of % in formation unit (wherein, adding up to 100 moles of %) that contains the terminal olefin that is derived from the carbonatoms 3～20 beyond the ethene to be derived from from the formation unit of ethene with the formation of the terminal olefin that is derived from carbonatoms 3～20 is unitary.
As the preferred implementation of the present invention's (5) propylene polymer composition, can enumerate and contain:
Syndiotactic propene polymer (AA) 98～40 weight parts,
Propylene-alpha-olefin copolymers (B2) 2～60 weight parts (wherein, with (AA) and (B2) add up to 100 weight parts) and
With respect to (AA) and 100 weight parts of total (B2), be the ethene-alpha-olefin copolymer (C0) of 1～100 weight part,
And; This polymkeric substance (AA) fully satisfies following condition (a), and this multipolymer (B2) fully satisfies following condition (b '), and this multipolymer (C0) fully satisfies the propylene polymer composition (X2) (hereinafter is called said composition (X2i) sometimes) of following condition (c '); Wherein
(a): adopt 13The syndiotactic five unit composition ratio (rrrr divides rate) that C-NMR measures are more than 85%; And utilize fusing point (Tm) that DSC tries to achieve more than 145 ℃; The unitary content of formation that is derived from propylene surpasses 90 moles of % (being 100 moles of % with the unitary total amount of formation in this polymkeric substance (AA) wherein)
(b '): the unitary content of formation that is derived from propylene is 65～90 moles of %; The unitary content of formation that is derived from least a alkene in the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20 be 10～35 moles of % (wherein; Add up to 100 moles of % so that the formation unit that is derived from propylene and the formation of the terminal olefin (but not comprising propylene) that is derived from carbonatoms 2～20 are unitary); According to JIS K-6721; 230 ℃, 2.16kg load down the MFR of mensuration be 0.01～100g/10 minute scope, and satisfy following condition (b-1) or (b-2) in any more than:
(b-1): adopt 13The syndiotactic triad branch rate (rr divides rate) that the C-NMR method is measured is more than 60%,
(b-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] (dL/g) satisfies following relational expression with above-mentioned MFR (g/10 minute, 230 ℃, 2.16kg load):
1.50×MFR (-0.20)≤[η]≤2.65×MFR (-0.20)。
The unitary content of formation that (c ') is derived from propylene is 60～95 moles of %; The unitary content of formation that is derived from the terminal olefin of the carbonatoms 3～20 beyond the ethene is 5～40 moles of % (wherein, adding up to 100 moles of % so that the formation unit that is derived from ethene and the formation of the terminal olefin that is derived from carbonatoms 3～20 are unitary).
In addition, as the preferred implementation of the present invention (5), can enumerate and contain:
Syndiotactic propene polymer (AA) 100 weight parts and
Ethene-alpha-olefin copolymer (C0) 1～100 weight part,
And this polymkeric substance (AA) fully satisfies following condition (a), and this multipolymer (C0) fully satisfies the propylene polymer composition (X2) (after this, sometimes said composition being called " compsn (X2ii) ") of following condition (c '), wherein,
(a): adopt 13The syndiotactic five unit composition ratio (rrrr divides rate) that C-NMR measures are more than 85%; And utilize fusing point (Tm) that DSC tries to achieve more than 145 ℃; The unitary content of formation that is derived from propylene surpasses 90 moles of % (being 100 moles of % with the unitary total amount of formation in this polymkeric substance (AA) wherein)
The unitary content of formation that (c ') is derived from ethene is 60～95 moles of %; The unitary content of formation that is derived from the terminal olefin of the carbonatoms 3～20 beyond the ethene is 5～40 moles of % (wherein, adding up to 100 moles of % so that the formation unit that is derived from ethene and the formation of the terminal olefin that is derived from carbonatoms 3～20 are unitary).
Above-mentioned compsn (X2), (X2i) or (X2ii) for example be preferably (1) and use the hypocrystalline time (t in 110 ℃ the isothermal crystal that differential scanning calorimeter tries to achieve 1/2) scope below 1000sec.
In addition, above-mentioned compsn (X2), (X2i) or (X2ii) for example be preferably (2) pin to go into temperature be more than 145 ℃.
Be preferably limiting viscosity [η] that aforesaid propylene-alpha-olefinic polymer (B2) measures scope in 135 ℃ of naphthane, the MWD (Mw/Mn, the Mn: number-average molecular weight, Mw: that use GPC to try to achieve weight-average molecular weight) below 3.5 at 0.1～10dL/g.
Be preferably above-mentioned ethene-alpha-olefin copolymer (C0) according to JIS K-6721,190 ℃, 2.16kg load down the MFR of mensuration be 0.01～100g/10 minute scope, density is 0.910～0.850 (g/cm 3).
And the present invention's (5) molding is characterised in that, uses aforesaid propylene based polymer composition (X2) to process.
The present invention's (6) propylene polymer composition (X3) is characterised in that, contains:
Syndiotactic propene polymer (AA) 10～95 weight parts; With
Propylene-alpha-olefin copolymers (B3) 90～5 weight parts (wherein, with (AA) and (B3) add up to 100 weight parts),
And this polymkeric substance (AA) fully satisfies following condition (a), and this multipolymer (B3) fully satisfies following condition (b), wherein:
(a): adopt 13The syndiotactic five unit composition ratio (rrrr divides rate) that C-NMR measures are more than 85%; And utilize fusing point (Tm) that DSC tries to achieve more than 145 ℃; The unitary content of formation that is derived from propylene surpasses 90 moles of % (being 100 moles of % with the unitary total amount of formation in this polymkeric substance (AA) wherein)
(b): the unitary content of formation that is derived from propylene is 30～90 moles of %; The unitary content of formation that is derived from least a alkene in the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20 be 10～70 moles of % (wherein; Add up to 100 moles of % so that the formation unit that is derived from propylene and the formation of the terminal olefin (but not comprising propylene) that is derived from carbonatoms 2～20 are unitary); According to JIS K-6721; 230 ℃, 2.16kg load down the MFR of mensuration be 0.01～100g/10 minute scope, and satisfy more than following condition (b-1) or (b-2) any:
(b-1): adopt 13The syndiotactic triad branch rate (rr divides rate) that the C-NMR method is measured is more than 60%,
(b-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] (dL/g) satisfies following relational expression with above-mentioned MFR (g/10 minute, 230 ℃, 2.16kg load):
1.50×MFR (-0.20)≤[η]≤2.65×MFR (-0.20)。
Preferred implementation as the propylene polymer composition (X3) (hereinafter referred is " compsn (X3) ") of the present invention (6); Can enumerate total 100 weight parts, also contain (C1) and be selected from more than one the propylene polymer composition (hereinafter sometimes said composition being called " compsn (X3i) ") of resin 0.1～100 weight part in rosin series resin, terpenic series resin and the petroleum resin with respect to above-mentioned syndiotactic propene polymer (AA) and aforesaid propylene-alpha-olefin copolymer (B3).
Preferred implementation as above-mentioned compsn (X3) and compsn (X3i); Can enumerate aforesaid propylene-alpha-olefin copolymer (B3) and be the unitary content of formation that is derived from propylene is 30～90 moles of %; The formation unit that is derived from ethene and the unitary total amount of formation that is derived from the terminal olefin of carbonatoms 4～20 be 10～70 moles of % (wherein; Unitaryly add up to 100 moles of % with the formation unit that is derived from propylene, the formation unit and the formation of the terminal olefin that is derived from carbonatoms 4～20 that are derived from ethene) the alpha-olefin copolymer of propylene-ethylene-carbonatoms 4～20, and the unitary ratio of formation that will be derived from ethene is made as P E(mole %) is made as P with the unitary ratio of the formation of the terminal olefin that is derived from carbonatoms 4～20 HAOUnder the situation of (mole %), P E≤P HAOPropylene polymer composition (X3).
Preferred implementation as the propylene polymer composition (X3) of the present invention (6); Can enumerate total 100 weight parts, also contain (1) of the present invention described propylene polymer composition (after this sometimes said composition being called " compsn (X3ii) ") of noncrosslinking or partial cross-linked ethylene series thermoplastic elastomer (C2) 0.1～500 weight part with respect to above-mentioned syndiotactic propene polymer (AA) and propylene-alpha-olefin copolymers (B3).
In above-mentioned compsn (X3); Be preferably limiting viscosity [η] that above-mentioned syndiotactic propene polymer (AA) measures in the 135 ℃ of naphthane scope at 0.1～10dL/g, the melting heat of using differential scanning calorimeter (DSC) to measure to try to achieve (Δ H) is as more than the 40mJ/mg.
Be preferably in above-mentioned compsn (X3) MWD that the use GPC of aforesaid propylene-alpha-olefinic polymer (B3) tries to achieve (Mw/Mn, Mn: number-average molecular weight, Mw: weight-average molecular weight) below 3.5.
The present invention's (6) molding uses above-mentioned compsn (X3) to process.
Catalyst for olefines polymerizing (1) using the present invention (1) makes under the situation of the alpha-olefine polymerizings of carbonatoms more than 3 such as propylene; Not only under normal temperature condition; Be exactly under hot conditions; Also the sufficiently high alpha-olefinic polymer of fusing point height and molecular weight be can obtain, and, excellent activity and the sufficiently high ethylene-based polymer of molecular weight also can be obtained having using same catalyzer to make under the hot conditions under the situation of the alpha-olefine polymerizing that contains some ethene at least with good activity; That is, the manufacturing to far-ranging olefin polymer demonstrates high-performance.
And; Make olefin polymer through using such catalyst for olefines polymerizing; Under hot conditions; Also can obtain the sufficiently high alpha-olefinic polymer of fusing point height and molecular weight, and use same catalyzer under hot conditions, to make the alpha-olefines polymerization that contains some ethene at least fashionable, also can obtain the ethylene-based polymer that has excellent activity and have sufficiently high molecular weight with good activity.
According to the method for manufacture of the propylene series copolymer (B1) of the present invention (2), can obtain copolymerization performance excellence, propylene series copolymer (B1) that molecular weight is high.So just can make the inaccessiable high-molecular weight propylene series copolymer of existing solution polymerization with high-level efficiency.In addition, when making the propylene series copolymer of same molecular weight,, therefore can make propylene series copolymer with high-level efficiency owing to can under higher temperature, realize polymerization than existing catalyst for olefines polymerizing.
According to the present invention (3), plasticity, excellent heat resistance can be provided, the syndiotactic propene polymer that especially plasticity, thermotolerance, the transparency, rigidity, tensile break strength are excellent and contain the molding of this polymkeric substance.
Plasticity, the excellent heat resistance of the present invention's (3) the compsn that contains syndiotactic propene polymer (A).The excellent heat resistance of the molding that obtains by the compsn that contains syndiotactic propene polymer (A) of the present invention.
Plasticity, the excellent heat resistance of the present invention's (4) propylene polymer composition, and the transparency, flexibility, anti-impaired property are also excellent.
The present invention's (4) molding excellent heat resistance, and the transparency, flexibility, anti-impaired property are also excellent.
Use the present invention's (4) pellet, can obtain plasticity, excellent heat resistance, flexibility, the transparency, anti-impaired property be the thermoplastic polymer composition of excellence also.
Use the present invention's (4) thermoplastic polymer to use properties-correcting agent, can obtain plasticity, excellent heat resistance, flexibility, the transparency, anti-impaired property be the thermoplastic polymer composition of excellence also.The present invention's (4) thermoplastic resin composition's method of manufacture can be made plasticity, excellent heat resistance with high productivity, and flexibility, the transparency, anti-impaired property be the thermoplastic polymer composition of excellence also.
Plasticity, the excellent heat resistance of the present invention's (5) propylene polymer composition (X2), and the transparency, flexibility, low-temperature impact resistance are also excellent.
The excellent heat resistance of the present invention's (5) molding, and the transparency, flexibility, low-temperature impact resistance are also excellent.
Plasticity, the excellent heat resistance of the present invention's (6) propylene polymer composition (X3).
In addition, the present invention's (6) propylene polymer composition (X3) is being P with the unitary ratio of the formation that is derived from ethene E(mole %) is P with the unitary ratio of formation of the terminal olefin that is derived from carbonatoms 4～20 HAOUnder the situation of (mole %), as long as satisfy P E≤P HAO, then plasticity, thermotolerance, anti-impaired property, wearability, vibration damping property are excellent.
In addition; Added under more than one the situation of resin that is selected from rosin series resin, terpenic series resin and the petroleum resin at the propylene polymer composition (X3) of the present invention (6), plasticity, thermotolerance, anti-impaired property, wearability, vibration damping property, flexibility are excellent.
In addition, the propylene polymer composition (X3) in the present invention (6) has added under the situation of thermoplastic elastomer, plasticity, thermotolerance, anti-impaired property, wearability, flexibility, low-temperature impact resistance excellence.
Description of drawings
Fig. 1 is the present invention's (3) the embodiment and the specific isothermal crystal temperature (T of the described syndiotactic propene polymer of comparative example Iso) with this temperature under hypocrystalline time (t 1/2) the graphic representation of relation.Wherein, the part that surrounds of thick line is represented the zone of the defined parameter inequality of condition [3] (Eq-1) defined among the present invention (3).
Fig. 2 is the embodiment of the present invention (4)～(6) and the specific isothermal crystal temperature (T of the described syndiotactic propene polymer of comparative example Iso) with this temperature under hypocrystalline time (t 1/ 2) the graphic representation of relation.Wherein, the part that surrounds of thick line is represented the zone of inequality (Eq-1) defined of the preferred property of syndiotactic propene polymer (AA) used in the present invention (4)～(6).
Fig. 3 is (AA) composition used in the present invention (4) and (5) or (B2) graphic representation of MFR and the relation of [η] of composition corresponding polymer and isotactic acrylic polymer.Wherein, the part that thick line surrounds is represented the zone of condition (b-2) defined of one of preferred property of (B2) composition used in the present invention (4) and (5), and dotted line is represented the preferable range of (b-2).
Fig. 4 is (AA) composition used among the present invention (6) or (B3) graphic representation of MFR and the relation of [η] of composition corresponding polymer and isotactic acrylic polymer.Wherein, the part that thick line surrounds is represented the zone of condition (b-2) defined of one of preferred property of (B3) composition used among the present invention (6), and dotted line is represented the preferable range of (b-2).
Embodiment
<Catalyst for olefines polymerizing (1)>
At first, the catalyst for olefines polymerizing (1) to the present invention (1) is elaborated.
The present invention's (1) catalyst for olefines polymerizing (1) is characterised in that, contains:
(a-1) the crosslinked metallocene compound of above-mentioned general formula [1-1] expression and
(b) be selected from (b-1) Organoaluminoxy compound,
(b-2) with the right compound of above-mentioned crosslinked metallocene compound (a-1) reacting forming ion and
(b-3) at least a kind of compound in the organo-aluminium compound.
Below; To the used crosslinked metallocene compound (a-1) of the catalyst for olefines polymerizing (1) of the present invention (1), contain the olefin polymerization catalysis (1) of this crosslinked metallocene compound (a-1), the method for in the presence of this olefin polymerization catalysis (1), carrying out olefinic polymerization, the embodiment of explanation the best of being used to carry out an invention successively.
(a-1) crosslinked metallocene compound
Crosslinked metallocene compound (a-1) shown in the above-mentioned general formula [1-1] (in this specification sheets, being also referred to as " composition (a-1) ") on chemical structure, has following characteristics [m1-1]～[m1-2].
In [m1-1] two dentates, one of them is to have substituent cyclopentadienyl moiety, and another is to have substituent fluorenyl (hereinafter is also referred to as " replacement fluorenyl " sometimes).
The transition metal (M) that [m1-2] constitutes metallocene compound is titanium, zirconium or hafnium.
Below; After the having substituent cyclopentadienyl moiety, replace fluorenyl of the characteristic on used crosslinked metallocene compound (a-1) chemical structure, crosslinked and further feature describe to the present invention (1) successively; Preferred crosslinked metallocene compound [1-1] and example thereof to these characteristics are elaborated, and the polymerization method to the present invention (1) of using this crosslinked metallocene compound (a-1) is elaborated at last.
Can have substituent cyclopentadienyl moiety
Cyclopentadienyl moiety can be substituted, and also can not be substituted.Not substituted cyclopentadienyl moiety is meant the R that the cyclopentadiene base section in the above-mentioned general formula [1-1] is had 1, R 2, R 3And R 4All be the cyclopentadienyl moiety of Wasserstoffatoms, substituted cyclopentadienyl moiety can refer to R 1, R 2, R 3And R 4In can or contain silica-based (f2) substituted cyclopentadienyl moiety by alkyl (f1) more than any.R 1, R 2, R 3And R 4In be that these bases can be the same or different under the situation of the base beyond the Wasserstoffatoms more than two.
As being used for R 1～R 4Alkyl (f1), do not form under the situation of ring at this substituting group with other substituting group, preferably can enumerate the alkyl (hereinafter is also referred to as " alkyl (f1 ') ") of total carbon atom number 1～20.
And as R 2And R 3Be the situation of alkyl (f1), also can enumerate R 2And R 3Interosculate and form the situation of ring (hereinafter is also referred to as " ring (f ") ").In the case, for making the for example syndiotactic poly-alpha olefins of high stereospecific property, more preferably R 1～R 4In R only 2And R 3Form ring.
For example, in substituent R 2And R 3Interosculate under the situation of ring, although above-mentioned R 2And R 3Preferred carbonatoms separately is 1～20, but the total of two substituent carbonatomss of Cheng Huan is preferably 2～40, more preferably 3～30, further is preferably 4～20.
And in substituent R 2And R 3Interosculate and form under the situation of ring; The a part of Wasserstoffatoms that directly links to each other with this substituent carbon can be by halogen atom, contain oxygen base, nitrogenous base, contain silica-based replacement; In the case, the total that forms two substituent carbonatomss of ring also comprise above-mentionedly contain oxygen base, nitrogenous base, contain silica-based in contained carbonatoms.
In addition, the alkyl of total carbon atom number 1～20 (f1 ') is meant alkyl, thiazolinyl, alkynyl or the aryl that only contains carbon and hydrogen.
The alkyl of total carbon atom number 1～20 (f1 ') is except the alkyl that only contains carbon and hydrogen, thiazolinyl, alkynyl, the aryl, also comprise a part of Wasserstoffatoms of directly linking to each other with these carbon by halogen atom, contain oxygen base, nitrogenous base, contain the silica-based substituted heteroatomic alkyl that contains.As these alkyl (f1 '), can enumerate:
Straight chain shape alkyl such as methyl, ethyl, n-propyl, allyl group (allyl), normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl;
Sec.-propyl, the tertiary butyl, amyl group, 3-methyl amyl, 1; 1-diethylammonium propyl group, 1; 1-dimethylbutyl, 1-methyl isophthalic acid-propyl group butyl, 1,1-propyl group butyl, 1,1-dimethyl--2-methyl-propyl, 1-methyl isophthalic acid-sec.-propyl-branched alkyl such as 2-methyl-propyl;
Cyclic saturated hydrocarbon bases such as cyclopentyl, cyclohexyl, suberyl, ring octyl group, norcamphyl, adamantyl;
Ring-type unsaturated alkyl and these nuclear alkyl replacement bodies such as phenyl, naphthyl, xenyl, phenanthryl, anthryl;
The substituted saturated hydrocarbyl of aryl such as benzyl, cumyl;
Methoxyl group, oxyethyl group, phenoxy, N-methylamino, trifluoromethyl, trisbromomethyl, pentafluoroethyl group, pentafluorophenyl group, fluorophenyl, chloro-phenyl-, bromophenyl, benzyl chloride base, luorobenzyl, bromobenzyl, dichloro benzyl, difluorobenzyl, trichlorine benzyl, trifluoro-benzyl etc. contain heteroatomic alkyl.
Contain silica-based (f2) and be meant to have the base that forms the Siliciumatom of covalent linkage with the ring carbon of cyclopentadienyl moiety, be specially alkyl tin groups, alkyl silane groups, aryl-silane base.As preferably containing silica-based (f2), do not form under the situation of ring at this substituting group with other substituting group, can enumerate containing of total carbon atom number 1～20 silica-based (f2 '), for example, can enumerate examples such as TMS, tri-phenyl-silane base.
In this cyclopentadienyl moiety, preferred R 1And R 4Be identical atom or identical base, R 2With R 3In conjunction with forming ring or being identical atom or identical base, more preferably R 1And R 4Be Wasserstoffatoms, preferred especially R 1, R 2, R 3And R 4Be Wasserstoffatoms.
Replace fluorenyl
Fluorenyl part shown in the above-mentioned general formula [1-1] that in the polymerization method of the present invention (1), uses in the chemical structural formula, important first aspect are the R in the above-mentioned general formula [1-1] 6, R 7, R 10, R 11Four bases are not Wasserstoffatomss.R 6, R 7, R 10And R 11Being selected from alkyl and containing silica-basedly, also can be that above-mentioned alkyl (f1) or above-mentioned contains silica-based (f2).
In addition, important second aspect is R in the fluorenyl part 6With R 7And R 10With R 11Do not mutually combine and form ring.In the present invention (1) in the used crosslinked metallocene compound (a-1), R 6, R 7, R 10, R 11Four bases are not Wasserstoffatomss, and R 6With R 7And R 10With R 11Not interosculating forms ring, just can reach the inaccessiable polymerization activity of existing polymerization thus, and can make the alpha-olefinic polymer of dystectic carbonatoms more than 3, for example propene polymer.
In addition, R 5, R 8, R 9, R 12Can be to be selected from hydrogen, alkyl (f1), to contain identical or different atom or the base of difference in silica-based (f2), be selected from R 5With R 6, R 7With R 8, R 8With R 9, R 9With R 10, and R 11With R 12In more than one adjacent base combination in, this adjacent group also can interosculate and form ring.
As in substituent R 5～R 12In the alkyl (f1) that uses, under the situation of this substituting group, preferably can enumerate the alkyl (alkyl (f1 ')) of total carbon atom number 1～20 for the base that do not form ring with other substituting group.
In addition, as substituent R 5～R 12Under the situation for alkyl (f1), also can enumerate this substituting group and substituent R 5～R 12In adjacent other substituting group in the scope of above-mentioned adjacent base combination, interosculate into the situation of ring.At this moment, R 5～R 12In interosculate between the adjacent substituting group form ring (ring (f ' ")).
In addition, as in the scope of above-mentioned adjacent base combination, substituent R 5～R 12In interosculate between the adjacent substituting group and form the situation of ring, be preferably substituent R 5～R 12In adjacent two interosculate and form the situation of ring.
For example,, two adjacent substituting groups (are being selected from R under interosculating the situation that forms ring 5With R 6, R 7With R 8, R 8With R 9, R 9With R 10, and R 11With R 12In more than one adjacent base combination in form the situation of ring), above-mentioned R 5～R 12Preferred separately carbonatoms be 1～20, but the total that forms two substituent carbonatomss of ring is preferably 2～40, more preferably 3～30, further is preferably 4～20.
In addition; Interosculate at adjacent substituting group and to form under the situation of ring; The a part of Wasserstoffatoms that directly links to each other with this substituent carbon also can be by halogen atom, contain oxygen base, nitrogenous base, contain silica-based replacement; In the case, the total that forms a plurality of substituent carbonatomss of ring also comprise above-mentionedly contain oxygen base, nitrogenous base, contain silica-based in contained carbonatoms.
From the viewpoint of the synthetic aspect of the present invention's (1) catalyzer, R 6And R 11Be preferably same atom or same base, R 7And R 10Be preferably same atom or same base.Preferred base as alkyl (f1) is alkyl (f1 '), the ring structure (f ' " of above-mentioned total carbon atom number 1～20), the preference that contains silica-based (f2) is aforesaid this substituting group does not form total carbon atom number 1～20 under the situation of ring with other substituting group contain silica-based (f2 ').
In the present invention (1), for obtaining not only under the polymerizing condition at normal temperatures, and under the high temperature polymerization condition, the polymkeric substance of the also equal even terminal olefin of carbonatoms more than 3 that molecular weight more than it is high of fusing point, R with existing goods 6And R 11Be preferably following any especially:
1) is being alkyl, and do not forming under the situation of ring, respectively independently for carbonatoms more than 2, be preferably alkyl more than 4 more preferably more than 3, especially with adjacent base;
2) be respectively contain silica-based.
And, contain silica-based in, be preferably carbonatoms and Siliciumatom number add up to more than 3, be preferably more than 4 contain silica-based.And, for further improving the present invention's (1) effect, at R 6For not forming hydrocarbon, the R of ring with adjacent base 7For not forming under the situation of the alkyl that encircles preferred R with adjacent base 6Carbonatoms and R 7Carbonatoms identical or on this.And at R 6, R silica-based for containing 7For containing under the silica-based situation preferred R 6Siliciumatom and the total number and the R of carbon atom 7The total number of Siliciumatom and carbon atom identical or on this.And at R 6For not forming the alkyl of ring, R with adjacent base 7For containing under the silica-based situation preferred R 6Carbonatoms and R 7The total number of Siliciumatom and carbon atom identical or on this.And at R 6Silica-based for containing, R 7Under the situation for the alkyl that do not form ring, preferred R 6Siliciumatom and the total number and the R of carbon atom 7Carbonatoms identical or on this.
As R 6And R 11Be preferably aryl or substituted aryl, specifically can enumerate phenyl, o-tolyl, a tolyl, p-methylphenyl, tert-butyl-phenyl, naphthyl, 3,5-dimethylphenyl, trimethylphenyl, xenyl, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, adjacent trifluorophenyl, a trifluorophenyl, to trifluorophenyl etc.
The R that replaces fluorenyl 6, R 11Be above-mentioned 1) or 2) in any situation under; When under the same polymeric condition, comparing because of having; Can obtain that fusing point is higher, molecular weight and existing goods are equal even the polymkeric substance of the terminal olefin of the carbonatoms more than it more than 3, perhaps have not only under the polymerizing condition at normal temperatures, and under the high temperature polymerization condition; When under the same polymeric condition, comparing; Can obtain the advantage of the polymkeric substance and so on of the equal even terminal olefin of carbonatoms 3 or more that the molecular weight more than it is high of fusing point and existing goods, therefore, manufacturability is isostatic fine terminal olefin based polymer especially.
Covalently cross-linked
It is covalently cross-linked to have substituent cyclopentadienyl moiety and the main chain portion that replaces fluorenyl bonded key and be the divalence that contains a carbon atom or Siliciumatom.
Important part among the present invention (1) in covalently cross-linked of used crosslinked metallocene compound (a-1) is that the crosslinked atom Y in the above-mentioned general formula [1-1] has R 13, R 14, they are atom or the substituting groups that are selected from the base of Wasserstoffatoms, the alkyl except methyl and silicon atoms, mutually can be identical also can be different, this substituting group also can interosculate and form ring.
At Y is under the situation of carbon, R 13And R 14Be preferably the alkyl except methyl respectively or contain silica-based; At Y is under the situation of silicon, R 13And R 14Be preferably the alkyl except methyl respectively.
Wherein, preferred Y is carbon, R 13, R 14Alkyl with carbonatoms 2～20.
Through with these covalently cross-linked and above-mentioned replacement fluorenyl combinations, just can realize the manufacturing of the HMP propene polymer under the irrealizable high temperature polymerization condition of existing polymerization.
As R 13And R 14The middle alkyl except methyl that uses is at R 13And R 14Not interosculating forms under the situation of ring, preferably can enumerate the alkyl (hereinafter is also referred to as " alkyl (f1 ") ") of total carbon atom number 2～20.And as R 13And R 14Be the situation of alkyl, can enumerate R 13And R 14Interosculate into the situation of ring (ring (f " ").
(f1 ") is meant the alkyl that from the alkyl (f1 ') of total carbon atom number 1～20, removes demethyl to the alkyl of total carbon atom number 2～20.
Wherein, at R 13And R 14Interosculate and form under the situation of ring, although above-mentioned R is arranged 13And R 14Be respectively the regulation of the preferable range of carbonatoms 2～20, but form the R of ring structure 13And R 14The carbonatoms summation be preferably 4～40, this ring structure is one of preferred implementation with above-mentioned alkyl equally also.
And at R 13And R 14Interosculate and form under the situation of ring, with this R 13Or R 14A part of Wasserstoffatoms of directly linking to each other of carbon also can be by halogen atom, contain oxygen base, nitrogenous base, contain silica-based replacement; In the case, the total that forms a plurality of substituent carbonatomss of ring also comprise above-mentionedly contain oxygen base, nitrogenous base, contain silica-based in contained carbonatoms.
(f1 "), for example preferably enumerating, alkyl, substituted alkyl (comprising haloalkyl), naphthenic base, substituted cycloalkyl (comprising haloalkyl), arylalkyl, substituted aryl alkyl (comprising halogenated aryl alkyl, haloalkyl substituted aryl alkyl), alkylaryl, substituted alkyl aryl (comprising haloalkyl aryl, haloalkyl substituted alkyl aryl), aryl (aromatic series base), bivalent hydrocarbon radical (mean R as alkyl 13And R 14In conjunction with the structure under the situation that forms ring), replace bivalent hydrocarbon radical etc.In addition, also can preferably enumerate substituted aryl (comprising halogenated aryl, haloalkyl substituted aryl).Wherein, in substituted aryl alkyl, substituted alkyl aryl, substituting group both can be at the aryl position Cheng Jian, also can be at the alkyl position Cheng Jian.
Contain silica-based (f2) and be meant the base that has with the covalently bound Siliciumatom of ring carbon of cyclopentadienyl moiety, be specially alkyl tin groups, alkyl silane groups and aryl-silane base.For example, do not form contain silica-based (f2 ') of total carbon atom number 1～20 under the situation of ring, can enumerate examples such as TMS, triethyl silyl, tri-phenyl-silane base with other substituting group as this substituting group.
As R 13And R 14, wherein be preferably:
Alkyl such as ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl; Naphthenic base such as cyclopentyl, cyclohexyl, suberyl; Aryl such as phenyl, xenyl, naphthyl; Alkylaryls such as o-tolyl, a tolyl, p-methylphenyl;
Arylalkyl such as benzyl, phenylbenzyl;
Between-halogen atom such as (trifluoromethyl) phenyl, right-(trifluoromethyl) phenyl, two (trifluoromethyl) phenyl, a chloro-phenyl-, rubigan, dichlorophenyl is introduced into substituent substituted aryl;
M-chloro benzyl, p-chlorobenzyl, a luorobenzyl, to luorobenzyl, a bromobenzyl, halogen atoms such as bromobenzyl, dichloro benzyl, difluorobenzyl, trichlorine benzyl, trifluoro-benzyl are introduced into substituent substituted alkyl aryl,
Introducing under the substituent situation to the aromatic series of aryl or arylalkyl, be preferably between being positioned at the compound of position and/or contraposition.
Wherein, more preferably alkyl, arylalkyl, substituted aryl alkyl (comprising halogenated aryl alkyl, haloalkyl substituted aryl alkyl), alkylaryl.Especially in this case, add above-mentioned characteristic, can under the temperature more than the normal temperature, make the alpha-olefinic polymer that fusing point is high, molecular weight is also high.
Wherein, as crosslinked metallocene compound (a-1) used among the present invention (1), the easy degree of making according to it is preferably used R 13And R 14Mutual identical compound.
The further feature of crosslinked metallocene compound (a-1)
In above-mentioned general formula [1-1], Q is neutrality, conjugation or non-conjugated diene below 10 of the alkyl that is selected from halogen, carbonatoms 1～10, carbonatoms, anion binding base and can be with the identical or different combination in the lone-pair electron coordinate neutral dentate.As the concrete example of halogen, can enumerate fluorine, chlorine, bromine, iodine; As the concrete example of alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, 2-methyl-propyl, 1,1-dimethyl propyl, 2; 2-dimethyl propyl, 1,1-diethylammonium propyl group, 1-ethyl-1-methyl-propyl, 1,1; 2,2-tetramethyl-propyl group, sec.-butyl, the tertiary butyl, 1,1-dimethylbutyl, 1; 1,3-trimethylammonium butyl, neo-pentyl, cyclohexyl methyl, cyclohexyl, 1-methyl isophthalic acid-cyclohexyl etc.
As the concrete example of neutrality, conjugation or the non-conjugated diene of carbonatoms below 10, can enumerate s-cis-η 4-1,3-butadiene or s-be trans-η 4-1,3-butadiene, s-cis-η 4-1,4-phenylbenzene-1,3-butadiene or s-be trans-η 4-1,4-phenylbenzene-1,3-butadiene, s-cis-η 4-3-methyl isophthalic acid, 3-pentadiene or s-be trans-η 4-3-methyl isophthalic acid, 3-pentadiene, s-cis-η 4-1,4-dibenzyl-1,3-butadiene or s-be trans-η 4-1,4-dibenzyl-1,3-butadiene, s-cis-η 4-2,4-hexadiene or s-be trans-η 4-2,4-hexadiene, s-cis-η 4-1,3-pentadiene or s-be trans-η 4-1,3-pentadiene, s-cis-η 4-1,4-two (tolyl)-1,3-butadiene or s-be trans-η 4-1,4-two (tolyl)-1,3-butadiene, s-cis-η 4-1, two (trimethylammonium tolyl)-1,3-butadienes of 4-or s-be trans-η 4-1, two (trimethylammonium the tolyl)-1,3-butadienes of 4-etc.
As the concrete example of anion binding base, can enumerate alkoxyl groups such as methoxyl group, tert.-butoxy, phenoxy; Carboxylic acid ester groups such as acetic ester, benzoic ether; Sulfonate group such as methanesulfonates, tosylate etc.
As can enumerating organo phosphorous compoundss such as trimethyl-phosphine, triethyl phosphine, triphenylphosphine, diphenyl methyl phosphine with the concrete example of lone-pair electron coordinate neutral dentate, or THF, diethyl ether 、 diox, 1, ethers such as 2-glycol dimethyl ether.
J is 1～4 integer, when j is 2 when above, Q can be identical also can be different.
Preferred crosslinked metallocene compound (a-1) and its example
The concrete example of the 4th group transition metal compound shown in the explanation above-mentioned general formula [1-1] below, but be not so limit the scope of the present invention (1) especially.
Can enumerate di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety (2; 7-two (2,4, the 6-trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-two (3, the 5-3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-two (4-aminomethyl phenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-dinaphthyl-3; 6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-two (4-tert-butyl-phenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride,
Diisobutyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety (2; 7-two (2,4, the 6-trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2; 7-two (3, the 5-3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2; 7-two (4-aminomethyl phenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2,7-dinaphthyl-3; 6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2,7-two (4-tert-butyl-phenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride,
Dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride [is also referred to as 1,3-phenylbenzene isopropylidene (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride sometimes.Hereinafter omits this another name], the dibenzyl methylene radical (cyclopentadienyl moiety (2,7-two (2,4, the 6-trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-two (3, the 5-3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-two (4-aminomethyl phenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dinaphthyl-3; 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two (4-tert-butyl-phenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride,
Two styroyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two styroyl methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (diphenyl-methyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (diphenyl-methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (cumyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (cumyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (1-phenyl-ethyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (1-phenyl-ethyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (cyclohexyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (cyclohexyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (cyclopentyl-methyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (cyclopentyl-methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (naphthyl methyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (naphthyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (xenyl methyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (xenyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride,
(benzyl) (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (normal-butyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, inferior cyclobutyl (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, inferior cyclobutyl (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, inferior suberyl (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, inferior suberyl (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride,
Dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-dimethyl--butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-dimethyl--butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-diisopropylbenzyl-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-diisopropylbenzyl-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-two (TMS)-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-two (TMS)-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-phenylbenzene-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-phenylbenzene-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-dibenzyl-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-dibenzyl-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-dimethyl--butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-dimethyl--butyl fluorenyl) zirconium dichloride,
Phenylbenzene methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethylphenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to the tertiary butyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to the tertiary butyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to normal-butyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to normal-butyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride,
Two (to xenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to xenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (1-naphthyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (1-naphthyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (naphthyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (naphthyl methyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (p-isopropyl phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-isopropyl phenyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (xenyl methyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (xenyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene silicylene (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene silicylene (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride,
Two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-dimethyl--butyl fluorenyl) zirconium dichloride, two (3-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-dimethyl--butyl fluorenyl) zirconium dichloride, two (4-bromobenzyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-dimethyl--butyl fluorenyl) zirconium dichloride, two (3-bromobenzyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-dimethyl--butyl fluorenyl) zirconium dichloride, two (4-luorobenzyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-dimethyl--butyl fluorenyl) zirconium dichloride, two (3-luorobenzyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-dimethyl--butyl fluorenyl) zirconium dichloride, two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-dimethyl--butyl fluorenyl) zirconium dichloride, two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2; 7-dinaphthyl-3; 6-dimethyl--butyl fluorenyl) zirconium dichloride, two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-two { p-methylphenyl }-3,6-dimethyl--butyl fluorenyl) zirconium dichloride, two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2; 7-two { o-tolyl }-3; 6-dimethyl--butyl fluorenyl) zirconium dichloride, two (4-phenylbenzyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-two { rubigan }-3; 6-di-t-butyl fluorenyl) example such as zirconium dichloride, two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-two { rubigan }-3,6-di-t-butyl fluorenyl) zirconium dichloride.
In addition; Compound or " dichloride " that " zirconium " of above-mentioned illustrated compound replaces with " hafnium " or " titanium " replace with " difluoride ", " dibromide ", " diiodide ", or " dichloride " to replace with the metallocene compound of " dimethyl-" or " methylethyl " etc. be the relevant metallocene compound of catalyst for olefines polymerizing (1) of the present invention (1) too.Especially in above-mentioned catalyst structure,, can synthesize dystectic syndiotactic alpha-olefinic polymer through using the metallocene compound of Cs symplex structure.
Above-mentioned (a-1) crosslinked metallocene compound can utilize the known method manufacturing, and method of manufacture is had no particular limits.As known method of manufacture, for example can enumerate WO2001/27124 number and the method for manufacture of WO2004/087775 pph record of the applicant's application.
Above-mentioned metallocene compound can use separately, also can make up more than 2 kinds and use.
Olefin polymerization catalysis
Below explanation will above-mentioned crosslinked metallocene compound (a-1) preferred implementation during as the polymerizing catalyst use of the present invention's (1) olefine polymerizing process.
When above-mentioned crosslinked metallocene compound (a-1) was used as olefin polymerization catalysis, catalyst component contained:
(a-1) the crosslinked metallocene compound of above-mentioned general formula [1-1] expression and
(b) be selected from (b-1) Organoaluminoxy compound,
(b-2) with the right compound of above-mentioned crosslinked metallocene compound (a-1) reacting forming ion and
(b-3) at least a kind of compound in the organo-aluminium compound (in this manual, being also referred to as " composition (b) ") as required, also contains (c) granular carrier.Below, each composition is specified.
(b-1) Organoaluminoxy compound
As above-mentioned Organoaluminoxy compound (b-1) (being also referred to as " composition (b-1) " in this manual), can directly use existing known aikyiaiurnirsoxan beta, specifically can enumerate with formula [2] and/or general formula [3] is the compound of representative,
In above-mentioned formula [2], R representes the alkyl of carbonatoms 1～10 independently of one another, and n is the integer more than 2,
In above-mentioned formula [3], R representes the alkyl of carbonatoms 1～10, and n is the integer more than 2.Especially preferably utilize R to be more than 3, to be preferably the MAO more than 10 for methyl, n.In these alumina alkanes, also can sneak into some organo-aluminium compounds.
Characteristic in the present invention's (1) the high temperature solution polymerization also can be suitable for the insoluble Organoaluminoxy compound of the illustrational benzene of japanese kokai publication hei 2-78687 communique.And, also be suitable for utilizing the described Organoaluminoxy compound of japanese kokai publication hei 2-167305 communique, japanese kokai publication hei 2-24701 communique, the described aikyiaiurnirsoxan beta of japanese kokai publication hei 3-103407 communique etc. with two or more alkyl.Wherein, " benzene is insoluble " Organoaluminoxy compound is meant that dissolved Al composition is scaled the Al atom usually below 10%, preferably below 5%, particularly preferably in below 2% in 60 ℃ benzene; And, be the Organoaluminoxy compound of insoluble or insoluble with respect to benzene.
In addition, also can enumerate the modified methylaluminoxane shown in the following formula [4] etc. as Organoaluminoxy compound (b-1).
Figure GSA00000105371100341
In formula [4], R representes the alkyl of carbonatoms 1～10, and m, n represent the integer more than 2 independently of one another.
This modified methylaluminoxane can use trimethylaluminium and the aluminum alkyls except that trimethylaluminium to modulate.Such modified methylaluminoxane is commonly called MMAO.The method that this MMAO can adopt US4960878 and US5041584 to lift is modulated.In addition, use the trimethylaluminium that derives from Tosoh Fine Chem company etc. and the synthetic R of triisobutyl aluminium also to be used for commercial prodn with titles such as MMAO, TMAO as the goods of isobutyl-.Such MMAO has improved the solvability of all kinds of SOLVENTS and the aikyiaiurnirsoxan beta of stability in storage, particularly, with such insoluble of compound shown in above-mentioned formula [2], [3] or to be insoluble in the aikyiaiurnirsoxan beta of benzene different, dissolves in aliphatic hydrocarbon or clicyclic hydrocarbon.
Moreover, also can enumerate the Organoaluminoxy compound of the boracic shown in the formula [5] as above-mentioned Organoaluminoxy compound (b-1).
In the formula [5], R cThe alkyl of expression carbonatoms 1～10, R dEach other can be identical, also can be different, the alkyl of expression Wasserstoffatoms, halogen atom or carbonatoms 1～10.
(b-2) with the right compound of crosslinked metallocene compound (a-1) reacting forming ion
As the compound (b-2) right (following be also referred to as sometimes " ionic compound (b-2) " or " composition (b-2) "), can enumerate Lewis acid, ionic compound, borane compound and the carborane compound etc. put down in writing in japanese kokai publication hei 1-501950 communique, japanese kokai publication hei 1-502036 communique, japanese kokai publication hei 3-179005 communique, japanese kokai publication hei 3-179006 communique, japanese kokai publication hei 3-207703 communique, japanese kokai publication hei 3-207704 communique, USP5321106 number etc. with crosslinked metallocene compound (a-1) reacting forming ion.In addition, also can enumerate heteropoly compound and with the polyvoltine compound.
In the present invention, the preferred ionic compound (b-2) that adopts is the compound shown in the formula [6].
Figure GSA00000105371100351
In the formula [6], as R E+, can enumerate H +, carbocation, oxygen positively charged ion, ammonium cation 、 phosphonium cation, suberyl trialkenyl positively charged ion, have the ferrocene cation (ferrocenium cation) of transition metal etc.R f～R iCan be identical also can be different, be organic radical, be preferably aryl.
As above-mentioned carbocation, specifically can enumerate triphenylcarbenium positively charged ion, three (aminomethyl phenyl) carbocation, three (3,5-dimethylphenyl) carbocation etc. three and replace carbocation etc.
As above-mentioned ammonium cation, specifically can enumerate trialkyl ammonium positively charged ions such as trimethyl ammonium positively charged ion, triethyl ammonium positively charged ion, three n-propyl ammonium cations, triisopropyl ammonium cation, three normal-butyl ammonium cations, triisobutyl ammonium cation; N, accelerine positively charged ion, N, N-Diethyl Aniline positively charged ion, N, N-2,4, N such as 6-pentamethylaminobenzene positively charged ion, N-dialkyl aniline positively charged ion; Dialkyl ammonium positively charged ions such as di-isopropyl ammonium cation, dicyclohexyl ammonium cation etc.
As Shang Shu phosphonium cation, specifically can enumerate triphenyl phosphonium positively charged ion, three (aminomethyl phenyl) phosphonium cation, three (San Fang Ji phosphonium cation such as 3,5-dimethylphenyl) phosphonium cation etc.
As stated, wherein,, be preferably carbon ion, ammonium cation etc., be preferably triphenylcarbenium positively charged ion, N especially, accelerine positively charged ion, N, N-Diethyl Aniline positively charged ion as Re+.
As carbon salt; Specifically can enumerate triphenylcarbenium tetraphenyl borate salts, triphenylcarbenium four (pentafluorophenyl group) borate, triphenylcarbenium four (3; 5-two trifluoromethyls) borate, three (4-aminomethyl phenyl) carbon four (pentafluorophenyl group) borate, three (3, the 5-3,5-dimethylphenyl) carbon four (pentafluorophenyl group) borate etc.
As ammonium salt, can enumerate trialkyl substituted ammonium salt, N, N-dialkyl benzene ammonium salt, dialkyl ammonium salt etc.
As the trialkyl substituted ammonium salt; Specifically can enumerate for example triethyl ammonium tetraphenyl borate salts, tripropyl ammonium tetraphenyl borate salts, three normal-butyl ammonium tetraphenyl borate salts, trimethyl ammonium four p-methylphenyl borates, trimethyl ammonium neighbours tolyl borate, three normal-butyl ammonium four (pentafluorophenyl group) borates, triethyl ammonium four (pentafluorophenyl group) borate, tripropyl ammonium four (pentafluorophenyl group) borate, tripropyl ammonium four (2; The 4-3,5-dimethylphenyl) borate, three normal-butyl ammoniums four (3; The 5-3,5-dimethylphenyl) borate, three normal-butyl ammoniums four (4-trifluoromethyl) borate, three normal-butyl ammoniums four (3; 5-two trifluoromethyls) borate, three normal-butyl ammonium neighbours tolyl borates, two (octadecyl) ammonium methyl tetraphenyl borate salts, two (octadecyl) ammonium methyl, four p-methylphenyl borates, two (octadecyl) ammonium methyl neighbours tolyl borate, two (octadecyl) ammonium methyl four (pentafluorophenyl group) borate, two (octadecyl) ammonium methyl four (2; The 4-3,5-dimethylphenyl) borate, two (octadecyl) ammonium methyl four (3; The 5-3,5-dimethylphenyl) borate, two (octadecyl) ammonium methyl four (4-trifluoromethyl) borate, two (octadecyl) ammonium methyls four (3,5-two trifluoromethyls) borate, two (octadecyl) ammonium methyl etc.
As N, N-dialkyl benzene amine salt specifically can be enumerated for example N, accelerine tetraphenyl borate salts, N; Accelerine four (pentafluorophenyl group) borate, N, accelerine four (3,5-two trifluoromethyls) borate, N, N-Diethyl Aniline tetraphenyl borate salts, N; N-Diethyl Aniline four (pentafluorophenyl group) borate, N, N-Diethyl Aniline four (3,5-two trifluoromethyls) borate, N; N-2,4,6-pentamethylaminobenzene tetraphenyl borate salts, N; N-2,4,6-pentamethylaminobenzene four (pentafluorophenyl group) borate etc.
As dialkyl ammonium salt, specifically can enumerate for example two (1-propyl group) ammonium four (pentafluorophenyl group) borates, two (cyclohexyl) ammonium tetraphenyl borate salts etc.
In addition, also can unrestrictedly use the applicant to disclose the ionic compound of (TOHKEMY 2004-51676 communique).
And above-mentioned ionic compound (b-2) can mix use more than 2 kinds.
(b-3) organo-aluminium compound
As (b-3) organo-aluminium compound that forms olefin polymerization catalysis (in this manual; Be also referred to as " composition (b-3) "); Can enumerate the for example organo-aluminium compound shown in the formula [7], the 1st family's metal shown in the formula [8] and the complexing alkynylene of aluminium etc.
R a mAl(OR b) nH pX q [7]
In the formula [7], R aAnd R bEach other can be identical also can be different, expression carbonatoms 1～15, be preferably 1～4 alkyl, X representes halogen atom, m is that the number of 0＜m≤3, the number that n is 0≤n＜3, number, the q that p is 0≤p＜3 are the number of 0≤q＜3, and m+n+p+q=3.
As the concrete example of this compounds, can enumerate three positive aluminum alkylss such as trimethylaluminium, triethyl aluminum, three n-butylaluminum, three hexyl aluminium, trioctylaluminum;
Three branched-chain alkyl aluminium such as triisopropylaluminiuand, triisobutyl aluminium, three sec.-butyl aluminium, tri-tert aluminium, three (2-methylbutyl) aluminium, three (3-methyl hexyl) aluminium, three (2-ethylhexyl) aluminium;
Tricyclic alkyl aluminium such as thricyclohexyl aluminium, three ring octyl group aluminium;
Triaryl aluminums such as triphenyl aluminum, trimethylphenyl aluminium;
Dialkyl group aluminum hydride such as di-isopropyl aluminum hydride, diisobutyl aluminium hydride;
General formula (i-C 4H 9) xAl y(C 5H 10) z(in the formula, x, y, z are positive number, and z≤2x) waits the thiazolinyl aluminium such as prenyl aluminium of expression;
Alkyl aluminium alkoxides (alkyl aluminiumalkoxide) such as isobutyl carbinol aluminium, isobutyl-aluminum ethylate;
Dialkyl group aluminium alkoxides such as dimethyl methyl aluminium alcoholates, diethylammonium aluminum ethylate, dibutyl aluminium butoxide;
Alkyl sesquialter aluminium alkoxides (alkylaluminium sesquialkoxide) such as ethyl sesquialter aluminum ethylate, butyl sesquialter aluminium butoxide;
Has general formula R a 2.5Al (ORb) 0.5Deng the expression average composition by part alkoxylated alkyl group aluminium;
Alkyl-aryloxy aluminium such as diethylammonium phenoxy aluminium, diethylammonium (2,6-di-t-butyl-4-methylphenoxy) aluminium;
Dialkylaluminum halides such as dimethylaluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethylammonium aluminum bromide, diisobutyl aluminum chloride;
Alkyl sesquialter aluminum halides such as ethyl sesquialter aluminum chloride, butyl sesquialter aluminum chloride, ethyl sesquialter aluminum bromide;
Alkyl dihalide aluminium such as ethylaluminum dichloride etc. are by partially halogenated aluminum alkyls;
Dialkyl group aluminum hydride such as ADEH, dibutyl aluminum hydride;
Other of alkyl aluminum dihydride such as ethyl dihydroaluminium, propyl group aluminum dihydride etc. is by partially hydrogenated aluminum alkyls;
Ethyl oxyethyl group aluminum chloride, butyl butoxy aluminum chloride, ethyl oxyethyl group aluminum bromide etc. are by part alkoxylate and halogenated aluminum alkyls etc.
M 2AlR a 4 [8]
In the formula [8], M 2Expression Li, Na or K, R aRepresent carbonatoms 1～15, be preferably 1～4 alkyl.
Can enumerate LiAl (C as this compounds 2H 5) 4, LiAl (C 7H 15) 4Deng.
In addition, also can use and the compound similar compounds shown in the above-mentioned general formula [8], for example, can enumerate and utilize nitrogen-atoms to make plural aluminum compound bonded organo-aluminium compound.As such compound, specifically can enumerate (C 2H 5) 2AlN (C 2H 5) Al (C 2H 5) 2Deng.
Consider from being easy to obtain angle,, preferably use trimethylaluminium, triisobutyl aluminium as organo-aluminium compound (b-3).
In addition; Catalyst for olefines polymerizing (1) among the present invention (1); Catalyst component uses the crosslinked metallocene compound shown in (a-1) above-mentioned general formula [1-1]; (b) be selected from the right compound of (b-1) Organoaluminoxy compound, (b-2) and above-mentioned crosslinked metallocene compound (a-1) reacting forming ion and (b-3) at least a kind of compound in the organo-aluminium compound, can also use carrier (c) simultaneously as required.
(c) carrier
Above-mentioned carrier (c) (in this manual, being also referred to as " composition (c) ") is mineral compound or organic cpds, is particulate state or microgranular solid.Wherein, as mineral compound, be preferably porous matter oxide compound, butter, clay, clay mineral or ion exchangeable lamellar compound.
As porous matter oxide compound, specifically can use SiO 2, Al 2O 3, MgO, ZrO, TiO 2, B 2O 3, CaO, ZnO, BaO, ThO 2Deng, or contain their mixture or mixture, for example, can use natural or synthetic zeolite, SiO 2-MgO, SiO 2-Al 2O 3, SiO 2-TiO 2, SiO 2-V 2O 5, SiO 2-Cr 2O 3, SiO 2-TiO 2-MgO etc.Wherein, be preferably with SiO 2And/or Al 2O 3Be staple.
In addition, above-mentioned inorganic oxide also can contain minor N a 2CO 3, K 2CO 3, CaCO 3, MgCO 3, Na 2SO 4, Al 2(SO 4) 3, BaSO 4, KNO 3, Mg (NO 3) 2, Al (NO 3) 3, Na 2O, K 2O, Li 2Carbonate such as O, vitriol, nitrate salt, oxide components.
This type porous matter oxide compound is according to kind and method for making, and its proterties is also different, and the particle diameter of above-mentioned carrier (c) is 3～300 μ m, be preferably 10～300 μ m, 20～200 μ m more preferably, and specific surface area is 50～1000m 2/ g, be preferably 100～700m 2The scope of/g, void content (porevolume) is preferably at 0.3～3.0cm 3The scope of/g.Such carrier can be fired use as required under 100～1000 ℃, preferred 150～700 ℃.
As inorganic halides, can use MgCl 2, MgBr 2, MnCl 2, MnBr 2Deng.Can directly use as butter, ball mill also capable of using, oscillating mill are pulverized the back and are used.In addition, also can after inorganic halides being dissolved in the pure equal solvent, use the microgranular precipitate that utilizes precipitation agent to separate out.
Above-mentioned clay is that staple constitutes usually with the clay mineral.In addition, above-mentioned ion exchangeable lamellar compound is to have between the face that is made up of ionic linkage etc. the compound of the crystalline texture of parallel overlapping lamination with faint bonding force, and contained ion is commutative.Most clay mineral is the ion exchangeable lamellar compound.In addition, be not limited to natural product, also can use the synthetic material as these clays, clay mineral, ion exchangeable lamellar compound.Moreover, as clay, clay mineral or ion exchangeable lamellar compound, can enumerate clay, clay mineral or six sides meter accumulation type, antimony type, CdCl 2Type, CdI 2Types etc. have the ionic crystal property compound of layered crystal structure etc.
Such clay, clay mineral can be enumerated kaolin, wilkinite, knaur clay, frog order clay, malthacite, canbyite, pyrophyllite, mica crowd, smectite crowd, vermiculite, chlorite crowd, polygorskite, kaolinite, nakrite, dickite, halloysite etc., can enumerate α-Zr (HAsO as the ion exchangeable lamellar compound 4) 2H 2O, α-Zr (HPO 4) 2, α-Zr (KPO 4) 23H 2O, α-Ti (HPO 4) 2, α-Ti (HAsO 4) 2H 2O, α-Sn (HPO 4) 2H 2O, γ-Zr (HPO 4) 2, γ-Ti (HPO 4) 2, γ-Ti (NH 4PO 4) 2H 2The crystallinity acid-salt of polyvalent metals such as O etc.
Such clay, clay mineral or ion exchangeable lamellar compound be preferably the above void content of measuring with mercury penetration method of radius
Figure GSA00000105371100391
be 0.1cc/g above, be preferably the material of 0.3～5cc/g especially.Wherein, Void content is measured the scope of pore radius
Figure GSA00000105371100392
through using the mercury penetration method of mercury porosimeter.
Under the situation of void content of using more than the radius
Figure GSA00000105371100393
, might be difficult to reach high polymerization activity less than the carrier of 0.1cc/g.
Above-mentioned clay, clay mineral preferably pass through chemical treatment.As chemical treatment, any processing such as processing that can adopt the surface treatment of the impurity of removing surface attachment, the crystalline texture of clay is exerted one's influence.As chemical treatment, specifically can enumerate s.t., alkaline purification, salt processing, organism processing etc.S.t. also can be separated out through making positively charged ion dissolvings such as Al in the crystalline texture, Fe, Mg except the impurity of removing the surface, increases surface-area.In alkaline purification, the crystalline texture of clay is damaged, and caly structure is changed.In addition, in salt processing, organism are handled, form ion complex body, molecular complex, organic derivative etc., can change surface-area and interfloor distance etc.
Above-mentioned ion exchangeable lamellar compound also can be to utilize ion exchangeable, with the IX of the exchangeability ion and other the big volume of interlayer, and the lamellar compound of the state that enlarged of interlayer thus.The effect that the big volume ion of this type is being undertaken the pillar that supports laminate structure is commonly referred to as " post (pillar) ".In addition, the behavior that imports other material of this interlayer to lamellar compound is known as " inserting (intercalation) ".As object (guest) compound that inserts, can enumerate TiCl 4, ZrCl 4Etc. the cationic mineral compound; Ti (OR) 4, Zr (OR) 4, PO (OR) 3, B (OR) 3Deng metal alkoxides (R is an alkyl etc.); [Al 13O 4(OH) 24] 7+, [Zr 4(OH) 14] 2+, [Fe 3O (OCOCH 3) 6] +In metal hydroxides ion etc.These compounds can use separately, also can two or more combinations use.In addition, when inserting these compounds, also can make Si (OR) 4, Al (OR) 3, Ge (OR) 4The polymkeric substance, the SiO that get Deng metal alkoxide hydrolysis such as (R are an alkyl etc.) 2Etc. coexistences with it such as colloidal state mineral compound.In addition,, can enumerate the oxide compound that generates through thermal dehydration etc. with after between above-mentioned metal hydroxides ion interposed layer as " post ".Wherein, be preferably clay and clay mineral, be preferably smectite, vermiculite, stellite, taincolite and synthetic mica especially.
Clay, clay mineral, ion exchangeable lamellar compound can directly use, and also can after implementing processing such as ball milling, screening, use.In addition, also can after adding water absorption or thermal dehydration processing again, use.In addition, both can use separately, also can two or more combinations use.
Under the situation of using the ion exchangeable layered silicate, except function as carrier, the also character of this ion exchangeable capable of using and laminate structure, the usage quantity of Organoaluminoxy compounds such as minimizing alkylaluminoxane.The ion exchangeable layered silicate is in the staple output of occurring in nature mainly as clay mineral, but is not limited to natural output especially, also can be the synthetic material.The concrete example of clay, clay mineral, ion exchangeable layered silicate can be enumerated kaolinite, smectite (montmorillonite), hectorite, wilkinite, smectite (smectite), vermiculite, taincolite, synthetic mica, synthetic li-montmorillonite etc.
In addition, as organic cpds, can enumerate particle diameter 3～300 μ m, the particulate state that is preferably 10～300 mu m ranges or microgranular solid.Specifically can enumerate terminal olefin with carbonatomss 2～14 such as ethene, propylene, 1-butylene, 4-methyl-1-pentenes and be (be total to) polymkeric substance that staple generates or be (being total to) polymkeric substance of staple generation with vinyl cyclohexane, vinylbenzene; Or multipolymer, or example such as the polymkeric substance that obtains of these polymkeric substance and vinylformic acid, propenoate, maleic anhydride isopolarity monomer copolymerization or graft polymerization or modification body with polar functional base.These granular carriers can use separately, also can two or more combinations use.
In addition; The catalyst component of the present invention's (1) catalyst for olefines polymerizing is except the crosslinked metallocene compound shown in (a-1) above-mentioned general formula [1]; (b) be selected from the right compound of (b-1) Organoaluminoxy compound, (b-2) and above-mentioned crosslinked metallocene compound (a-1) reacting forming ion and (b-3) at least a kind of compound in the organo-aluminium compound; And carrier as required (c) in addition, also can contain as required just like back described specific organic compound ingredient (d).
(d) organic compound ingredient
In the present invention, (d) organic compound ingredient (being also referred to as in this manual, " composition (d) ") is to use with the rerum natura that generates polymkeric substance in order to improve polymerization as required.Such organic compound ingredient (d) can be enumerated alcohols, phenoloid, carboxylic acid, phosphorus compound and sulphonate etc., but is not limited to this.
Use the method for manufacture of polymkeric substance of the alkene of above-mentioned olefin polymerization catalysis (1)
In the present invention (1), can select method of use, the interpolation order of each composition during polymerization arbitrarily, as polymerization method, can enumerate the method that is described below.
(1) adds composition (a-1) in the polymerizer method separately;
(2) add composition (a-1) and composition (b) in the polymerizer method with random order;
(3) composition (a-1) is stated from the carrier (c) obtains catalyst component, add this catalyst component and composition (b) in the polymerizer method with random order;
(4) composition (b) is stated from the carrier (c) obtains catalyst component, add this catalyst component and composition (a-1) in the polymerizer method with random order;
(5) composition (a-1) and composition (b) are stated from that carrier (c) is gone up and catalyst component add the method in the polymerizer to.
In each method of above-mentioned (2)～(5), also can make the contact in advance more than at least two of each catalyst component.
In each method of carrying above-mentioned (4) hold composition (b), (5), also can add with random order as required and carried the composition of holding (b).In this case, composition (b) can be identical also can be different.
In addition; Be carried with the solid catalyst component of composition (a-1) on the mentioned component (c), be carried with the solid catalyst component of composition (a-1) and composition (b) on the composition (c), can make the alkene prepolymerization earlier; Also can on prepolymerized solid catalyst component, carry again and hold catalyst component.
In the polymerization method of the present invention's (1) alkene, in the presence of aforesaid catalyst for olefines polymerizing,, obtain olefin polymer through making olefinic polymerization or copolymerization.
In the present invention (1), polymerization can be adopted any enforcement in liquid polymerizations such as solution polymerization, suspension polymerization or the gaseous polymerization.As the torpescence hydrocarbon medium that uses in the liquid polymerization, specifically can enumerate aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, 12 carbon alkane, kerosene; Clicyclic hydrocarbons such as pentamethylene, hexanaphthene, methylcyclopentane; Aromatic hydrocarbonss such as benzene,toluene,xylene; Halohydrocarbon such as ethylene chloride, chlorobenzene, methylene dichloride or their mixture etc. also can be with polymeric alkene itself as solvents.
When using aforesaid catalyst for olefines polymerizing to carry out olefinic polymerization, the consumption of composition (a-1) is that per 1 liter of reaction volume is generally 10 -9～10 -1The mole, be preferably 10 -8～10 -2Mole.
The consumption of composition (b-1) does, the mol ratio of all transition metal atoms (M) in composition (b-1) and the composition (a-1) [(b-1)/and M] be generally 0.01～5000, be preferably 0.05～2000.The consumption of composition (b-2) does, the mol ratio of the transition metal atoms (M) in composition (b-2) and the composition (a-1) [(b-2)/and M] be generally 1～10, be preferably 1～5.The consumption of composition (b-3) does, the mol ratio of all transition metal (M) in aluminium atom in the composition (b-3) and the composition (a-1) [(b-3)/and M] be generally 10～5000, be preferably 20～2000.
The consumption of composition (d) is under the situation of composition (b-1) at composition (b), and mol ratio [(d)/(b-1)] is generally 0.01～10, is preferably 0.1～5; At composition (b) is under the situation of composition (b-2), and mol ratio [(d)/(b-2)] is generally 0.01～10, is preferably 0.1～5; At composition (b) is under the situation of composition (b-3), and mol ratio [(d)/(b-3)] is generally 0.01～2, is preferably 0.005～1.
In addition, use the polymerization temperature of the alkene of above-mentioned olefin polymerization catalysis to be generally-50～+ 200 ℃, be preferably 0～170 ℃, more preferably 25～170 ℃, further be preferably 40～170 ℃ scope.Polymerization pressure is generally normal pressure～10MPa gauge pressure, is preferably normal pressure～condition of 5MPa gauge pressure, and polyreaction can adopt any method in intermittent type, semi continuous, the continous way.Also can polymerization be divided into reaction conditions carried out more than the two different stages.Whether the olefin polymer molecular weight of gained can be regulated through making to have hydrogen in the polymerization system or change polymerization temperature.In addition, also can regulate according to the amount of the composition (b) that uses.Under the situation of adding hydrogen, its amount is relatively more suitable about 0.001～100NL for every 1kg alkene.
In the present invention (1); The alkene that is used for polyreaction is more than one the monomer that is selected from the terminal olefin of carbonatoms more than 2; As terminal olefin; Can enumerate carbonatoms and be 2～20 the straight chain shape or the terminal olefin of branched; For example, can enumerate ethene, propylene, 1-butylene, 2-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.
And in the polymerization method of the present invention (1), also can enumerate carbonatoms 3～30, be preferably 3～20 cyclic olefin, for example cyclopentenes, suberene, norbornylene, 5-methyl-2-norbornylene, tetracyclododecen, 2-methyl isophthalic acid, 4; 5,8-dimethano--1,2; 3,4,4a; 5,8, the 8a-octalin;
Vinylformic acid, methylacrylic acid, fumaric acid, maleic anhydride, methylene-succinic acid, itaconic anhydride and dicyclo (2; 2,1)-and 5-heptene-2, α such as 3-dicarboxylic anhydride; Beta-unsaturated carboxylic acid isopolarity monomer, and their metal-salts such as sodium salt, sylvite, lithium salts, zinc salt, magnesium salts and calcium salt;
α such as methyl acrylate, n-butyl acrylate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, NSC 20949, tert-butyl acrylate, the own ester of vinylformic acid 2-normal-butyl, TEB 3K, n-BMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the beta-unsaturated carboxylic acid ester;
Vinyl esters such as vinyl-acetic ester, propionate, vinyl caproate, capric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, vinyl trifluoroacetate;
Unsaturated glycidyl esters such as glycidyl acrylate, SY-Monomer G, methylene-succinic acid list glycidyl ester etc.
In addition, also can be at vinyl cyclohexane, diene or polyenoid;
Aromatic ethenyl compound; For example vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, neighbour, align monoalkylated benzenes ethene or polyalkylbenzene ethene such as butylstyrene at right-dimethyl styrene, adjacent n-butylbenzene ethene, a n-butylbenzene ethene;
Methoxy styrene, phenetole ethene, vinyl TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M., vinyl TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. methyl esters, benzylacetic acid vinyl acetate, hydroxy styrenes, chloro styrene, chloro-styrene, Vinylstyrene etc. contained functional group's styrene derivatives; With
3-phenyl propylene, 4-phenyl propylene, alpha-methyl styrene etc. coexist as under the situation in the reaction system and promote polymerization.
In the present invention's (1) the method for manufacture; As an example; To can be used for making the formation unit that contains from the a kind of monomer (for example propylene) in the terminal olefin that is selected from carbonatoms 3～20 be 100～90 moles of %, be preferably 100～91 moles of %, 100～96 moles of % more preferably; With from the terminal olefin that is selected from carbonatoms 2～20 (not comprising propylene) more than a kind, and the monomeric formation unit different with above-mentioned monomer is 10～0 moles of %, is preferably 9～0 moles of %, the manufacturing of the polymkeric substance of 4～0 moles of % more preferably.As an example wherein, the manufacturing that can enumerate alfon.Wherein, such alpha-olefinic polymer preferably has the syndiotactic structure, and for example, the rrrr value of measuring according to following method is more than 70%, is preferably more than 85%.
And the present invention's (1) method of manufacture; As an example; Can be used for containing formation unit from ethene and be 100～50 moles of % and be the manufacturing of the polymkeric substance of 50～0 moles of % from the monomeric formation unit more than a kind in the terminal olefin that is selected from carbonatoms 3～20.As this example, can enumerate the manufacturing of Alathon etc.
In addition, the present invention's (1) method of manufacture can certainly be used when the polymkeric substance of making in addition.
Then, in the presence of the catalyzer of the transistion metal compound that contains the present invention (1), measure the rerum natura of the polymkeric substance that obtains through olefinic polymerization, the method for proterties describes.
[limiting viscosity ([η])]
Limiting viscosity is to use the naphthane solvent 135 ℃ of values of measuring down.That is, the granulation pellet with about 20mg dissolves mensuration specific viscosity η in 135 ℃ oil bath in the 15ml naphthane SpAfter in this naphthane solution, adding 5ml naphthane solvent cut, measure specific viscosity η equally SpRepeating 2 times should operate in dilution, and the concentration of trying to achieve (C) is extrapolated to 0 o'clock η SpThe value of/C is as limiting viscosity.
[η]＝lim(η sp/C) (C→0)
[fusing point (T m)]
Use differential scanning calorimetry (DSC), will be cooled to 30 ℃ at 200 ℃ of polymer samples that kept 10 minutes down, keeps after 5 minutes, the crystallization melting peak according to 10 ℃ of/minute speed intensifications the time calculates.Wherein, in the acrylic polymer of in embodiment of the invention I, being put down in writing, observe a peak or two peaks,, the low temperature side peak is designated as Tm detecting under two the situation 1, the high temperature side peak is designated as Tm 2Under one situation, be designated as Tm 2
In addition, taxis (rrrr) by 13The C-NMR spectrum is measured and is calculated.That is, rrrr divide rate by 13The absorption intensity of Prrrr (from the absorption intensity of the 3rd unitary methyl in 5 propylene units successive syndiotactic bonded positions) in the C-NMR spectrum and Pw (from the absorption intensity of whole methyl of propylene units) is tried to achieve according to following formula (1).
Rrrr divides rate (%)=100 * Prrrr/Pw (1)
NMR measures for example to be described below and carries out.That is, with 0.35g sample heating for dissolving in the 2.0ml hexachlorobutadiene.After this solution filtered with glass filter (G2), add 0.5ml deuterate benzene, the NMR pipe of the internal diameter 10mm that packs into.Use the system GX-500 of NEC type NMR determinator then, under 120 ℃, carry out 13C-NMR measures.Cumulative frequency is more than 10,000 times.
<u ><The Zhi Zaofangfa > of propylene series copolymer (B1);</u>
Then, the method for manufacture to the propylene series copolymer (B1) of the present invention (2) is elaborated.
The method of manufacture of the present invention's (2) propylene series copolymer (B1) is characterised in that, is containing:
(a-2) the crosslinked metallocene compound shown in the above-mentioned general formula [1-2] and
(b) be selected from (b-1) Organoaluminoxy compound,
(b-2) with the right compound of above-mentioned crosslinked metallocene compound (a-2) reacting forming ion and
(b-3) under the existence of the catalyst for olefines polymerizing of at least a kind of compound in the organo-aluminium compound (2), make propylene and be selected from least a monomer polymerization in terminal olefin and the polyenoid.
[1] (a-2) crosslinked metallocene compound
Crosslinked metallocene compound (a-2) shown in the above-mentioned general formula [1-2] (in this specification sheets, being also referred to as " composition (a-2) ") on chemical structure, has following characteristics [m2-1]～[m2-3].
In [m2-1] two dentates, one of them is to have substituent cyclopentadienyl moiety, and another is to have substituent fluorenyl (hereinafter is also referred to as " replacement fluorenyl " sometimes).
Covalently cross-linked (hereinafter is also referred to as " containing the covalently cross-linked of aryl or substituted aryl " sometimes) of containing carbon atom or Siliciumatom that [m2-2] two dentate utilizations have aryl or substituted aryl combines.
The transition metal (M) that [m2-3] constitutes crosslinked metallocene compound is titanium, zirconium or hafnium.
Below; Can have substituent cyclopentadienyl moiety, replace fluorenyl, crosslinked portion the characteristic on above-mentioned crosslinked metallocene compound (a-2) chemical structure successively; And after other characteristic describes; Preferred crosslinked metallocene compound and example thereof to these characteristics are elaborated, and the polymerization method to the present invention (2) of using this crosslinked metallocene compound (a-2) is elaborated at last.
Can have substituent cyclopentadienyl moiety
Cyclopentadienyl moiety can be substituted, and also can not be substituted.Not substituted cyclopentadienyl moiety is meant the R that the cyclopentadiene base section in the above-mentioned general formula [1-2] is had 1, R 2, R 3And R 4All be the cyclopentadienyl moiety of Wasserstoffatoms, substituted cyclopentadienyl moiety is meant R 1, R 2, R 3And R 4In can or contain silica-based (f2) substituted cyclopentadienyl moiety by alkyl (f1) more than any.In addition, R 1～R 4Adjacent substituting group any combination Cheng Huan mutually.R 1, R 2, R 3And R 4In be under the substituent situation beyond the Wasserstoffatoms more than two, these substituting groups can be identical also can be different.
As being used for substituent R 1～R 4Alkyl (f1), form under the situation of ring at this substituting group with other substituting group, preferably can enumerate the alkyl (hereinafter is also referred to as " alkyl (f1 ') ") of total carbon atom number 1～20.
And as R 2And R 3Be the situation of alkyl (f1), also can enumerate R 2And R 3Interosculate and form ring (hereinafter be also referred to as " ring (f ' ") ") situation.As substituent R 2And R 3Interosculate and form the situation of ring, more preferably R 1～R 4In R only 2And R 3Form ring.
For example, in substituent R 2And R 3Interosculate and form under the situation of ring, although above-mentioned R 2And R 3Preferred carbonatoms separately is 1～20, and the total that forms two substituent carbonatomss of ring is preferably 2～40, more preferably 3～30, further is preferably 4～20.
In addition, in substituent R 2And R 3Interosculate and form under the situation of ring; The a part of Wasserstoffatoms that directly links to each other with this substituent carbon can be by halogen atom, contain oxygen base, nitrogenous base, contain silica-based replacement; In the case, the total that forms two substituent carbonatomss of ring also comprise above-mentionedly contain oxygen base, nitrogenous base, contain silica-based in contained carbonatoms.
In addition, the alkyl of total carbon atom number 1～20 (f1 ') is meant alkyl, thiazolinyl, alkynyl or the aryl that only contains carbon and hydrogen.
And the alkyl of total carbon atom number 1～20 (f1 ') is except the alkyl that only contains carbon and hydrogen, thiazolinyl, alkynyl or the aryl, also comprise a part of Wasserstoffatoms of directly linking to each other with these carbon by halogen atom, contain oxygen base, nitrogenous base, contain the silica-based substituted heteroatomic alkyl that contains.These alkyl (f1 ') can be enumerated:
Straight chain shape alkyl such as methyl, ethyl, n-propyl, allyl group (allyl), normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl;
Sec.-propyl, the tertiary butyl, amyl group, 3-methyl amyl, 1; 1-diethylammonium propyl group, 1; 1-dimethylbutyl, 1-methyl isophthalic acid-propyl group butyl, 1,1-propyl group butyl, 1,1-dimethyl--2-methyl-propyl, 1-methyl isophthalic acid-sec.-propyl-branched alkyl such as 2-methyl-propyl;
Cyclic saturated hydrocarbon bases such as cyclopentyl, cyclohexyl, suberyl, ring octyl group, norcamphyl, adamantyl;
Ring-type unsaturated alkyl and their nuclear alkyl replacement bodies such as phenyl, naphthyl, xenyl, phenanthryl, anthryl;
The replacement saturated hydrocarbyl of aryl such as benzyl, cumyl;
Methoxyl group, oxyethyl group, phenoxy, N-methylamino, trifluoromethyl, trisbromomethyl, pentafluoroethyl group, pentafluorophenyl group, fluorophenyl, chloro-phenyl-, bromophenyl, benzyl chloride base, luorobenzyl, bromobenzyl, dichloro benzyl, difluorobenzyl, trichlorine benzyl, trifluoro-benzyl etc. contain heteroatomic alkyl.
Contain silica-based (f2) and be meant to have the group that forms the Siliciumatom of covalent linkage with the ring carbon of cyclopentadienyl moiety, be specially alkyl tin groups, alkyl silane groups, aryl-silane base.As preferably containing silica-based (f2); Do not form under the situation of ring at this substituting group with other adjacent substituting group; Containing of total carbon atom number 1～20 silica-based (f2 ') can be enumerated, for example, the base of such as the Siliciumatom of TMS, tri-phenyl-silane base etc. can be enumerated by 3 hydrocarbyl substituted.
In this cyclopentadienyl moiety, preferred R 1And R 4Be identical atom or identical base, R 2With R 3In conjunction with forming ring or R 2And R 3Be identical atom or identical base, more preferably R 1And R 4Be Wasserstoffatoms, be preferably R especially 1, R 2, R 3And R 4Be Wasserstoffatoms.
Replace fluorenyl
Fluorenyl part in the chemical structural formula shown in the above-mentioned general formula [1-2], importantly R 6And R 11For being selected from hydrogen, alkyl, containing identical atom or identical base in silica-based, R 7And R 10For being selected from hydrogen, alkyl, containing identical atom or identical base in silica-based, R 6, R 7, R 10And R 11Be not Wasserstoffatoms simultaneously.Therefore, R 6, R 7, R 10And R 11Can be above-mentioned alkyl (f1), also can be above-mentioned contain silica-based (f2).
In addition, R 5, R 8, R 9, R 12Both can be respectively to be selected from hydrogen, alkyl (f1), to contain identical or different atom or base in silica-based (f2), R 5～R 12Adjacent substituting group also can interosculate arbitrarily and form ring.
As being used for substituent R 5～R 12Alkyl (f1), do not form under the situation of ring at this substituting group with other substituting group, preferably can enumerate the alkyl (hereinafter is also referred to as " alkyl (f1 ') ") of total carbon atom number 1～20.
And R 5～R 12Under the situation for alkyl (f1), also can enumerate this substituting group and R 5～R 12In adjacent substituting group interosculate and form the situation of ring.At this moment, R 5～R 12In interosculate between the adjacent substituting group form ring (" ring (f ' ") ").
And as R 5～R 12In interosculate between the adjacent substituting group form ring (f ' ") situation, can enumerate R 5～R 12In adjacent two, three or four interosculate and form the situation of ring.Be preferably R especially 5～R 12In adjacent two form ring.
For example, in substituent R 5～R 12In (the R for example that interosculates between adjacent two under the situation that forms ring 6And R 7The situation that the formation of interosculating encircles etc.), although above-mentioned R 5～R 12Preferred separately carbonatoms be 1～20, but the total that forms two substituent carbonatomss of ring is preferably 2～40, more preferably 3～30, further is preferably 4～20.
And in for example substituent R 5～R 12In (the R for example that interosculates between adjacent three under the situation that forms ring 5, R 6And R 7The situation that the formation of interosculating encircles etc.), above-mentioned R 5～R 12Preferred separately carbonatoms be 1～20, the total that forms three substituent carbonatomss of ring is preferably 3～60, more preferably 5～40, further is preferably 7～30.
And in for example substituent R 5～R 12In (R for example under adjacent four situation that form ring of interosculating 5, R 6, R 7And R 8The situation that the formation of interosculating encircles etc.), above-mentioned R 5～R 12Preferred separately carbonatoms be 1～20, the total that forms two substituent carbonatomss of ring is preferably 4～80, more preferably 7～60, further is preferably 10～40.
And at R 5～R 12Adjacent substituting group interosculate and form under the situation of ring; The a part of Wasserstoffatoms that directly links to each other with this substituent carbon can be by halogen atom, contain oxygen base, nitrogenous base, contain silica-based replacement; In the case, the total that forms a plurality of substituent carbonatomss of ring also comprise above-mentionedly contain oxygen base, nitrogenous base, contain silica-based in contained carbonatoms.
From the viewpoint that the polymer of the molecular weight of the polymerization activity of the present invention's (2) polymerization method or generation quantizes, preferred R 6, R 7, R 10And R 11All be the base beyond the Wasserstoffatoms, that is, and R 6And R 11Be preferably and be selected from alkyl and the identical base that contains in silica-based, and R 7And R 10Be preferably and be selected from alkyl and the identical base that contains in silica-based.
Especially R 6And R 11Be preferably following any especially:
1) is being alkyl, and do not forming under the situation of ring, independent respectively expression carbonatoms more than 2, be preferably alkyl more than 4 more preferably more than 3, especially with adjacent base;
2) under the situation that is alkyl, R 6With R 7, R 11With R 10Form ring respectively;
3) be respectively contain silica-based.
And, contain silica-based in, the adding up to more than 3 of preferred carbonatoms and Siliciumatom number, more preferably more than 4 contain silica-based.In addition, for further improving the present invention's (2) effect, at R 6For not forming the hydrocarbon of ring, R with adjacent base 7For not forming under the situation of the alkyl that encircles preferred R with adjacent base 6Carbonatoms and R 7Carbonatoms identical or on this.And at R 6, R silica-based for containing 7For containing under the silica-based situation preferred R 6Siliciumatom and the total number and the R of carbon atom 7The total number of Siliciumatom and carbon atom identical or on this.And at R 6For not forming the hydrocarbon of ring, R with adjacent base 7For containing under the silica-based situation preferred R 6Carbonatoms and R 7The total number of Siliciumatom and carbon atom identical or on this.And at R 6Silica-based for containing, R 7Under the situation for the alkyl that do not form ring, preferred R 6Siliciumatom and the total number and the R of carbon atom 7Carbonatoms identical or on this.
As R 6, R 7, R 10, R 11Alkyl, contain silica-based; Can enumerate aforesaid base; Be preferably above-mentioned alkyl (f1 '), ring (f ' "), the containing of total carbon atom number 1～20 silica-based (f2 ') etc., as concrete substituting group, be preferably the tertiary butyl, methylcyclohexyl, methyl adamantane base, phenyl, naphthyl etc. especially.In addition, one of most preferred embodiment of the replacement fluorenyl of above-mentioned crosslinked metallocene compound (a-2) can be enumerated: as stated, and R 6, R 7, RW, R 11Not to exist but R as independent substituting group respectively 6And R 7, R 10And R 11Can interosculate and form ring.
Contain the covalently cross-linked of aryl or substituted aryl
In conjunction with having the main chain portion of substituent cyclopentadienyl moiety with the key that replaces fluorenyl is that to contain the divalence of a carbon atom or Siliciumatom covalently cross-linked.Important part in the present invention's (2) the polymerization method is, covalently cross-linked crosslinked atom Y is preferably that have can identical specific base that also can be different, is preferably to have specific aryl or substituted aryl [R 13And R 14].Through will can identical specific base, preferred specific aryl or substituted aryl that also can be different introducing crosslinked atom (Y) mutually; In the polymerization method of the present invention (2), just can efficiently make the high-molecular weight olefin polymer that utilizes existing polymerization not obtain.
Wherein, R 13And R 14Be the aryl that is selected from carbonatoms 6～18, the alkyl of carbonatoms 1～40, the alkylaryl of carbonatoms 6～40, the fluoro aryl of carbonatoms 6～20, the fluoroalkyl aryl of carbonatoms 7～40, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40; They can be identical also can be different, R 13And R 14In at least one be the aryl that is selected from carbonatoms 7～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40.
Preferred R 13And R 14Be the aryl that is selected from carbonatoms 6～18, the fluoroalkyl aryl of carbonatoms 7～40, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40; They can be identical also can be different, R 13And R 14In at least one is the aryl that is selected from carbonatoms 7～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40.
As an example of aryl or substituted aryl, can enumerate and be substituted basic substituted base more than one in aryl and these aromatic series hydrogen (sp2 type hydrogen) of carbonatomss 6～18 such as phenyl, naphthyl, anthryl, phenanthryl.
Wherein, As preference; Can enumerate carbonatomss such as phenyl and be 6 aryl; Carbonatomss such as naphthyl are 10 aryl; Carbonatomss 11～18 such as xenyl, anthryl, phenanthryl, be preferably the aryl of carbonatoms 11～14, carbonatomss such as chloro-phenyl-, dichlorophenyl are 6～20 chlorine aryl, the bromine aryl of carbonatomss such as bromophenyl, dibromo phenyl 6～20; The iodine aryl of carbonatomss 6～20 such as iodophenyl, diiodo-phenyl; Carbonatomss 7～40 such as (trichloromethyl) phenyl, two (trichloromethyl) phenyl, be preferably the chlorine alkylaryl of carbonatoms 7～20, carbonatomss 7～40 such as (trisbromomethyl) phenyl, two (trisbromomethyl) phenyl, be preferably the bromine alkylaryl of carbonatoms 7～20, carbonatomss 7～40 such as (three iodomethyls) phenyl, two (three iodomethyls) phenyl, be preferably the iodine alkylaryl of carbonatoms 7～20; Carbonatomss 7～40 such as (trifluoromethyl) phenyl, two (trifluoromethyl) phenyl, be preferably the fluoroalkyl aryl of carbonatoms 7～20 etc., be preferably especially these substituting groups be positioned between the substituted-phenyl of position and/or contraposition.
In the present invention (2), wherein be preferably the aryl that is selected from carbonatoms 11～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40 especially.
As preferred concrete example, can enumerate an xenyl, to xenyl, a chloro-phenyl-, rubigan, a trifluorophenyl, to trifluorophenyl, rubigan, to iodophenyl, 3,5-two (trifluorophenyl), 5-chloronaphthyl, methylnaphthyl, 6-chloronaphthyl, methylnaphthyl etc.
In addition, in the present invention (2), R 13And R 14Be the aryl that is selected from carbonatoms 6～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40; They can be identical also can be different, R 13And R 14In at least one be preferably the aryl that is selected from carbonatoms 11～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40.
Preferred especially R 13And R 14Both are the aryl that is selected from carbonatoms 7～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40; Can be identical also can be different, R 13And R 14Both are preferably the aryl that is selected from carbonatoms 11～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40, they can be identical also can be different.
Wherein, in above-mentioned crosslinked metallocene compound (a-2), the easy degree of making according to it is preferably used R 13And R 14Mutual identical compound.
The further feature of crosslinked metallocene compound (a-2)
In above-mentioned general formula [1-2], Q is for being selected from neutrality, conjugation or non-conjugated diene below 10 of halogen, alkyl (being preferably the alkyl of carbonatoms 1～10), carbonatoms, anion binding base and can be with the identical or different combination in the lone-pair electron coordinate neutral dentate.
As the concrete example of halogen, can enumerate fluorine, chlorine, bromine, iodine.
As the concrete example of alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, 2-methyl-propyl, 1,1-dimethyl propyl, 2; 2-dimethyl propyl, 1,1-diethylammonium propyl group, 1-ethyl-1-methyl-propyl, 1,1; 2,2-tetramethyl-propyl group, sec.-butyl, the tertiary butyl, 1,1-dimethylbutyl, 1; 1,3-trimethylammonium butyl, neo-pentyl, cyclohexyl methyl, cyclohexyl, 1-methyl isophthalic acid-cyclohexyl etc.
As the concrete example of neutrality, conjugation or the non-conjugated diene of carbonatoms below 10, can enumerate s-cis-η 4-1,3-butadiene or s-be trans-η 4-1,3-butadiene, s-cis-η 4-1,4-phenylbenzene-1,3-butadiene or s-be trans-η 4-1,4-phenylbenzene-1,3-butadiene, s-cis-η 4-3-methyl isophthalic acid, 3-pentadiene or s-be trans-η 4-3-methyl isophthalic acid, 3-pentadiene, s-cis-η 4-1,4-dibenzyl-1,3-butadiene or s-be trans-η 4-1,4-dibenzyl-1,3-butadiene, s-cis-η 4-2,4-hexadiene or s-be trans-η 4-2,4-hexadiene, s-cis-η 4-1,3-pentadiene or s-be trans-η 4-1,3-pentadiene, s-cis-η 4-1,4-xylyl-1,3-butadiene or s-be trans-η 4-1,4-xylyl-1,3-butadiene, s-cis-η 4-1,4-two (TMS)-1,3-butadiene or s-be trans-η 4-1,4-two (trimethyl silyl)-1,3-butadiene etc.
As the concrete example of anion binding base, can enumerate alkoxyl groups such as methoxyl group, tert.-butoxy, phenoxy; Carboxylic acid ester groups such as acetic ester, benzoic ether; Sulfonate group such as methanesulfonates, tosylate etc.
As can enumerating organo phosphorous compoundss such as trimethyl-phosphine, triethyl phosphine, triphenylphosphine, diphenyl methyl phosphine with the concrete example of lone-pair electron coordinate neutral dentate, or THF, diethyl ether 、 diox, 1, ethers such as 2-glycol dimethyl ether.
J is 1～4 integer, when j is 2 when above, Q can be identical also can be different.
Preferred crosslinked metallocene compound (a-2) and example thereof
Below, disclose the concrete example of the represented crosslinked metallocene compound (a-2) of above-mentioned general formula [1-2], but be not thus the present invention's (2) scope to be made special qualification.In addition, herein, prestox octahydro dibenzo fluorenes is meant the structure shown in the formula [10], and prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenes are meant the structure shown in the formula [11], and the dibenzo fluorenes is meant the structure shown in the formula [12].
Figure GSA00000105371100531
Two (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-two uncles] basic fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (bromophenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (bromophenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (bromophenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (bromophenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (bromophenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (bromophenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (bromophenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (bromophenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (bromophenyl) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (bromophenyl) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (to iodophenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (to iodophenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to iodophenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (to iodophenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (to iodophenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (to iodophenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to iodophenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to iodophenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to iodophenyl) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to iodophenyl) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-(trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-(trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (to trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (to trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (to trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (to trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (to trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-(trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-(trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (trichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (3,5-two (trifluoromethyl)-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-di-t-butyl fluorenyl) zirconium dichloride, two (3; 5-two (trifluoromethyl)-phenyl) methylene radical (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride, two (3,5-two (trifluoromethyl)-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (3; 5-two (trifluoromethyl)-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (3,5-two (trifluoromethyl)-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (3,5-two (trifluoromethyl)-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (3,5-two (trifluoromethyl)-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (3,5-two (trifluoromethyl)-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (3,5-two (trifluoromethyl)-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (3,5-two (trifluoromethyl)-phenyl) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (3,5-dichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-di-t-butyl fluorenyl) zirconium dichloride, two (3; 5-dichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichlorides, two (3,5-dichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (3; 5-dichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (3,5-dichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (3,5-dichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (3,5-dichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (3,5-dichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (3,5-dichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (3,5-dichloromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (4-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (4-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (4-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (4-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (4-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (4-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (4-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (3-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (3-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (3-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (3-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (3-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (3-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (3-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (3-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (3-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (3-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (5-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (5-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (5-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (5-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (5-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (5-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (5-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (5-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (5-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (5-chloronaphthyl, methylnaphthyl) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Phenyl (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, phenyl (rubigan) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, phenyl (rubigan) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, phenyl (rubigan) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, phenyl (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (rubigan) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Phenyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, phenyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, phenyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, phenyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, phenyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Phenyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-(trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, phenyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
Naphthyl (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (rubigan) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, naphthyl (rubigan) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, naphthyl (rubigan) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, naphthyl (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (rubigan) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Naphthyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, naphthyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, naphthyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, naphthyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Naphthyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-(trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, naphthyl (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
(p-methylphenyl) (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (rubigan) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, (p-methylphenyl) (rubigan) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, (p-methylphenyl) (rubigan) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, (p-methylphenyl) (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-(trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (rubigan) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
(p-methylphenyl) (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, (p-methylphenyl) (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, (p-methylphenyl) (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, (p-methylphenyl) (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2,7-(trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
(p-methylphenyl) (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, (p-methylphenyl) (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, (p-methylphenyl) (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, (p-methylphenyl) (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-(trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, (p-methylphenyl) (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,3; 6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (4-xenyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride (above-claimed cpd also is generically and collectively referred to as " crosslinked metallocene compound (a-2a) ") and
Two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (4-[p-trifluoromethyl phenyl]-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (4-[p-trifluoromethyl phenyl]-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (4-[p-trifluoromethyl phenyl]-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (4-[p-trifluoromethyl phenyl]-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-[p-trifluoromethyl phenyl]-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-[p-trifluoromethyl phenyl]-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (4-[p-trifluoromethyl phenyl]-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-[p-trifluoromethyl phenyl]-phenyl) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride,
Two (4-[rubigan]-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (4-[rubigan]-phenyl) methylene radical (cyclopentadienyl moiety) (prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenyl) zirconium dichloride, two (4-[rubigan]-phenyl) methylene radical (cyclopentadienyl moiety) (dibenzo fluorenyl) zirconium dichloride, two (4-[rubigan]-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-[rubigan]-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-[rubigan]-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-(trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (4-[rubigan]-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-(3,5-dimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-[rubigan]-phenyl) methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride (above-claimed cpd also is generically and collectively referred to as " crosslinked metallocene compound (a-2b) ") etc.
In addition; Compound or " dichloride " that " zirconium " of (the crosslinked metallocene compound (a-2a) and (a-2b)) of above-mentioned illustrated compound replaces with " hafnium " or " titanium " replace with " difluoride ", " dibromide ", " diiodide ", or " dichloride " to replace with the metallocene compound of " dimethyl-" or " methylethyl " etc. be the represented metallocene compound of general formula [1-2] too.
Above-mentioned crosslinked metallocene compound (a-2) can be with reference to the known method manufacturing.As known method of manufacture, for example can enumerate the applicant in the method for manufacture described in the WO04/029062 pph.
Aforesaid metallocene compound can use a kind of separately, also can two or more combinations use.
[2] olefin polymerization catalysis (2)
Preferred implementation when the crosslinked metallocene compound of explanation above-mentioned (a-2) is as the polymerizing catalyst of the present invention's (2) olefine polymerizing process below.
When above-mentioned crosslinked metallocene compound (a-2) was used as olefin polymerization catalysis, catalyst component comprised:
(a-2) the crosslinked metallocene compound of above-mentioned general formula [1-2] expression and
(b) be selected from (b-1) Organoaluminoxy compound,
(b-2) with the right compound of above-mentioned crosslinked metallocene compound (a-2) reacting forming ion and
(b-3) at least a kind of compound in the organo-aluminium compound.
Wherein, " compound (b-2) right with crosslinked metallocene compound (a-2) reacting forming ion " is identical with above-mentioned " compound (b-2) right with crosslinked metallocene compound (a-1) reacting forming ion (ionic compound (b-2)) ", and above-mentioned Organoaluminoxy compound (b-1), above-mentioned ionic compound (b-2) and above-mentioned organo-aluminium compound (b-3) specify as stated.
In addition; Above-mentioned olefin polymerization catalysis (2) is as catalyst component; Except containing the crosslinked metallocene compound shown in (a-2) above-mentioned general formula [1-2] and (b) being selected from the right compound of (b-1) Organoaluminoxy compound, (b-2) and above-mentioned crosslinked metallocene compound (a-2) reacting forming ion and (b-3) at least a kind of compound in the organo-aluminium compound, as required, also can contain above-mentioned carrier (c); Above-mentioned each composition, also capable of loading and carrying going up in granular above-mentioned carrier (c) used.
In addition, above-mentioned olefin polymerization catalysis (2) also can contain above-mentioned organic compound ingredient (d) as required as catalyst component.
Specifying described in the explanation of the catalyst for olefines polymerizing (1) of the present invention (1) of above-mentioned carrier (c) and above-mentioned organic compound ingredient (d).
The method of manufacture of propylene series copolymer (B1)
During propylene series copolymer (B1) polymerization, method of use, the interpolation order of each composition can be selected arbitrarily, following method can be enumerated.
(1) adds composition (a-2) and composition (b) in the polymerizer method with random order;
(2) add composition (a-2) and composition (b) in the polymerizer method with random order;
(3) composition (a-2) is carried to be held on the carrier (c) obtain catalyst component, add this catalyst component and composition (b) in the polymerizer method with random order;
(4) composition (b) is supported on the carrier (c) obtains catalyst component, add this catalyst component and composition (a-2) in the polymerizer method with random order;
(5) composition (a-2) and composition (b) are supported at that carrier (c) is gone up and the catalyst component that obtains adds the method in the polymerizer to.
In each method of above-mentioned (2)～(5), also can make the contact in advance more than at least two of each catalyst component.
In above-mentioned (4) that are carried with composition (b), (5) each method, also can add with random order as required and not carry the composition of holding (b).In this case, composition (b) can be identical also can be different.
In addition; Be carried with the solid catalyst component of composition (a-2) on the mentioned component (c); Be carried with the solid catalyst component of composition (a-2) and composition (b) on the composition (c), can make olefinic polymerization in advance, also can on prepolymerized solid catalyst component, carry again and hold catalyst component.
In the manufacturing of aforesaid propylene based copolymer (B1), polymerization can be adopted any enforcement in liquid polymerizations such as solution polymerization, suspension polymerization or the gaseous polymerization.As the torpescence hydrocarbon medium that uses in the liquid polymerization, specifically can enumerate aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, 12 carbon alkane, kerosene; Clicyclic hydrocarbons such as pentamethylene, hexanaphthene, methylcyclopentane; Aromatic hydrocarbonss such as benzene,toluene,xylene; Halohydrocarbon such as vinylchlorid, chlorobenzene, methylene dichloride or their mixture etc. also can be with polymeric alkene itself as solvents.
When using aforesaid catalyst for olefines polymerizing to carry out olefinic polymerization, the consumption of composition (a-2) is that per 1 liter of reaction volume is generally 10 -9～10 -1The mole, be preferably 10 -8～10 -2Mole.
The consumption of composition (b-1) does, makes the mol ratio [(b-1)/M] of all transition metal atoms (M) in composition (b-1) and the composition (a-2) be generally 0.01～5,000, be preferably 0.05～2,000.The consumption of composition (b-2) does, makes the mol ratio [(b-2)/M] of aluminium atom and all transition metal atoms (M) in the composition (a-2) in the composition (b-2) be generally 1～1,000, be preferably 1～500.The consumption of composition (b-3) does, makes the mol ratio [(b-3)/M] of the transition metal atoms (M) in composition (b-3) and the composition (a-2) be generally 1～10,000, be preferably 1～5,000.
In the present invention (2), in the presence of aforesaid catalyst for olefines polymerizing (2), make propylene and at least a monomer copolymerization under common liquid phase state that is selected from terminal olefin and the polyenoid.At this moment, generally use hydrocarbon solvent, but also can terminal olefin be used as solvent.Copolymerization can adopt any method in batch process or the continuous processing to implement.
As can be used for the polymeric terminal olefin, can enumerate for example ethene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.Terminal olefin can use a kind of separately, also can two or more combinations use.
As can be used for the polymeric polyenoid, specifically can enumerate
1,4-pentadiene, 1,5-hexadiene, 1; 4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1; 6-octadiene, 1; 7-octadiene, ENB, vinyl norbornene, Dicyclopentadiene (DCPD), 7-methyl isophthalic acid, 6-octadiene, 4-ethylidene-8-methyl isophthalic acid, non-conjugated dienes such as 7-nonadiene;
Divinyl, isoprene equiconjugate diene;
6,10-dimethyl--1,5,9-11 carbon triolefins, 4,8-dimethyl--1; 4,8-triolefin in the last of the ten Heavenly stems, 5,9-dimethyl--1,4,8-triolefin in the last of the ten Heavenly stems, 6; 9-dimethyl--1,5,8-triolefin in the last of the ten Heavenly stems, 6,8,9-trimethylammonium-1; 5,8-triolefin in the last of the ten Heavenly stems, 6-ethyl-10-methyl isophthalic acid, 5,9-11 carbon triolefins, 4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1; 6-octadiene, 4-ethylidene-8-methyl isophthalic acid, 7-nonadiene (EMND), 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl--4-ethylidene-1; 6-octadiene, 6,7-dimethyl--4-ethylidene-1,6-nonadiene, 4-ethylidene-1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl group-4-ethylidene-1; 6-octadiene, 4-ethylidene-1,7-nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1, non-conjugated triolefins such as 7-11 carbon diene;
1,3,5-hexatriene equiconjugate triolefin.
Above-mentioned diene can use a kind of separately, also can two or more combinations use, and aforesaid triolefin can use a kind of separately, also can two or more combinations use.In addition, but also the combination of triolefin and diene use.
Moreover, also can aforesaid terminal olefin and polyenoid combination be used.
Using catalyst for olefines polymerizing, adopting batch process to implement under the situation of copolymerization, the concentration of metallocene compound is that per 1 liter of polymerization volume is generally 0.00005～1 mmole, is preferably 0.0001～0.50 mmole in the polymerization system.
And the reaction times (average retention time when implementing copolymerization with continuous processing) because of conditions such as catalyst concn, polymerization temperature are different, is generally 5 minutes～3 hours, is preferably 10 minutes～1.5 hours.
Aforesaid propylene is supplied with polymerization system respectively according to reaching as stated the amount of the propylene series copolymer of specific composition (B1) respectively with at least a monomer that is selected from terminal olefin and the polyenoid.
During this external copolymerization, also can use hydrogen equimolecular quantity regulator.
With propylene during with at least a monomer copolymerization that is selected from terminal olefin and the polyenoid, propylene series copolymer (B1) obtains containing the polymeric solution of this multipolymer usually as stated.Adopt ordinary method to handle this polymeric solution, obtain propylene series copolymer (B1).
Copolyreaction usually 40～200 ℃ of temperature, be preferably in 40 ℃～180 ℃, more preferably 50 ℃～150 ℃ the scope, surpass 0～10Mpa at pressure, be preferably 0.5～10Mpa, more preferably carry out under the condition of the scope of 0.5～7Mpa.
According to the present invention (2), for example under the condition of polymerization temperature more than 65 ℃, also can obtain the propylene series copolymer of HMW (particularly, [η]＞2.0).
[3] propylene series copolymer (B1)
Limiting viscosity [η] (135 ℃ are measured in naphthane) by the propylene series copolymer (B1) of the present invention's (2) method of manufacture gained is 0.1～10dl/g, be preferably 0.3～7dl/g, 0.5～5dl/g more preferably.And melt flow rate(MFR) (the MFR:ASTM D 1238 of propylene series copolymer (B1); 190 ℃, the load 2.16kg) be 0.01～200g/10 minute, be preferably 0.05～100g/10 minute, more preferably 0.05～80g/10 minute, be preferably 0.05～20g/10 minute especially.
Propylene content (the formation quantity of units from propylene in the propylene series copolymer (B1)) by the propylene series copolymer (B1) of the present invention's (2) method of manufacture gained is 95～51 moles of %, be preferably 90～51 moles of %, the scope of 90～55 moles of % more preferably.
Terminal olefin composition as aforesaid propylene based copolymer (B1); For example be preferably and be selected from least a in ethene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene and the 1-decene, the formation unit from terminal olefin in propylene series copolymer (B1) is 5～49 moles of %, be preferably 10～49 moles of %, more preferably in the scope of 10～45 moles of %.The terminal olefin composition both can contain a kind of, also can contain two or more.
Wherein, in the propylene series copolymer (B1) from the formation unit content of propylene and the 100 moles of % that add up to from the formation unit content of terminal olefin.
And polyenoid is preferably selected from diene or triolefin, preferably in propylene series copolymer (B1), constitutes unit content in the scope of 0～20 mole of % from polyenoid.In propylene series copolymer (B1), contain under the situation of polyenoid composition; In propylene series copolymer (B1); With respect to 100 moles of % of total of propylene and terminal olefin (except propylene) (to add up to 100 moles of %), constitute unitary content for being higher than 0 mole of %, 20 moles below the % from polyenoid from the formation unit of propylene with from the formation of terminal olefin (except propylene) is unitary.
As diene, specifically can enumerate above-mentioned non-conjugated diene, conjugated diolefine.Wherein, be preferably diolefine with norbornylene skeleton.
The formation unit that is derived from aforesaid diene can contain a kind of, also can contain two or more.
As triolefin, specifically can enumerate above-mentioned non-conjugated triolefin, conjugated triene.Wherein, be preferably 4,8-dimethyl--1,4,8-triolefin in the last of the ten Heavenly stems, 4-ethylidene-8-methyl isophthalic acid, 7-nonadiene (EMND).
The formation unit that is derived from aforesaid triolefin can contain a kind of, also can contain two or more.In addition, can also contain formation unit that is derived from triolefin and the formation unit that is derived from diene.In these polyenoid compositions, be preferably especially and be derived from polyenoid formation unit with norbornylene skeleton.
The aforesaid iodine number that contains the propylene series copolymer (B1) of polyenoid composition is generally 1～80, is preferably 5～60.
The method of manufacture of (2) according to the present invention; Just can be easy to make the prior art manufacturing propylene series copolymer that contains the terminal olefin of a large amount of carbonatomss more than 4 difficulty, that molecular weight is high; In the aforesaid propylene based copolymer (B1) that obtains thus, be taken as P at the unitary mole fraction of formation that for example will be derived from ethene E, the unitary mole fraction of formation of the alkene in the terminal olefin that is derived from carbonatomss 4～20 such as being selected from 1-butylene or 1-octene is taken as P HAOSituation under, its ratio P E/ P HAOFor for example 0～0.80, be preferably 0～0.60, more preferably 0～0.50.And be under the necessary information at ethene, its ratio P E/ P HAOFor for example 0.05～0.80, be preferably 0.06～0.60, more preferably 0.10～0.50 scope.And not containing ethene also is a kind of preferred implementation.
<Syndiotactic propene polymer (A)>
Then, to the present invention's (3) syndiotactic propene polymer (A) (acrylic polymer (A)) with, the preferred forms that is used for embodiment of the present invention is described by the molding that this propene polymer is processed.
Characteristic properties, the representative method of manufacture of this polymkeric substance, the method for this polymkeric substance that is shaped and these the specific embodiment of syndiotactic propene polymer (A) are described specifically, below.
Syndiotactic propene polymer (A)
The present invention's (3) syndiotactic propene polymer (A) is to be derived from the acrylic polymer (constitute unitary add up to 100mol%) of the unitary content of formation of propylene above 90mol%.
The present invention's (3) syndiotactic propene polymer (A) so long as possess above-mentioned condition [1] and [2-1], be preferably the acrylic polymer of satisfy the requirements [1], [2-2] and [3], more preferably satisfy the requirements [1]～[4]; More preferably except satisfy condition [1]～[4]; Also satisfy condition [a]～acrylic polymer of [d]; Both can be alfon, also can be the random copolymers of the terminal olefin (not comprising propylene) of propylene-carbonatoms 2～20, can also be propylene-based block copolymer; Be preferably the random copolymers of the terminal olefin (not comprising propylene) of alfon or propylene and carbonatoms 2～20; Be preferably alfon especially, the multipolymer of the terminal olefin of the multipolymer of the terminal olefin of propylene and ethene or carbonatoms 4～10 and propylene and ethene, carbonatoms 4～10.
Wherein, As the terminal olefin of the carbonatoms except propylene 2～20, can enumerate ethene, 1-butylene, 3-methyl-1-butene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.And the present invention's (3) acrylic polymer contains the formation unit that is derived from propylene (being 100mol% with the unitary total amount of formation in this polymkeric substance (A) wherein) that is higher than 90mol%.Usually; Surpass 90mol% for containing the formation unit that is derived from propylene, below the 100mol%; Above with the formation unit 0mol% of the terminal olefin that is derived from carbonatoms 2～20 (not comprising propylene), as to be lower than 10mol% acrylic polymer (wherein, constituting the unitary 100mol% of adding up to); Be preferably and contain more than the formation unit 91mol% that is derived from propylene, below the 100mol%;, acrylic polymer 9mol% below (wherein, constitute unitary add up to 100mol%) above with the formation unit 0mol% of the terminal olefin that is derived from carbonatoms 2～20 (not comprising propylene); More preferably contain more than the formation unit 96mol% that is derived from propylene, below the 100mol%;, acrylic polymer 4mol% below (wherein, constitute unitary add up to 100mol%) above with the formation unit 0mol% of the terminal olefin that is derived from carbonatoms 2～20 (not comprising propylene).
Wherein, Syndiotactic propene polymer in the present invention (3) is under the situation of propylene-alpha-olefin random copolymers, preferably contains the amount of the formation unit 0.1～8mol% of formation unit 94～99.9mol% that is derived from propylene and the terminal olefin that is derived from carbonatoms 2～20 (not comprising propylene); The amount that preferably contains the formation unit 0.1～7mol% of formation unit 93～99.9mol% that is derived from propylene and the terminal olefin that is derived from carbonatoms 2～20 (not comprising propylene); The amount that more preferably contains the formation unit 0.1～6mol% of formation unit 94～99.9mol% that is derived from propylene and the terminal olefin that is derived from carbonatoms 2～20 (not comprising propylene).
In these syndiotactic propene polymers, consider aspects such as thermotolerance, more preferably alfon.
In addition; The limiting viscosity of in 135 ℃ of naphthane, measuring [η] of the present invention (3) syndiotactic propene polymer (A) is generally 0.01～10.00dL/g, is preferably 0.10～9.00dL/g, more preferably 0.50～8.00dL/g, further be preferably 0.95～8.00dL/g, be preferably 1.00～8.00 especially, further be preferably the scope of 1.40～8.00dL/g; Wherein, be preferably the scope of 1.40～5.00dL/g.
The present invention's (3) syndiotactic propylene copolymer (A) is characterised in that, satisfies following condition [1] and [2-1], is preferably to satisfy following condition [1], [2-2] and [3].
[1] adopts 13The syndiotactic five unit composition ratio (rrrr divides rate) that C-NMR measures are more than 85%.
The fusing point (Tm) that [2-1] use differential scanning calorimeter (DSC) is tried to achieve is more than 145 ℃.
[2-2] uses fusing point (Tm) that differential scanning calorimeter (below be called DSC) tries to achieve more than 145 ℃, and melting heat (Δ H) is more than the 40mJ/mg.
[3] be T with the isothermal crystal temperature of using differential scanning calorimeter to try to achieve Iso, the hypocrystalline time in the isothermal crystal is t 1/2Situation under, at 110≤T Iso≤150 (℃) scope in, satisfy following formula (Eq-1).
1.67×10 -4exp(0.10×T iso)≤t 1/2≤5.56×10 -4exp(0.12×T iso) (Eq-1)
Such syndiotactic propene polymer (A) is under the situation that is used to be shaped, and plasticity, thermotolerance, the transparency, rigidity and tensile break strength are excellent.Below, condition [1]～[3] are specified.
Condition [1]
(rrrr divides rate to the syndiotactic five unit composition ratio of measuring according to the NMR method of the syndiotactic propene polymer that the present invention is used; Five unit group syndiotactic property) more than 85%, be preferably more than 90%, more preferably more than 93%, further be preferably more than 94%; Rrrr divides plasticity, thermotolerance and the transparency of the syndiotactic propene polymer (A) of rate in this scope excellent; Characteristic as crystalline polypropylene is good, and is therefore preferred.Wherein, rrrr divides the upper limit of rate not special qualification, but below 100%, is generally for example below 99%.
These syndiotactic five unit composition ratio (rrrr branch rate) are described below and measure.
Rrrr divide rate by 13The absorption intensity of Prrrr (from the absorption intensity of the 3rd unitary methyl in 5 propylene units successive syndiotactic bonded positions) in the C-NMR spectrum and Pw (from the absorption intensity of all methyl of propylene units) is tried to achieve according to following formula (1).
Rrrr divides rate (%)=100 * Prrrr/Pw (1)
NMR measures and for example carries out according to being described below.That is, with 0.35g sample heating for dissolving in the 2.0ml hexachlorobutadiene.This solution with after glass filter (G2) filtration, is added deuterate benzene 0.5ml, the NMR pipe of the internal diameter 10mm that packs into.Then, use the system GX-500 of NEC type NMR determinator, under 120 ℃, carry out 13C-NMR measures.Cumulative number is more than 10,000 times.
Rrrr divides plasticity, thermotolerance and the mechanical characteristics of the syndiotactic propene polymer of rate in this scope excellent, and is good as crystalline Vestolen PP 7052 characteristic, therefore preferred.Through using as the described catalyst system in back, set as the described polymerizing condition in back, can make the syndiotactic propene polymer of rrrr branch rate in this scope.
Condition [2-1] and [2-2]
The fusing point (Tm) that the use differential scanning calorimeter (DSC) of syndiotactic propene polymer (A) records more than 145 ℃, preferably more than 150 ℃, more preferably more than 155 ℃, be preferably more than 156 ℃ especially.In addition, the melting heat that obtains simultaneously (Δ H) is above for 40mJ/mg, be preferably 50mJ/mg above, more preferably 52mJ/mg above, be preferably more than the 55mJ/mg especially.And the upper limit of Tm is not special to be limited, and is generally for example below 170 ℃.
The differential scanning calorimetry for example is described below and carries out.5mg left and right sides sample is being filled in the special-purpose aluminium dish; The DSCPyris1 or the DSC7 that use PerkinElmer company to produce; Speed according to 320 ℃/min is warmed up to 200 ℃ by 30 ℃, 200 ℃ down keep 5 minutes after, cool to 30 ℃ with the speed of 10 ℃/min by 200 ℃; After under 30 ℃, keeping 5 minutes, the endothermic curve when heating up with the speed of 10 ℃/min is then tried to achieve fusing point (Tm) again.In addition, when DSC measures, detect under the situation at a plurality of peaks, the detected peak of highest temperature side is defined as fusing point (Tm).
The plasticity of the syndiotactic propene polymer (A) of fusing point (Tm) in this scope, thermotolerance and mechanical characteristics are excellent, and be good as crystalline Vestolen PP 7052 characteristic, therefore preferred.Through using as the described catalyst system in back, set as the described polymerizing condition in back, can make the syndiotactic propene polymer of fusing point (Tm) in this scope.
Condition [3]
Isothermal crystal temperature with the syndiotactic propene polymer that utilizes differential scanning calorimeter (DSC) to measure to try to achieve is T Iso, the isothermal crystal temperature T IsoThe hypocrystalline time be t 1/2Situation under, at 110≤T Iso≤150 (℃) scope in, satisfy following formula (Eq-1),
1.67×10 -4exp(0.10×T isp)≤t 1/2≤5.56×10 -4exp(0.12×T iso) (Eq-1)
Be preferably and satisfy following formula (Eq-2)
1.67×10 -4exp(0.10×T iso)≤t 1/2≤3.71×10 -4exp(0.12×T iso) (Eq-2)
More preferably satisfy following formula (Eq-3)
1.67×10 -4exp(0.10×T iso)≤t 1/2≤2.23×10 -4exp(0.12×T iso) (Eq-3)
Hypocrystalline time (the t that utilizes isothermal crystal mensuration to try to achieve 1/2) be to be under the situation of total heat with DSC heat curve in the isothermal crystal process and the area between the baseline, reach the time [with reference to the high molecular rerum natura of new polymer experiment lecture 8-(the upright altogether Co., Ltd. that publishes)] of 50% heat.
Hypocrystalline time (t 1/2) measure to be described below and implement.5mg left and right sides sample is being filled in the special-purpose aluminium dish; The DSCPyris1 or the DSC7 that use PerkinElmer company to produce; According to being warmed up to 200 ℃ by 30 ℃ with 320 ℃/min; After keeping 5 minutes under 200 ℃, cool to each isothermal crystal temperature by this temperature (200 ℃) with 320 ℃/min, the DSC curve that keeps this isothermal Tc to obtain obtains.Wherein, hypocrystalline time (t 1/2) under the condition that is made as t=0 the isothermal crystal process time opening (moment when reaching the isothermal crystal temperature by 200 ℃), try to achieve.Syndiotactic propene polymer of the present invention can be tried to achieve t as stated 1/2, under certain isothermal crystal temperature, for example under 110 ℃ of non crystallized situation, through under the isothermal crystal temperature below 110 ℃, get a plurality of points and measure easily, ask for hypocrystalline time (t by its extrapolated value 1/2).
The syndiotactic propene polymer of [3] of satisfying condition is compared with existing syndiotactic propene polymer, and plasticity is especially excellent.Wherein, have excellent formability be meant implement injection, inflation, blowing, extrude or situation that compacting etc. is shaped under, short from molten state to solidifying the required time.In addition, excellences such as the forming period property of such syndiotactic propene polymer, shape stability, long-term production property.
Use as the described catalyst system in back, set as the described polymerizing condition in back, can make fully the syndiotactic propene polymer of satisfy condition [3].
Syndiotactic propene polymer of the present invention (A) is except above-mentioned condition [1]～[3], preferably also satisfy following condition [4] simultaneously.
Condition [4]
The amount that dissolves in the n-decane part of syndiotactic propene polymer is preferably below 0.8 (wt%), more preferably below 0.6 (wt%) below 1 (wt%).This amount that dissolves in the n-decane part is and the closely-related index of the blocking characteristics of syndiotactic propene polymer and molding therefrom that the amount that dissolves in the n-decane part usually just means that less low-crystalline becomes component few.That is the syndiotactic propene polymer (A ') of [4] of, also satisfying condition possesses fabulous anti-blocking characteristics.
The present invention's (3) syndiotactic propene polymer (A), be preferably syndiotactic propene polymer (A '), preferably also satisfy following condition [a]～[d]:
[a] modulus in tension is the scope of 500～2000 (MPa);
[b] tensile break strength is more than 20 (MPa);
The inside turbidity value of the compacting sheet material of [c] thickness 1mm is below 50%;
[d] pin is gone into temperature more than 145 ℃.
Below, condition [a]～[d] is elaborated.
Condition [a]
The present invention's (3) syndiotactic propene polymer (A), the modulus in tension that is preferably syndiotactic propene polymer (A ') are the scope of 500MPa～2000MPa, are preferably 600MPa～1800MPa, the scope of 600MPa～1500MPa more preferably.
Particularly, this modulus in tension is the value of measuring according to following working order.At first,, use the JIS3 dumb-bell test piece, be used to estimate sample with O dumbbell (オ one ダ one Application ベ Le) punching press with the standard of the thick compacting sheet material of 1mm according to JIS K6301.When mensuration, for example, the tensile testing machine Inston 1123 that uses Instron company to produce under distance between bench marks: 30mm, draw speed 30mm/min, measures modulus in tension down at 23 ℃, asks the MV of 3 mensuration.
The mechanical characteristics and the excellent strength of the syndiotactic propene polymer of modulus in tension in this scope are good as crystalline polyacrylic characteristic, therefore preferred.Use as the described catalyst system in back, set as the described polymerizing condition in back, can make the polymkeric substance of modulus in tension in this scope.
Condition [b]
The present invention's (3) syndiotactic propene polymer (A), the tensile break strength that is preferably syndiotactic propene polymer (A ') are more than 20 (MPa), are preferably more than 22 (MPa), more preferably more than 25 (MPa), further are preferably more than 30 (MPa).
Particularly, this tensile break strength is the value of measuring according to following working order.At first,, use the JIS3 dumb-bell test piece, be used to estimate sample with O dumbbell punching press with the standard of the thick compacting sheet material of 1mm according to JIS K6301.When mensuration, for example, the tensile testing machine Inston 1123 that uses Instron company to produce under distance between bench marks: 30mm, draw speed 30mm/min, measures modulus in tension down at 23 ℃, asks the MV of 3 mensuration.
The mechanical characteristics and the excellent strength of the syndiotactic propene polymer of tensile break strength in this scope are good as crystalline polyacrylic characteristic, therefore preferred.Use as the described catalyst system in back, set as the described polymerizing condition in back, can make the polymkeric substance of tensile break strength in this scope.
Condition [c]
The present invention's (3) syndiotactic propene polymer (A), the inside turbidity value that is preferably syndiotactic propene polymer (A ') are preferably below 45%, more preferably below 30% below 50%.
This inside turbidity value is to use the compacting sheet material test film of thickness 1mm, the MV of twice mensuration when the digital turbidometer of producing with Japanese electric look Industrial Co., Ltd " NDH-20D " is measured inner turbidity.
The transparency of the syndiotactic propene polymer of inner turbidity in this scope is excellent, and is good as crystalline polyacrylic characteristic, therefore preferred.Use as the described catalyst system in back, set as the described polymerizing condition in back, can make the polymkeric substance of inner turbidity value in this scope.
Condition [d]
The present invention's (3) syndiotactic propene polymer (A), the pin that is preferably syndiotactic propene polymer (A ') are gone into temperature more than 145 ℃, more preferably more than 150 ℃.
Pin is gone into temperature (also be called as TMA and measure the softening temperature of trying to achieve) and is described below and measures.
Use the SS-120 of Jinggong Co., Ltd's production or the Q-400 that TA Instrument company produces, the compacting sheet material test film of used thickness 1mm with the heat-up rate of 5 ℃/min, applies 2Kgf/cm on the pressure head of the plane of Φ 1.8mm 2Pressure, by the TMA curve try to achieve pin go into temperature (℃).
Pin is gone into the excellent heat resistance of the syndiotactic propene polymer of temperature in this scope; Good as crystalline polyacrylic characteristic; Therefore preferred, and under the situation as the transparency of the characteristic of syndiotactic propylene, excellences such as thermotolerance, rigidity, the strength of materials; Good as crystalline polyacrylic characteristic, therefore preferred.Use as the described catalyst system in back, set as the described polymerizing condition in back, can be manufactured on the polymkeric substance in this scope.
The present invention (3) relate to syndiotactic propene polymer (A), be preferably syndiotactic propene polymer (A '), more preferably the syndiotactic propene polymer (A ") be shaped and molding.
The method of manufacture of syndiotactic propene polymer
As the present invention's (3) syndiotactic propene polymer (A) and after state catalyzer (3) that the present invention (4), (5) and (6) used syndiotactic propene polymer (AA) use when making and be fit to use catalyst for polymerization (cat-1) or this catalyzer (cat-1) to be supported on the granular carrier and the polyalcohol catalyst (cat-2) that forms; The proterties of [1]～[3] but as long as the polymkeric substance that demonstrates generation satisfies condition; The catalyzer that uses in the manufacturing of the present invention's (3) syndiotactic propene polymer (A); And after state the catalyzer that uses when the used syndiotactic propene polymer (AA) of the present invention (4), (5) and (6) is made, this catalyzer is had no qualification.Above-mentioned catalyst for polymerization (cat-1) contains:
(a-3) the crosslinked metallocene compound shown in the formula [1-3] (being also referred to as in this manual, " composition (a-3) ") and
(b) be selected from (b-1) Organoaluminoxy compound,
(b-2) with the right compound of above-mentioned crosslinked metallocene compound (a-3) reacting forming ion and
(b-3) compound more than at least a kind in the organo-aluminium compound.
Figure GSA00000105371100751
In above-mentioned general formula [1-3], R 1, R 2, R 3And R 4Be selected from Wasserstoffatoms, alkyl and contain silica-based, R 2And R 3Can mutually combine and form ring, R 5, R 6, R 8, R 9, R 11And R 12Be selected from hydrogen, alkyl and contain silica-based, R 7, R 10These two bases are not Wasserstoffatomss, be selected from alkyl with contain silica-based, can be identical also can be different, be selected from R 5And R 6, R 7And R 8, R 8And R 9, R 9And R 10, and R 11And R 12In more than one adjacent base combination in, this adjacent base can interosculate into ring.
R 17And R 18Be alkyl that is selected from Wasserstoffatoms, carbonatoms 1～20 or the base that contains Siliciumatom, can be identical also can be different, substituting group can interosculate and form ring.
M is Ti, Zr or Hf, and Y is a carbon, and Q can be from from halogen, alkyl, anion binding base and can be selecting the identical or different combination of lone-pair electron coordinate neutral dentate, and j is 1～4 integer.
Below, composition (crosslinked metallocene compound) concrete example (a-3) that satisfies this definition is described, can enumerate:
Cyclopropylidene (cyclopentadienyl moiety) (3,6-two uncle's fluorenyls) zirconium dichloride, inferior cyclobutyl (cyclopentadienyl moiety) (3,6-two uncle's fluorenyls) zirconium dichloride, cyclopentylidene (cyclopentadienyl moiety) (3; 6-two uncle's fluorenyls) zirconium dichloride, cyclohexylidene (cyclopentadienyl moiety) (3,6-two uncle's fluorenyls) zirconium dichloride, inferior suberyl (cyclopentadienyl moiety) (3,6-two uncle's fluorenyls) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety (2; 7-two (2,4, the 6-trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-two (3, the 5-3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-two (4-aminomethyl phenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-dinaphthyl-3,6-di-t-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-two (4-tert-butyl-phenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride,
Diisobutyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, (2,7-two (2 for diisobutyl methylene radical (cyclopentadienyl moiety); 4,6-trimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2,7-two (3, the 5-3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2,7-two (4-aminomethyl phenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2,7-dinaphthyl-3,6-di-t-butyl fluorenyl) zirconium dichloride, diisobutyl methylene radical (cyclopentadienyl moiety) (2,7-two (4-tert-butyl-phenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride (also are called as 1 in addition; 3-phenylbenzene isopropylidene (cyclopentadienyl moiety) (2,7-dimethyl--3,6-two tert-pentyls) zirconium dichloride hereinafter omits another name), dibenzyl methylene radical (cyclopentadienyl moiety (2; 7-two (2,4, the 6-trimethylphenyl)-3; 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-two (3, the 5-3,5-dimethylphenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2; 3,6,7-tetra-tert fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-two (4-aminomethyl phenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dinaphthyl-3; 6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two (4-tert-butyl-phenyl)-3,6-di-t-butyl fluorenyl) zirconium dichloride,
Two styroyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two styroyl methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (diphenyl-methyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (diphenyl-methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (cumyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (cumyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (1-phenyl-ethyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (1-phenyl-ethyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (cyclohexyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (cyclohexyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (cyclopentyl-methyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (cyclopentyl-methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (naphthyl methyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (naphthyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (xenyl methyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (xenyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride,
(benzyl) (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (normal-butyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, inferior cyclobutyl (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, inferior cyclobutyl (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, inferior suberyl (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, inferior suberyl (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride,
Dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-dimethyl--butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-dimethyl--butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-diisopropylbenzyl-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-diisopropylbenzyl-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-two (TMS)-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-two (TMS)-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-phenylbenzene-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-phenylbenzene-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-dibenzyl-butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-dibenzyl-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-dimethyl--butyl fluorenyl) zirconium dichloride, di-n-butyl methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-dimethyl--butyl fluorenyl) zirconium dichloride,
Phenylbenzene methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to bromophenyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to the tertiary butyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to the tertiary butyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (to normal-butyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to normal-butyl-phenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride,
Two (to xenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (to xenyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (1-naphthyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (1-naphthyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (naphthyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride, two (naphthyl methyl) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (p-isopropyl phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-isopropyl phenyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, two (xenyl methyl) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride, two (xenyl methyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride, phenylbenzene silicylene (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl fluorenyl) example such as zirconium dichloride, phenylbenzene silicylene (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride.
In addition; Compound or " dichloride " that " zirconium " of too can example above-mentioned illustrational compound replaces with " hafnium " or " titanium " replace with " difluoride ", " dibromide ", " diiodide ", or " dichloride " replaces with the crosslinked metallocene compound of " dimethyl-" or " methylethyl ".
Above-mentioned crosslinked metallocene compound (a-3) can be according to the known method manufacturing, the not special restriction of this method of manufacture.As known method of manufacture, can enumerate the applicant for example WO2001/27124 number with the method for manufacture described in the WO2004/087775 communique.In addition, above-mentioned crosslinked metallocene compound (a-3) can use a kind of separately, also can two or more combinations use.
Above-claimed cpd (b) be selected from above-mentioned Organoaluminoxy compound (b-1), with the right compound (b-2) of above-mentioned crosslinked metallocene compound (a-3) reacting forming ion and at least a kind of compound in the above-mentioned organo-aluminium compound (b-3).
Wherein, " compound (b-2) right with crosslinked metallocene compound (a-3) reacting forming ion " is identical with above-mentioned " compound (b-2) right with crosslinked metallocene compound (a-1) reacting forming ion (ionic compound (b-2)) ", and the particular content of above-mentioned Organoaluminoxy compound (b-1), above-claimed cpd (b-2) and above-mentioned organo-aluminium compound (b-3) as stated.
In addition; Above-mentioned catalyzer (3); Not only contain the crosslinked metallocene compound shown in (a-3) above-mentioned general formula [1-3] and (b) be selected from the right compound of (b-1) Organoaluminoxy compound, (b-2) and above-mentioned crosslinked metallocene compound (a-3) reacting forming ion and (b-3) at least a kind of compound in the organo-aluminium compound as catalyst component, as required; Also can contain above-mentioned carrier (c), capable of loading and carrying the going up in granular above-mentioned carrier (c) of above-mentioned each composition used.
In addition, above-mentioned catalyzer (3) also can contain above-mentioned organic compound ingredient (d) as catalyst component as required.
The particular content of above-mentioned carrier (c) and above-mentioned organic cpds (d) as stated.
The method of manufacture of syndiotactic propene polymer (A)
When the polymerization of the present invention's (3) syndiotactic propene polymer (A), can select method of use, the interpolation order of each composition arbitrarily, can enumerate the method that is described below as polymerization method:
(1) adds composition (a-3) in the polymerizer method separately;
(2) add composition (a-3) and composition (b) in the polymerizer method with random order;
(3) composition (a-3) is supported at carrier (c) and goes up and obtain catalyst component, add this catalyst component and composition (b) in the polymerizer method with random order;
(4) composition (b) is supported at carrier (c) and goes up and obtain catalyst component, add this catalyst component and composition (a-3) in the polymerizer method with random order;
(5) composition (a-3) and composition (b) are supported at that carrier (c) is gone up and the catalyst component that obtains adds the method in the polymerizer to.
In the method for above-mentioned (2)～(5), also can make the contact in advance more than at least two of each catalyst component.
In each method of carrying above-mentioned (4) hold composition (b), (5), also can add with random order as required and carried the composition of holding (b).In this case, composition (b) can be identical also can be different.
In addition; Be carried with the solid catalyst component that is carried with composition (a-3) and composition (b) on the solid catalyst component, composition (c) of composition (a-3) on the mentioned component (c); Can make olefinic polymerization earlier, also can on prepolymerized solid catalyst component, carry again and hold catalyst component.
In the manufacturing of the present invention's (3) syndiotactic propene polymer (A), polymerization can be adopted any enforcement in liquid polymerizations such as solution polymerization, suspension polymerization or the gaseous polymerization.As the torpescence hydrocarbon medium that uses in the liquid polymerization, specifically can enumerate aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, 12 carbon alkane, kerosene; Clicyclic hydrocarbons such as pentamethylene, hexanaphthene, methylcyclopentane; Aromatic hydrocarbonss such as benzene,toluene,xylene; Halohydrocarbon such as ethylene chloride, chlorobenzene, methylene dichloride or their mixture etc. also can be with being used as solvent by polymeric alkene itself.
When using aforesaid catalyst for olefines polymerizing to carry out olefinic polymerization, the consumption of composition (a-3) is that per 1 liter of reaction volume is generally 10 19～10 -1The mole, be preferably 10 -8～10 -2Mole.
The consumption of composition (b-1) does, makes the mol ratio [(b-1)/M] of all transition metal atoms (M) in composition (b-1) and the composition (a-3) be generally 0.01～5000, be preferably 0.05～2000.The consumption of composition (b-2) does, makes the mol ratio [(b-2)/M] of the transition metal atoms (M) in composition (b-2) and the composition (a-3) be generally 1～10, be preferably 1～5.The consumption of composition (b-3) does, makes the mol ratio [(b-3)/M] of all transition metal (M) in aluminium atom and the composition (a-3) in the composition (b-3) be generally 10～5000, be preferably 20～2000.
The consumption of composition (d) is under the situation of composition (b-1) at composition (b). makes mol ratio [(d)/(b-1)] be generally 0.01～10, is preferably 0.1～5 amount; At composition (b) is under the situation of composition (b-2), makes mol ratio [(d)/(b-2)] be generally 0.01～10, is preferably 0.1～5 amount; At composition (b) is under the situation of composition (b-3), makes mol ratio [(d)/(b-3)] be generally 0.01～2, is preferably 0.005～1 amount.
In addition, use the polymerization temperature of the alkene of above-mentioned olefin polymerization catalysis to be generally-50～+ 200 ℃, be preferably 0～170 ℃ scope.Polymerization pressure is generally normal pressure～10MPa gauge pressure, is preferably normal pressure～condition of 5MPa gauge pressure, and under this condition, polyreaction can adopt any method in batch-type, semi continuous, the continous way to implement.Also can polymerization be divided into reaction conditions carried out more than the two different stages.The molecular weight of the olefin polymer of gained can be regulated through whether having hydrogen in the polymerization system or changing polymerization temperature.Moreover, also can regulate according to the amount of the composition (b) that uses.Under the situation of adding hydrogen, its appropriate addition is that every 1kg alkene is about 0.001～100NL.
The syndiotactic propene polymer (A) that obtains according to above-mentioned polymerization method also can utilize polar monomer that a part is wherein carried out graft modification.As this polar monomer, can enumerate the ethene property unsaturated compound that contains hydroxyl, the ethene property unsaturated compound that contains amino, the ethene property unsaturated compound that contains epoxy group(ing), aromatic ethenyl compound, unsaturated carboxylic acid or derivatives thereof, vinyl ester compound, vinylchlorid, the silicoorganic compound that contain vinyl, carbodiimide compound etc.
As polar monomer, be preferably the unsaturated carboxylic acid or derivatives thereof especially especially.As the unsaturated carboxylic acid or derivatives thereof, can enumerate the unsaturated compound with 1 above carboxylic acid group, compound and alkyl alcohol with carboxylic acid group ester, have 1 above acid anhydride's unsaturated compound etc.; As unsaturated group, can enumerate vinyl, vinylidene, unsaturated cyclic hydrocarbon radical etc.As concrete compound; For example can enumerate vinylformic acid, toxilic acid, fumaric acid, tetrahydrophthalic acid, methylene-succinic acid, citraconic acid, butenoic acid, methylacrylic acid, Nadic acid (trade mark) unsaturated carboxylic acids such as (internally-oriented cis-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylicacid); Or derivatives thereof, for example acid halide (acid halide), acid amides, imide, acid anhydride, ester etc.As the concrete example of these verivates, can enumerate for example Malaysia acyl chlorides, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, toxilic acid glycidyl ester etc.These unsaturated carboxylic acids and/or its verivate can use a kind of separately, also can two or more combinations use.Wherein, be fit to use unsaturated dicarboxylic acid or its acid anhydrides, especially preferably use toxilic acid, Nadic acid (trade mark) or their acid anhydrides.
Modification syndiotactic propene polymer obtains through making aforesaid syndiotactic propene polymer (A) and polar monomer graft polymerization.When syndiotactic propene polymer and aforesaid polar monomer graft polymerization, the consumption of polar monomer does, with respect to 100 weight part syndiotactic propene polymers (A), usually with 1～100 weight part, preferably use with the amount of 5～80 weight parts.This graft polymerization is carried out in the presence of radical initiator usually.
As radical initiator, can use organo-peroxide or azo cpd etc.
Radical initiator can directly mix the back use with syndiotactic propene polymer and polar monomer, also may be dissolved in a spot of organic solvent and uses afterwards.As this organic solvent, can use so long as can dissolve the organic solvent of radical initiator, remove this not special qualification.
In addition, when syndiotactic propene polymer (A) and polar monomer graft polymerization, also can use reducing substances.When using reducing substances, can improve the grafting amount of polar monomer.
Syndiotactic propene polymer (A) utilizes the graft modification of polar monomer to carry out according to existing known method; For example; Can then, polar monomer and radical initiator etc. be added in the solution through syndiotactic propene polymer (A) is dissolved in the organic solvent; 70～200 ℃, be preferably under 80～190 ℃ the temperature, react 0.5～15 hour, be preferably 1～10 hour and react and carry out.
And, also can use forcing machine etc., under solvent-free condition, make syndiotactic propene polymer (A) and polar monomer reaction, make modification syndiotactic propene polymer.It specifically is under 120～250 ℃ temperature more than the fusing point of ethylene-based polymer that this reaction is preferably common, carries out usually 0.5～10 minute.
The modification amount of the modification syndiotactic propene polymer that obtains like this (the grafting amount of polar monomer) is generally 0.1～50 weight %, is preferably 0.2～30 weight %, 0.2～10 weight % more preferably.
Contain under the situation of above-mentioned modification syndiotactic propene polymer in the present invention's (3) the syndiotactic propene polymer (A), excellent with binding property, the intermiscibility of other resin, and can also improve the wellability on molding surface sometimes.
And the present invention's (3) modification syndiotactic propene polymer also can be suitable for as crosslinked electric wire, crosslinked pipeline sometimes through crosslinked.
And, in the present invention's (3) the syndiotactic propene polymer (A),, that is,, also can cooperate nucleator as specific any composition for improving Tc, accelerating crystallization velocity for further improving its plasticity.In the case; For example nucleator is that dibenzylidene sorbitol is that nucleator, phosphate ester salt are that nucleator, rosin series nucleator, TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. metal-salt are nucleator, fluoro Vilaterm, 2; 2-methylene-bis (4, the 6-di-tert-butyl-phenyl) sodium phosphate, pimelic acid and salt, 2 thereof, 6-naphthalene diacid dicyclohexyl acid amides etc.; The not special restriction of its use level, being preferably with respect to 100 weight part syndiotactic propene polymers (A) is about 0.1～1 weight part.Not special restriction on cooperation opportunity can be between polymerization period, after the polymerization or be shaped to add and add man-hour.
In the present invention's (3) the syndiotactic propene polymer (A); In the scope of goal of the invention, can cooperate additives such as weather-proof stablizer, heat-resisting stabilizing agent, static inhibitor, slipproofing agent, antiblocking agent, whipping agent, crystallization auxiliary, antifogging agent, transparent nucleater, lubricant, pigment, dyestuff, softening agent, inhibitor, hydrochloric acid absorbent, inhibitor, releasing agent, shock resistance activator, anti-UV agent as required.
Syndiotactic propene polymer (A) can be through adopting various known method to make in aforesaid scope each composition; For example adopt continous way or the multistage polymeric method of batch-type with slurry phase, solution phase or gas phase; Use method of mixing such as Henschel mixing roll, V-Mixer, ribbon blender (ribbon blender), drum tumbler; Or after mixing; Behind melting mixings such as single screw extrusion machine, twin screw extruder, kneader, Banbury, the method for carrying out granulation or pulverizing.
In addition, of the present invention contain acrylic polymer (A) if compsn contain (A), remove this not special qualification.
The molding that manufacturing process and this method of use obtain
The syndiotactic propene polymer (A) that obtains according to the method described above or plasticity, the excellent heat resistance of its modification body; And can obtain the excellent molding of plasticity, thermotolerance, the transparency, rigidity and tensile break strength; Therefore; Can be widely used in and use existing syndiotactic polypropylenes unapproachable polyolefine purposes in practicality, especially can with syndiotactic propene polymer (A) be configured as sheet material for example, not stretching or oriented film, filament, other different shape molding and utilize.And; The molding that uses syndiotactic propene polymer (A) and get; The part that both can be molding contains syndiotactic propene polymer (A), and promptly the part of molding is used syndiotactic propene polymer (A), also can all use syndiotactic propene polymer (A) by molding.Use the instance of syndiotactic propene polymer (A) can enumerate multilayer laminate as the part of molding.As multilayer laminate; Particularly; Be one of them layer for contain that syndiotactic propene polymer (A) gets layer multilayer body, the multilayer film multilayer body that can enumerate multilayer film and sheet material, laminated vessel, multilayered tube, contains etc. as one of moity of water-borne coatings.
The present invention's (3) syndiotactic propene polymer (A) can be shaped, extrude laminating molding, cast form, blow molding, extrusion-blown modling shaping, injection blow molding shaping, press forming, vacuum forming, calendaring molding, foaming and molding, the slush moulding known thermo shaping methods such as (powder slush molding) that is shaped through extrusion molding, injection forming, inflation and form.In addition, also can use fiber, single strand, non-woven fabrics etc.
These moldinies comprise the molding (multilayer body etc.) of part that contains syndiotactic propene polymer (A) and the part that contains other resin.Wherein, syndiotactic propene polymer (A) can use polymkeric substance crosslinked in the forming process.
As molding, specifically can enumerate the molding that obtains through known thermo shaping methods such as extrusion molding, injection forming, inflation shaping, blow molding, extrusion-blown modling shaping, injection blow molding shaping, press forming, vacuum forming, calendaring molding, foaming and molding, slush moulding shapings.Enumerate numerical example below and be illustrated as body.
The present invention's (3) molding is for for example to be extruded under the situation of body; To its shape and the not special qualification of goods kind; For example sheet material, film (not stretching), conduit (pipe), flexible pipe, wire covering materials, pipe (tube) etc. be can enumerate, sheet material (skin-material), film, pipe (tube), catheter (catheter), single strand (non-woven fabrics) etc. are preferably especially.
Excellences such as the syndiotactic propene polymer (A) that obtains according to the method described above or the transparency, shock resistance, thermotolerance, flexibility or the rigidity of its modification body, wearability, surface hardness, shrinkability, sound insulation property, vibration damping property, cutting, high-breakdown-voltage, radiation resistant property, resistance to deterioration, even foaming property, caoutchouc elasticity, flex resistance, retractility, creep properties, binding property, soft modification property, transparent modified property are therefore applicable to following purposes.
With regard to purposes, can enumerate usually food product containers, carafe, pipe (pipe), packaging material for food, high temperature steaming container, medical container, infusion bag, clothing case, transparency carrier, transparent sealant, sealing material, car interior-exterior finishing material, automobile skin-material, wear-resistant car interior-exterior finishing material, mole material, automobile with sealing material, building material surface material, shrinkable film, wrap film (wrap film), porous membrane, multilayer body, sound insulating member, shock absorber part, foam, foam material, cushioning material, mask, electric capacity with film, protective film, reflectance coating, granulation film (dicing film), multilayer body (comprising glass), electric wire, oriented film, shape-memory material and glass with film, bullet resistant material, splinter-proof glass with film, encapsulating material for solar cell, anti-radioactive rays film, anti-gamma-rays film, ripple (flow mark) is material modified, welding is material modified, non-woven fabrics, flexible nonwoven fabrics, material modified, jointing material, compatibility agent (graft modification) etc.
During syndiotactic propene polymer (A) extrusion molding; Can adopt existing known extrusion device and molding condition; For example; Can use single screw extrusion machine, mixing extruder, plunger-type extruder (ram extruder), gear forcing machine etc., the fused propylene compositions is extruded by specific mould etc., be configured as the shape of expection.
Oriented film stretches according to known drawing process such as for example tentering method (vertically and horizontally stretching, horizontal vertical stretching), the method for two-way stretch simultaneously, unilateral stretching methods through extrusion sheet or extrusion film as stated (not stretching) and obtains.
Stretching ratio when sheet material or non-stretched film stretch is generally about 20～70 times, and under the situation of unilateral stretching, is generally about 2～10 times under the situation of two-way stretch.Preferably obtain the oriented film about thickness 5～200 μ m through stretching.
In addition, as the film like molding, can make inflation film.Inflation is not prone to contraction (draw down) when being shaped.
The sheet material and the film shaped body that use syndiotactic propene polymer (A) to form are difficult for charged; Mechanical characteristics, thermotolerance, retractility, shock resistance, resistance to deterioration, the transparency, see-through, glossiness, rigidity, moistureproofness and gas barrier property (gas barrier) excellence can be widely used as packaging film etc.
In the case, the sheet material and the film shaped body that use syndiotactic propene polymer (A) to form both can be the multilevel shaping bodies, also can process the multilayer laminate that contains one deck syndiotactic propene polymer at least and use.
In addition, the filament molding can be made through fused syndiotactic propene polymer (A) is extruded through spinning top.Particularly, be fit to adopt spun-bond process, meltblown.The fiber that obtains so also can stretch again.As long as this stretching can make fiber at least one axially be the degree of molecular orientation, preferably carry out usually with about 5～10 times multiplying power.The fiber that contains syndiotactic propene polymer (A) is difficult for charged, and the transparency, flexibility, thermotolerance and shock resistance, retractility are excellent.
Being injected into body and can using existing known injection molding device for molding, adopt known condition, is the different shape manufacturing with syndiotactic propene polymer (A) injection forming.The body that is injected into that uses the aforesaid propylene compsn and get is difficult for charged; Excellences such as the transparency, rigidity, thermotolerance, shock resistance, surface gloss, resistance to chemical reagents, wearability, can be widely used in automobile interior trim with decorative material, automobile with the shell of decorative material, tame electrical article, container etc.
Be blow molded into body and can use existing known blow molding apparatus, adopt known condition, (A) blow molding of syndiotactic propene polymer is made.In the case, the body that is blow molded into that contains syndiotactic propene polymer (A) both can be the multilevel shaping body, and also one deck contains syndiotactic propene polymer (A) at least.
For example, in extrusion-blown modling was shaped, syndiotactic propene polymer (A) was under the molten state of 100 ℃～300 ℃ of resin temperatures; (die) extrudes the formation tubular parison through die head; After remaining on this parison in the mould with anticipated shape then, be blown into air, under 130 ℃～300 ℃ of resin temperatures; Be assemblied on the mould, just can make the hollow forming body.(blowing) multiplying power that stretches is preferably on the transverse direction about 1.5～5 times.
In addition, during injection blow molding was shaped, syndiotactic propene polymer (A) was under 100 ℃～300 ℃ of resin temperatures; Be expelled in the parison mould; Form parison, be blown into air after remaining on this parison in the mould of intended shape then, under 120 ℃～300 ℃ of resin temperatures; Be assemblied on the mould, just can make the hollow forming body.(blowing) multiplying power that stretches is preferably on the longitudinal direction on 1.1～1.8 times, transverse direction about 1.3～2.5 times.
Not only the transparency, rigidity or flexibility, thermotolerance and shock resistance are excellent for the body that is blow molded into that use syndiotactic propene polymer (A) forms, and moistureproofness is also excellent.
As compression forming body, can enumerate mold punching press (mold stamping) molding, for example base material and skin-material while press forming makes both compound, and the base material when being configured as one (mold drawing) can adopt the syndiotactic propene polymer to form.
Mold as such strikes out body, specifically can enumerate inner decoration material for vehicle such as door trim material, boot finishing material, backrest backboard, panel board.
The compression forming body that uses syndiotactic propylene polymkeric substance (A) and get is difficult for excellences such as charged, rigidity or flexibility, thermotolerance, the transparency, shock resistance, resistance to deterioration, surface gloss, resistance to chemical reagents, wearability.
The foam molding that uses syndiotactic propylene polymkeric substance (A) and get can reach high foamability, and has good injecting formability, and the high rigidity and the strength of materials have developed simultaneously.
Syndiotactic propylene polymkeric substance (A) can be made interior trim skin-material equal vacuum moldinies such as the panel board, door trim material of automobile.This molding is difficult for charged, excellences such as flexibility, thermotolerance, shock resistance, resistance to deterioration, surface gloss, resistance to chemical reagents, wearability.
Through forming the present invention's (3) acrylic polymer (A), can make slush moulding powder moldinies such as automobile component, tame electrical article, toy, general merchandise.This molding is difficult for charged, excellences such as flexibility, thermotolerance, shock resistance, resistance to deterioration, surface gloss, resistance to chemical reagents, wearability.
In addition, as the molding of the present invention (3), can enumerate the multilayer body that has the layer that one deck is made up of syndiotactic propene polymer (A) at least.
The present invention's (3) acrylic polymer is specially adapted to be extruded into body (film, sheet material etc.), is blown into body, is injected into body, is blow molded into body, filament; Consider the transparency and thermotolerance, be specially adapted to be extruded into body, be blown into body, be injected into body, be blow molded into body.
The present invention's (3) acrylic polymer is applicable to for example container or non-woven fabrics.As said vesse, can enumerate for example food product containers such as freezer storage container, high-temperature retort bag, bottle container etc.In addition, also can enumerate medical container, infusion bag etc.
And plasticity, the excellent heat resistance of the present invention's (3) the compsn that contains acrylic polymer (A) therefore, also can be used for such use (purposes of acrylic polymer (A)).
<Propylene polymer composition (X1)>
Below, specify the present invention (4).
The present invention's (4) propylene polymer composition (X1) contains specific (AA) syndiotactic propene polymer and specific (B2) propylene-alpha-olefin copolymers.
(AA) the syndiotactic propylene gathers golden thing
The present invention (4) and after state the used syndiotactic propene polymer (AA) in the present invention (5) and (6) as long as possess property; It then both can be alfon; It also can be the random copolymers of the terminal olefin (not comprising propylene) of propylene-carbonatoms 2～20; Can also be propylene-based block copolymer, be preferably the random copolymers of the terminal olefin of alfon or propylene-carbonatoms 2～20.Be preferably alfon especially, propylene and ethene or with the multipolymer of the terminal olefin of multipolymer, propylene and the ethene of the terminal olefin of carbonatoms 4～10, carbonatoms 4～10, especially consider thermotolerance etc., be preferably alfon.
Wherein, As the terminal olefin of the carbonatoms 2～20 beyond the propylene, can enumerate ethene, 1-butylene, 3-methyl-1-butene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.Wherein, usually with respect to 100 moles of % of the unitary total of the formation of the terminal olefin that is derived from carbonatoms 2～20 (comprising propylene), the unitary content of formation that is derived from propylene is higher than 90 moles of %, is preferably more than the 91mol%.In other words; Syndiotactic propene polymer of the present invention (AA) contain usually the unitary amount of the formation that is derived from propylene be higher than 90 moles of %, at 100 moles below the %; And the unitary amount of formation that contains the terminal olefin (not comprising propylene) that is derived from carbonatoms 2～20 0 mole more than the %, be lower than 10 moles of % (wherein, from the formation unit of propylene with add up to 100 moles of %) from the formation of the terminal olefin (not comprising propylene) of carbonatoms 2～20 is unitary; Be preferably especially contain the unitary amount of the formation that is derived from propylene be 91 moles of % above, 100 moles below the %, and the unitary amount of formation that contains the terminal olefin (not comprising propylene) that is derived from carbonatoms 2～20 be 0 mole of % above, 9 moles below the %.
At syndiotactic propene polymer (AA) is under the situation of propylene-alpha-olefin random copolymers, and the unitary amount of formation that preferably contains the terminal olefin (not comprising propylene) that is derived from carbonatoms 2～20 is 0.3～7 mole of %, be preferably 0.3～6 mole of %, more preferably 0.3～5 mole of %.
(rrrr divides rate to the syndiotactic five unit composition ratio of measuring according to the NMR method of above-mentioned syndiotactic propene polymer (AA); Five unit group syndiotactic property) more than 85%, be preferably more than 90%, more preferably more than 93%, further be preferably more than 94%; Rrrr divides plasticity, thermotolerance and the transparency of the syndiotactic propene polymer (AA) of rate in this scope excellent; Characteristic as crystalline polypropylene is good, and is therefore preferred.In addition, rrrr divides the upper limit of rate not special qualification, below 100%, is generally for example below 99%.
These syndiotactic five unit composition ratio (rrrr branch rate) are described below and measure.
Rrrr divide rate by 13The absorption intensity of Prrrr in the C-NMR spectrum (from the absorption intensity of the 3rd unitary methyl at 5 propylene units successive syndiotactic bonded positions) and Pw (from the absorption intensity of all methyl of propylene units) is tried to achieve according to following formula (1).
Rrrr divides rate (%)=100 * Prrrr/Pw (1)
NMR measures and for example carries out according to being described below.That is, with sample 0.35g heating for dissolving in the 2.0ml hexachlorobutadiene.This solution with after glass filter (G2) filtration, is added 0.5ml deuterate benzene, the NMR pipe of the internal diameter 10mm that packs into.Then, the GX-500 type NMR determinator that uses NEC to produce is implemented down at 120 ℃ 13C-NMR measures.Cumulative number is more than 10,000 times.
The limiting viscosity of in 135 ℃ of naphthane, measuring [η] of syndiotactic propene polymer (AA) is 0.1～10dL/g, be preferably 0.5～10dL/g.More preferably 0.50～8.00dL/g, further be preferably 0.95～8.00dL/g, be preferably 1.00～8.00 especially, further be preferably the scope of 1.40～8.00dL/g, wherein, be preferably the scope of 1.40～5.00dL/g.The syndiotactic propene polymer (AA) of such limiting viscosity [η] value demonstrates good flowability, is easy to and other components matching, and is expected to obtain the excellent molding of physical strength by the compsn of gained.
In addition, the fusing point (Tm) that records of the use differential scanning calorimeter (DSC) of syndiotactic propene polymer (AA) is more than 145 ℃, preferably more than 147 ℃, more preferably more than 150 ℃, further be preferably more than 155 ℃, be preferably more than 156 ℃ especially.Wherein, the upper limit of Tm is not special to be limited, and is generally for example below 170 ℃.And, syndiotactic propene polymer (AA) use the melting heat (Δ H) that differential scanning calorimeter (DSC) records above as 40mJ/mg, be preferably 45mJ/mg above, more preferably 50mJ/mg above, further be preferably 52mJ/mg above, be preferably more than the 55mJ/mg especially.
The differential scanning calorimetry for example is described below and carries out.Sample about 5.00mg is being filled in the special-purpose aluminium dish; The DSCPyris1 or the DSC7 that use PerkinElmer company to produce; According to being warmed up to 200 ℃ by 30 ℃, after keeping 5 minutes under 200 ℃, cool to 30 ℃ by 200 ℃ with 10 ℃/min with 320 ℃/min; After under 30 ℃, keeping 5 minutes, the endothermic curve when heating up with 10 ℃/min is then tried to achieve fusing point (Tm) and melting heat (Δ H) again.In addition, when DSC measures, when detecting a plurality of peak, the detected peak of highest temperature side is defined as fusing point (Tm).
The plasticity of the syndiotactic propene polymer (AA) of fusing point (Tm) in this scope, thermotolerance and mechanical characteristics are excellent, and be good as crystalline Vestolen PP 7052 characteristic, therefore preferred.Through using as the described catalyst system in back, set as the described polymerizing condition in back, can make the syndiotactic propene polymer (AA) of fusing point (Tm) in this scope.
Syndiotactic propene polymer (AA) is made as T in the isothermal crystal temperature that will utilize differential scanning calorimeter (DSC) mensuration to try to achieve Iso, the isothermal crystal temperature T IsoUnder the hypocrystalline time be made as t 1/2Situation under, at 110≤T Iso≤150 (℃) scope in, satisfy following formula (Eq-1),
1.67×10 -4exp(0.10×T iso)≤t 1/2≤5.56×10 -4exp(0.12×T iso) (Eq-1)
Be preferably and satisfy following formula (Eq-2)
1.67×10 -4exp(0.10×T iso)≤t 1/2≤3.71×10 -4exp(0.12×T iso) (Eq-2)
More preferably satisfy following formula (Eq-3)
1.67×10 -4exp(0.10×T iso)≤t 1/2≤2.23×10 -4exp(0.12×T iso) (Eq-3)
Hypocrystalline time (the t that utilizes isothermal crystal mensuration to try to achieve 1/2) be to be under the situation of total heat with DSC heat curve in the isothermal crystal process and the area between the baseline, reach the time [with reference to the high molecular rerum natura of new polymer experiment lecture 8-(the upright altogether Co., Ltd. that publishes)] of 50% heat.
Hypocrystalline time (t 1/2) measure to be described below and carry out.Sample about 5mg is filled in the special-purpose aluminium dish; The DSCPyris1 or the DSC7 that use PerkinElmer company to produce; According to being warmed up to 200 ℃ by 30 ℃ with 320 ℃/min; 200 ℃ down keep 5 minutes after, cool to each isothermal crystal temperature by this temperature (200 ℃) with 320 ℃/min, keep the DSC curve that this isothermal Tc obtains and obtain.Wherein, hypocrystalline time (t 1/2) under the condition that is made as t=0 the isothermal crystal process time opening (moment when reaching the isothermal crystal temperature by 200 ℃), try to achieve.To above-mentioned syndiotactic propene polymer (AA), can try to achieve t as stated 1/2, under certain isothermal crystal temperature, for example under 110 ℃ of non crystallized situation, can measure through under the isothermal crystal temperature below 110 ℃, getting a plurality of points easily, ask for hypocrystalline time (t by its extrapolated value 1/2).
Satisfy the syndiotactic propene polymer (AA) of above-mentioned (Eq-1) and compare with existing syndiotactic propene polymer, plasticity is especially excellent.Wherein, have excellent formability be meant inject, inflation, blowing, extrude or situation that compacting etc. is shaped under, short from molten state to solidifying the required time.In addition, excellences such as the forming period property of such syndiotactic propene polymer (AA), shape stability, long-term production property.
Use as the described catalyst system in back, set as the described polymerizing condition in back, can make the syndiotactic propene polymer (AA) that fully satisfies above-mentioned (Eq-1).
Preferred implementation as above-mentioned syndiotactic propene polymer (AA); Can enumerate except above-mentioned preferred implementation (satisfy Δ H >=40mJ/mg and satisfy above-mentioned (Eq-1)), also satisfy the embodiment of following condition (dissolving in the amount of n-decane part) simultaneously.
The amount that dissolves in the n-decane part of syndiotactic propene polymer (AA) is preferably below 0.8 (wt%), more preferably below 0.6 (wt%) below 1 (wt%).This amount that dissolves in the n-decane part is and the closely-related index of blocking characteristics of syndiotactic propene polymer (AA) and molding therefrom that the amount that dissolves in the n-decane part usually just means that less low-crystalline becomes component few.That is the syndiotactic propene polymer (AA) that, also satisfies this condition (dissolve in n-decane part amount) possesses fabulous anti-blocking characteristics.
Therefore, (AA) one of most preferred embodiment of composition is to contain the formation unit that is derived from propylene that surpasses 90 moles of %, adopts 13The syndiotactic five unit composition ratio (rrrr divides rate) that C-NMR measures are more than 85%; And use fusing point (Tm) that DSC tries to achieve more than 145 ℃, melting heat (Δ H) is more than 40mJ/mg; And satisfy above-mentioned (Eq-1), and dissolve in the syndiotactic propene polymer of amount below 1wt% of n-decane part.
When making above-mentioned syndiotactic propene polymer (AA); Be fit to use above-mentioned catalyst for polymerization (cat-1) or this catalyzer (cat-1) to be supported on the granular carrier and the above-mentioned catalyst for polymerization (cat-2) that obtains; But as long as the polymkeric substance that generates satisfies the condition as syndiotactic propene polymer (AA); The catalyzer that when making syndiotactic propene polymer (AA), uses; This catalyzer had no qualification; Wherein, catalyzer (cat-1) contain the crosslinked metallocene compound (a-3) shown in the above-mentioned general formula [1-3] and be selected from above-mentioned Organoaluminoxy compound (b-1), with right above-claimed cpd (b-2) of above-mentioned crosslinked metallocene compound (a-3) reacting forming ion and the compound more than at least a kind (b) in the above-mentioned organo-aluminium compound (b-3).
In addition, the particular content of mentioned component (a-3), composition (b-1), composition (b-2) and composition (b-3) as stated.
Also capable of loading and carrying as required the going up in granular above-mentioned carrier (c) of mentioned component (a-3), composition (b-1), composition (b-2) and composition (b-3) used.
In addition, the catalyst for olefines polymerizing (3) that uses in the manufacturing of above-mentioned syndiotactic propene polymer (AA) except above-mentioned each the composition, as required, also can contain above-mentioned organic compound ingredient (d).
Wherein, the particular content of mentioned component (c) and composition (d) as stated.
The method of manufacture of syndiotactic propene polymer (AA)
During polymerization, method of use, the interpolation order of each composition can be selected arbitrarily, the method that is described below can be enumerated.
(1) adds composition (a-3) in the polymerizer method separately;
(2) add composition (a-3) and composition (b) in the polymerizer method with random order;
(3) composition (a-3) is supported at carrier (c) and goes up and obtain catalyst component, add this catalyst component and composition (b) in the polymerizer method with random order;
(4) composition (b) is supported at carrier (c) and goes up and obtain catalyst component, add this catalyst component and composition (a-3) in the polymerizer method with random order;
(5) catalyst component that composition (a-3) and composition (b) is supported on the carrier (c) adds the method in the polymerizer to.
In each method of above-mentioned (2)～(5), also can make the contact in advance more than at least two of each catalyst component.
In each method of above-mentioned (4) that are carried with composition (b), (5), also can add with random order as required and do not carried the composition of holding (b).In this case, composition (b) can be identical also can be different.
In addition; Be carried with the solid catalyst component that is carried with composition (a-3) and composition (b) on the solid catalyst component, composition (c) of composition (a-3) on the mentioned component (c); Can make olefinic polymerization earlier, also can on prepolymerized solid catalyst component, carry again and hold catalyst component.
Syndiotactic propene polymer (AA) can be in the presence of aforesaid catalyst for olefines polymerizing, makes at least a olefinic polymerization or the copolymerization in propylene and the terminal olefin (except propylene) that is selected from carbonatoms 2～20 and obtains.
Polymerization can be adopted any enforcement in liquid polymerizations such as solution polymerization, suspension polymerization or the gaseous polymerization.As the torpescence hydrocarbon medium that uses in the liquid polymerization, specifically can enumerate aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, 12 carbon alkane, kerosene; Clicyclic hydrocarbons such as pentamethylene, hexanaphthene, methylcyclopentane; Aromatic hydrocarbonss such as benzene,toluene,xylene; Halohydrocarbon such as ethylene chloride, chlorobenzene, methylene dichloride or their mixture etc. also can be with alkene itself as solvents.
When using aforesaid catalyst for olefines polymerizing to make propylene with at least a olefinic polymerization that is selected from the terminal olefin (except propylene) of carbonatoms 2～20, the consumption of composition (a-3) is: per 1 liter of reaction volume is generally 10 -9～10 -1The mole, be preferably 10 -8～10 -2Mole.
The consumption of composition (b-1) does, makes the mol ratio [(b-1)/M] of all transition metal atoms (M) in composition (b-1) and the composition (a-3) be generally 0.01～5000, be preferably 0.05～2000 amount.The consumption of composition (b-2) does, makes the mol ratio [(b-2)/M] of the transition metal atoms (M) in composition (b-2) and the composition (a-3) be generally 1～10, be preferably 1～5 amount.The consumption of composition (b-3) does, makes the mol ratio [(b-3)/M] of all transition metal (M) in aluminium atom and the composition (a-3) in the composition (b-3) be generally 10～5000, be preferably 20～2000 amount.
The consumption of composition (d) is under the situation of composition (b-1) at composition (b), makes mol ratio [(d)/(b-1)] be generally 0.01～10, is preferably 0.1～5 amount; At composition (b) is under the situation of composition (b-2), makes mol ratio [(d)/(b-2)] be generally 0.01～10, is preferably 0.1～5 amount; At composition (b) is under the situation of composition (b-3), makes mol ratio [(d)/(b-3)] be generally 0.01～2, is preferably 0.005～1 amount.
In addition, use the polymerization temperature of the alkene of above-mentioned catalyst for olefines polymerizing to be generally-50～+ 200 ℃, be preferably 0～170 ℃ scope.Polymerization pressure is generally normal pressure～10MPa gauge pressure, is preferably normal pressure～condition of 5MPa gauge pressure, and with this understanding, polyreaction can adopt any method in batch-type, semi continuous, the continous way to carry out.Also can polymerization be divided into reaction conditions carried out more than the two different stages.Whether the molecular weight of the olefin polymer of gained can be regulated through making to have hydrogen in the polymerization system or change polymerization temperature.In addition, also can regulate according to the amount of the composition (b) that uses.Under the situation of adding hydrogen, its appropriate addition is that every 1kg alkene is about 0.001～100NL.
The alkene that is used for polyreaction is propylene and more than one alkene of the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20.Terminal olefin as carbonatoms 4～20; Carbonatoms 4～20 be can enumerate, 4～10 the straight chain shape or the terminal olefin of branched are preferably; For example, 1-butylene, 2-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.
(B2) propylene-alpha-olefin copolymers
Propylene-alpha-olefin copolymers (B2) is that to contain the unitary amount of the formation that is derived from propylene be 55～90 moles of %; Containing the unitary amount of formation that is derived from least a alkene in the alpha-olefin copolymer (not comprising propylene) that is selected from carbonatoms 2～20 is the propylene-alpha-olefin copolymers of 10～45 moles of %; It is characterized in that; With JIS K-6721 is standard; 230 ℃, 2.16kg load down the MFR of mensuration be 0.01～100g/ minute scope, and satisfy following condition (b-1) or (b-2) in any more than:
(b-1): adopt 13The syndiotactic triad that the C-NMR method is measured divides rate (rr) more than 60%;
(b-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] is a standard (dL/g) with JISK-6721,230 ℃, 2.16kg load down the MFR (g/10 minute) of mensuration satisfy following relational expression:
1.50×MFR (-0.20)≤[η]≤2.65×MFR (-0.20)。
It is 55～95 moles of % that propylene-alpha-olefin copolymers (B2) contains the unitary amount of the formation that is derived from propylene, and the unitary amount of formation that is derived from the terminal olefin (not comprising propylene) of carbonatoms 2～20 is 10～45 moles of %.
Under the situation about in the present invention (4), using; With respect to (AA) and (B2) add up to 100 weight parts; Syndiotactic propene polymer (AA) is under the above situation of 50 weight parts; To contain the unitary amount of the formation that is derived from propylene be 55～90 moles of %, be preferably 55～85 moles of %, 60～85 moles of % more preferably, and the unitary amount of formation in the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20 of being derived from is 10～45 moles of %, be preferably 15～45 moles of %, 15～40 moles of % more preferably.
Under the situation that propylene-alpha-olefin copolymers (B2) uses in the present invention (4); With respect to (AA) and (B2) add up to 100 weight parts; Syndiotactic propene polymer (AA) is lower than under the situation of 50 weight parts, and to contain the unitary amount of the formation that is derived from propylene be 55～90 moles of %, be preferably 65～85 moles of %, 70～85 moles of % more preferably; And to contain at least a above amount in formation unit in the terminal olefin (not comprising propylene) that is derived from carbonatoms 2～20 be 10～45 moles of %, be preferably 15～35 moles of %, 15～30 moles of % more preferably.
Wherein, the formation unit that is derived from propylene and the formation of the terminal olefin (not comprising propylene) that is derived from carbonatoms 2～20 be unitary to add up to 100 moles of %.
In addition; As the terminal olefin (not comprising propylene) of carbonatoms 2～20, can enumerate ethene, 3-methyl-1-butene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.Be preferably ethene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene especially.
In addition, in the aforesaid propylene-alpha-olefin copolymers (B2), propylene-ethylene copolymers also is one of preferred implementation.
In addition; In the aforesaid propylene-alpha-olefin copolymers (B2); Comprise formation unit, formation unit that is derived from ethene that is derived from propylene and the formation unit that is derived from any (being also referred to as the HAO comonomer sometimes) of 1-butylene, 1-hexene, 4-methyl-1-pentene or 1-octene, the unitary ratio of formation (mole %) that is derived from ethene is one of preferred implementation more than the propylene-ethylene-HAO multipolymer from the unitary ratio of the formation of HAO comonomer (mole %).
And in the propylene-ethylene copolymers of the polymkeric substance of these preferable range, propylene-ethylene-HAO multipolymer, preferably above-mentioned (b-1) and (b-2) all be met.
It is standard that aforesaid propylene-alpha-olefin copolymer (B2) is preferably with JIS K-6721,230 ℃, 2.16kg load down the MFR of mensuration be 0.01～100g/10 minute scope, 0.02～100g/10 minute scope more preferably.
Aforesaid propylene-alpha-olefin copolymer (B2) preferably satisfy following (b-1) and (b-2) at least one.
(b-1): adopt 13The syndiotactic triad branch rate (rr divides rate, triad syndiotactic property) that the C-NMR method is measured is more than 60%;
(b-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] (dL/g) satisfies following relational expression with above-mentioned MFR (g/10 minute, 230 ℃, 2.16kg load):
1.50×MFR (-0.20)≤[η]≤2.65×MFR (-0.20)。
Declaration condition (b-1) at first
(b-1): the employing of propylene-alpha-olefin copolymers (B2) 13(rr divides rate to the syndiotactic triad branch rate that the C-NMR method is measured; Triad syndiotactic property) more than 60%, be preferably more than 70%, more preferably more than 75%; Rr divides the propylene-alpha-olefin copolymers (B2) of rate in this scope good with the consistency of syndiotactic propene polymer (AA), and is therefore preferred.
The polymkeric substance that satisfies (b-1) can obtain propylene and alpha-olefin copolymer in the presence of the catalyzer that for example can make syndiotactic polypropylenes, in addition, also can for example use like the described catalyzer manufacturing in back.
Rr divide rate by 13The absorption intensity of Prr (from the absorption intensity of the 2nd unitary methyl in 3 propylene units successive syndiotactic bonded positions) in the C-NMR spectrum and Pw (from the absorption intensity of all methyl of propylene units) is tried to achieve according to following formula (2).
Rr divides rate (%)=100 * Prr/Pw (2)
Wherein, From the absorption of mr (in the unit from 3 propylene units, at least be the syndiotactic absorption that combines to combine both with isotactic, be used for determining Pmr (absorption intensity)), from the absorption of rr (from the absorption of the 2nd unitary methyl at 3 propylene units successive syndiotactic bonded positions, be used for determining Prr (absorption intensity)) or from the absorption of mm (from the absorption of the 2nd unitary methyl at 3 propylene units successive isotactic bonded positions, be used to determine Pmm (absorption intensity)) and under from the synergetic situation of the absorption of comonomer, do not deduct the contribution of comonomer composition and directly calculate.
Particularly; According to [0018]～[0023] section said enforcement in the explanation of the acquiring method of [0018]～[0031] section described " syndiotactic parameter (SP value) " of TOHKEMY 2002-097325 communique; According to the integrated intensity of the signal in first area, second area, the 3rd zone, calculate by above-mentioned formula (2) and to try to achieve.
And in the present invention (4), rr especially 1Value; The value of particularly, trying to achieve according to the acquiring method of (0018)～(0031) section described " syndiotactic parameter (SP value) " of TOHKEMY 2002-097325 communique is preferably more than 60%, more preferably more than 65%, further be preferably more than 70%.Rr 1Value; In other words; In the calculating of above-mentioned rr value; From the absorption of mr (in from 3 propylene units, at least be the syndiotactic absorption that combines to combine both with isotactic, be used for determining Pmr (absorption intensity)), from the absorption of rr (from the absorption of the 2nd unitary methyl at 3 propylene units successive syndiotactic bonded positions, be used for determining Prr (absorption intensity)) or from the absorption of mm (from the absorption of the 2nd unitary methyl at 3 propylene units successive isotactic bonded positions, be used to determine Pmm (absorption intensity)) and under from the synergetic situation of the absorption of comonomer, deduct the value of the contribution of comonomer composition.
In the mensuration of rr value and rr1 value, the mensuration of NMR for example is described below and carries out.That is, with 0.35g sample heating for dissolving in the 2.0ml hexachlorobutadiene.After filtering this solution with glass filter (G2), add 0.5ml deuterate benzene, the NMR pipe of the internal diameter 10mm that packs into.Use the system GX-400 of NEC type NMR determinator then, under 120 ℃, carry out 13C-NMR measures.Cumulative frequency is more than 8,000 times.
Following declaration condition (b-2)
(b-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] of aforesaid propylene-alpha-olefin copolymer (B2) (dL/g) and according to JIS K-6721,230 ℃, 2.16kg load down the MFR (g/10 minute) of mensuration satisfy following relational expression.
1.50×MFR (-0.20)≤[η]≤2.65×MFR (-0.20)
More preferably satisfy
1.80×MFR (-0.20)≤[η]≤2.50×MFR (-0.19)。
The propylene-alpha-olefin copolymers (B2) that fully satisfies this relational expression is good with the consistency of syndiotactic propene polymer (AA), and is therefore preferred.
The propylene-alpha-olefin copolymers (B2) that satisfies above-mentioned formula can be through for example in the presence of the catalyzer that can make syndiotactic polypropylenes, makes propylene and alpha-olefin copolymer and obtains, and in addition, also can for example use like the described catalyzer manufacturing in back.The consistency of such material and syndiotactic propene polymer (AA) is good, and is therefore preferred.
Satisfy the propylene-alpha-olefin copolymers of (b-2) and compare with existing isotactic propylene series copolymer, [η] demonstrates bigger MFR when identical.
This is at Macromolecules 31; Also on the books among the 1335-1340 (1998); According to thinking, be different owing to molecular weight (pointing out in the paper) between the binding site of molecular weight between the polyacrylic binding site of isotactic (pointing out in the paper) and syndiotactic polypropylenes into Me=2170 (g/mol) for Me=6900 (g/mol).That is, under same [η],, increase, so MFR increases with respect to material binding site with isotactic structure owing to have the syndiotactic structure.
As stated; Satisfy that (B2) propylene-alpha-olefin copolymers more than any is the polymkeric substance that possesses stereospecific property different with the propylene-alpha-olefin copolymers with isotactic structure among (b-1) and (b-2), the polymkeric substance of thinking to have the syndiotactic structure.Therefore, think that propylene-alpha-olefin copolymers (B2) is and the good polymkeric substance of (AA) composition intermiscibility.
The limiting viscosity [η] that propylene-alpha-olefin copolymers (B2) is preferably measured in 135 ℃ of naphthane is 0.1～10dL/g, be preferably 0.5～10dL/g, 0.5～7.0dL/g more preferably.
The percent crystallinity that this propylene-alpha-olefin copolymers (B2) adopts X-ray diffraction to measure is preferably below 20%, more preferably 0～15%.
This propylene-alpha-olefin copolymers (B2) has single second-order transition temperature, and the second-order transition temperature (Tg) that preferably uses differential scanning calorimeter (DSC) to measure to obtain is usually below 0 ℃.The second-order transition temperature (Tg) of propylene-alpha-olefin copolymers (B2) is in above-mentioned scope the time, and winter hardiness, cold property are excellent.
The differential scanning calorimetry for example is described below and carries out.10.00mg left and right sides sample is filled in the special-purpose aluminium dish; The DSCRDC220 that uses Seiko Instruments to produce is according to being warmed up to 200 ℃ with 200 ℃/min by 30 ℃, after keeping 5 minutes under 200 ℃; Cool to-100 ℃ with 10 ℃/min from 200 ℃; Maintenance is after 5 minutes down at-100 ℃ again, and the endothermic curve when heating up with 10 ℃/min is then tried to achieve above-mentioned second-order transition temperature (Tg).
In addition, this propylene-alpha-olefin copolymers (B2) utilize the MWD that GPC measures (Mw/Mn, with polystyrene conversion, Mw: weight-average molecular weight, Mn: number-average molecular weight) be preferably below 3.5, more preferably below 3.0, further be preferably below 2.5.
Aforesaid propylene-alpha-olefin copolymer (B2) can be in the presence of catalyst for olefines polymerizing; Propylene is made with being selected from least a olefinic polymerization in the terminal olefin (not comprising propylene) of carbonatoms 2～20; Above-mentioned catalyst for olefines polymerizing contain the crosslinked metallocene compound (a-2) shown in the following general formula [1-2] and be selected from above-mentioned Organoaluminoxy compound (b-1), with right above-claimed cpd (b-2) of above-mentioned crosslinked metallocene compound (a-2) reacting forming ion and the compound more than at least a kind (b) in the above-mentioned organo-aluminium compound (b-3); But as long as satisfy the condition as propylene-alpha-olefin copolymers (B2), then method of manufacture also is not limited thereto.
Figure GSA00000105371100991
In above-mentioned formula [1-2], R 1, R 2, R 3, R 4, R 5, R 8, R 9And R 12For being selected from Wasserstoffatoms, alkyl, containing atom or base in silica-based, separately can be identical also can be different;
R 6And R 11For being selected from Wasserstoffatoms, alkyl and containing same atom or the same group in silica-based;
R 7And R 10For being selected from Wasserstoffatoms, alkyl and containing same atom or the same group in silica-based;
R 6, R 7, R 10And R 11All be not Wasserstoffatoms simultaneously;
R 2And R 3Can interosculate and form ring;
R 5～R 12In adjacent base can interosculate each other and form ring;
R 13And R 14Be the aryl that is selected from carbonatoms 6～18, the alkyl of carbonatoms 1～40, the alkylaryl of carbonatoms 6～40, the fluoro aryl of carbonatoms 6～20, the fluoroalkyl aryl of carbonatoms 7～40, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40; Separately can be identical also can be different
R 13And R 14In at least one is the aryl that is selected from carbonatoms 7～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40;
M is Ti, Zr or Hf;
Y is carbon or silicon;
Q is selected from neutrality, conjugation or non-conjugated diene below 10 of halogen, alkyl, carbonatoms, anion binding base and can be with the identical or different combination of lone-pair electron coordinate neutral dentate;
J is 1～4 integer.
Below, the concrete example of the crosslinked metallocene compound shown in the for example clear above-mentioned general formula [1-2], but be not thus limit especially the present invention (4) and after state the scope of the present invention (5).Wherein prestox octahydro dibenzo fluorenes is meant the structure shown in the formula [10], and prestox tetrahydrochysene Dicyclopentadiene (DCPD) and fluorenes are meant the structure shown in the formula [11], and the dibenzo fluorenes is meant the structure shown in the formula [12].
Figure GSA00000105371101001
As the concrete example of this crosslinked metallocene compound (a-2), can enumerate above-mentioned crosslinked metallocene compound (a-2a) mentioned in the explanation of the present invention (2).
In addition, to replace with metallocene compound that " difluoride ", " dibromide ", " diiodide " or " dichloride " replace with " dimethyl-" or " methylethyl " etc. be the compound shown in the general formula [1-2] to " zirconium " of above-mentioned illustrated compound compound or " dichloride " of replacing with " hafnium " or " titanium " too.
Above-mentioned crosslinked metallocene compound (a-2) can be with reference to the known method manufacturing.As known method of manufacture, can enumerate the method for manufacture that the applicant for example narrates in the WO04/029062 pph.
Aforesaid metallocene compound can use a kind of separately, also can two or more combinations use.
The Organoaluminoxy compound (b-1) that uses in making as propylene-alpha-olefin copolymers (B2) can use and the used identical compound of Organoaluminoxy compound (b-1) during above-mentioned syndiotactic propene polymer (AA) is made.
The compound (b-2) right with crosslinked metallocene compound (a-2) reacting forming ion that uses in making as propylene-alpha-olefin copolymers (B2) can use and used compound (b-2) the identical compound right with crosslinked metallocene compound (a-2) reacting forming ion during above-mentioned syndiotactic propene polymer (AA) is made.
The organo-aluminium compound (b-3) that uses in making as propylene-alpha-olefin copolymers (B2) can use and the used identical compound of organo-aluminium compound (b-3) during above-mentioned syndiotactic propene polymer (AA) is made.
Also capable of loading and carrying as required the going up in granular above-mentioned carrier (c) of mentioned component (a-3), composition (b-1), composition (b-2) and composition (b-3) used.
The method of manufacture of propylene-alpha-olefin copolymers (B2)
When propylene-alpha-olefin copolymers (B2) polymerization, can select method of use, the interpolation order of each composition arbitrarily, can enumerate the method that is described below.
Add composition (a-2) and composition (b) in the polymerizer method with random order.
In aforesaid method, also can make the contact in advance more than at least two of each catalyst component.
When using aforesaid catalyst for olefines polymerizing to carry out olefinic polymerization, the consumption of composition (a-2) is: per 1 liter of reaction volume is generally 10 -9～10 -1The mole, be preferably 10 -8～10 -2Mole.
The consumption of composition (b-1) does, makes the mol ratio [(b-1)/M] of all transition metal atoms (M) in composition (b-1) and the composition (a-2) be generally 0.01～5,000, be preferably 0.05～2,000 amount.The consumption of composition (b-2) does, makes the mol ratio [(b-2)/M] of aluminium atom and all transition metal atoms (M) in the composition (a-2) in the composition (b-2) be generally 1～1,000, be preferably 1～500 amount.The consumption of composition (b-3) does, makes the mol ratio [(b-3)/M] of the transition metal atoms (M) in composition (b-3) and the composition (a-2) be generally 1～10,000, be preferably 1～5,000 amount.
Propylene-alpha-olefin copolymers (B2) is in the presence of aforesaid catalyst for olefines polymerizing, under common liquid phase, makes at least a olefin-copolymerization in propylene and the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20.At this moment, generally use hydrocarbon solvent, also can be with terminal olefin as solvent.As hydrocarbon solvent, specifically can enumerate and above-mentioned same hydrocarbon solvent.Copolymerization can adopt any method in batch process or the continuous processing to carry out.
As can be used for the polymeric terminal olefin, can enumerate for example ethene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.Terminal olefin can use a kind of separately, also can two or more combinations use.
Use catalyst for olefines polymerizing, adopt batch process to implement under the situation of copolymerization, the concentration of the metallocene compound in the polymerization system is: per 1 liter polymerization volume is generally 0.00005～1 mmole, is preferably the amount of 0.0001～0.50 mmole.
In addition, the reaction times (average retention time under the situation of copolymerization employing continuous processing enforcement) is different because of conditions such as catalyst concn, polymerization temperatures, is generally 5 minutes～3 hours, is preferably 10 minutes～1.5 hours.
Aforesaid propylene is supplied with polymerization system with the amount of the propylene-alpha-olefin copolymers (B2) that can obtain aforesaid specific composition respectively with at least a alkene that is selected from the terminal olefin (not comprising propylene) of carbonatoms 2～20.In addition, when copolymerization, can use hydrogen equimolecular quantity regulator.
With propylene during with at least a olefin-copolymerization that is selected from the terminal olefin (not comprising propylene) of carbonatoms 2～20, what propylene-alpha-olefin copolymers (B2) obtained usually is the polymeric solution that contains it as stated.This polymeric solution is handled with ordinary method, obtains propylene-alpha-olefin copolymers (B2).
Copolyreaction is 40～200 ℃ in temperature usually, be preferably in 40 ℃～180 ℃, more preferably 50 ℃～150 ℃ the scope, pressure for greater than 0 smaller or equal to 10Mpa, be preferably 0.5～10Mpa, more preferably carry out under the condition in the scope of 0.5～7Mpa.
Propylene polymer composition (X1)
The present invention's (4) propylene polymer composition (X1) contains:
(AA) above-mentioned syndiotactic propene polymer 10～95 weight parts, be preferably 15～90 weight parts and
(B2) aforesaid propylene-alpha-olefin copolymer 90～5 weight parts, be preferably 85～10 weight parts (wherein, with (AA) and (B2) add up to 100 weight parts).
In the time of in this scope, can obtain plasticity and excellent heat resistance, the transparency, flexibility, anti-impaired property be the propylene polymer composition of excellence also, and be therefore preferred.
In addition; Under the situation that needs the material that thermotolerance is high, rigidity is high, shock resistance is excellent; Be preferably syndiotactic propene polymer (AA) more than 50 weight parts, below 95 weight parts; More preferably 55 weight parts above, below 90 weight parts, propylene-alpha-olefin copolymers (B2) be preferably 5 weight parts above, below 50 weight parts, more preferably 10 weight parts above, below 45 weight parts (compsn (X1i)).
In addition; Under the situation that needs the excellent material of flexibility and caoutchouc elasticity, be preferably syndiotactic propene polymer (AA) more than 10 weight parts, be lower than 50 weight parts, more preferably 10 weight parts above, below 49 weight parts; Further be preferably 15～45 weight parts; Propylene-alpha-olefin copolymers (B2) be preferably be higher than 50 weight parts, below 90 weight parts, more preferably 51 weight parts above, below 90 weight parts, further be preferably 55～85 weight parts (compsn (X1ii)).
The plasticity of the present invention's (4) compsn and thermotolerance are especially excellent, and also excellence of the transparency, flexibility, anti-impaired property.
Wherein, have excellent formability be meant implement injection, inflation, blowing, extrude or situation that compacting etc. is shaped under, from molten state to solidifying the required time.Under the good situation of plasticity, excellences such as forming period property, shape stability, long-term production property.
Particularly, the time till extremely solidifying, the hypocrystalline time (t during 110 ℃ the isothermal crystal that uses differential scanning calorimeter (DSC) to try to achieve is measured 1/2) be preferably below the 1000sec, more preferably below the 500sec.Wherein, the hypocrystalline time (t during 110 ℃ the isothermal crystal that uses differential scanning calorimeter (DSC) to try to achieve is measured 1/2) be meant rerum natura (1).The present invention's (4) compsn is because of containing specific (AA) (B2) composition, compared with prior art, and t 1/2Tremendous raising is arranged, for example, can adopt with common used same moulding methodes such as isotactic Vestolen PP 7052 and have no to be shaped difficultly.
Utilize isothermal crystal to measure the hypocrystalline time (t that tries to achieve 1/2) be being under the situation of total heat with DSC heat curve in the isothermal crystal process and the area between the baseline, reach the time of 50% heat.Specifically can be with reference to new polymer experiment lecture 8 high molecular rerum naturas professional books such as (the upright altogether Co., Ltd. that publishes).Hypocrystalline time (t 1/2) mensuration be described below and carry out.5.00mg left and right sides sample is filled in the special-purpose aluminium dish; The DSCPyris1 or the DSC7 that use PerkinElmer company to produce; According to being warmed up to 200 ℃ by 30 ℃ with 320 ℃/min; After keeping 5 minutes under 200 ℃, cool to 110 ℃ of isothermal crystal temperature with 320 ℃/min by 200 ℃, temperature remains on the DSC curve that obtains under 110 ℃ and obtains.Wherein, hypocrystalline time (t 1/2) 110 ℃ of isothermal crystal process time openings (by 200 ℃ of moment that reach 110 ℃) are made as under the condition of t=0 and try to achieve.The present invention's (4) compsn can be tried to achieve t as stated 1/2, under 110 ℃ of non crystallized situation, through under the isothermal crystal temperature below 110 ℃, get a plurality of points and measure easily, ask for hypocrystalline time (t by its extrapolated value 1/2).
And, the pin of measuring to aforesaid propylene based polymer composition (X1) go into temperature (hereinafter is also referred to as rerum natura (2)) be preferably more than 145 ℃, more preferably 147 ℃, be preferably more than 150 ℃ especially.
Pin is gone into temperature (also be called as according to TMA and measure the softening temperature of trying to achieve) and can be described below and measure.
Use the SS-120 of Jinggong Co., Ltd's production or the Q-400 that TA Instrument company produces, the compacting sheet material test film of used thickness 1mm with the heat-up rate of 5 ℃/min, applies 2Kgf/cm on the pressure head of the plane of Φ 1.8mm 2Pressure, by the TMA curve try to achieve pin go into temperature (℃).
In addition, the measuring method of Izod shock strength (also being called as rerum natura (3)), modulus in tension (also being called as rerum natura (4)), turbidity (also being called as rerum natura (5)) is as follows.
The Izod shock strength is the test film that is struck out 12.7mm (wide) * 3.2mm (thick) * 64mm (length) by the thick compacting sheet material of 3mm, introduces the breach (notch) of mechanical workout, measure down at 0 ℃, and be the Izod impact value with three times MVs.
Modulus in tension is by the thick compacting sheet material of 1mm, according to JIS K6301, uses the JIS3 dumb-bell test piece with O dumbbell punching press, is used to estimate sample.When measuring, for example, use Instron corporate system tensile testing machine Inston 1123, under distance between bench marks: 30mm, draw speed 30mm/min, measure down at 23 ℃, with three times MVs as modulus in tension.
The compacting test film of used thickness 1mm is measured inner turbidity with the digital turbidometer " NDH-20D " that Japanese electric look Industrial Co., Ltd produces, and is turbidity value with twice MV.
In addition, in above-mentioned explanation, in each test, use pressing make-up machine at 200 ℃ down behind 5 minutes～10 minutes waste heats; Add at 10MPa and to depress, after being shaped with 1～2 minute, under 20 ℃; Depress cooling in adding of 10MPa, make the sheet material of specific thickness thus, obtain test film.
Under the situation of compsn (X1i), the terminal olefin (not comprising propylene) as the carbonatoms 2～20 of propylene-alpha-olefin copolymers (B2) is preferably ethene, or the combination of ethene and HAO comonomer, is preferably ethene especially.And the formation unit that more preferably is derived from terminal olefin is preferably 15 moles of %～45 mole %, is preferably 15～40 moles of % especially.In the time of in this scope, can form the especially excellent compsn of balance of thermotolerance, the transparency and shock resistance.
Under the situation of compsn (X1i), the hypocrystalline time (1) is preferably below the 1000sec, more preferably below 500sec;
Pin go into temperature (2) be preferably more than 145 ℃, more preferably more than 147 ℃;
Izod shock strength (3) is preferably above, the 100J/m more preferably of 50J/m;
Modulus in tension (4) preferably in the scope of 100MPa～2000MPa, more preferably in the scope of 200MPa～1500MPa, further is preferably the scope of 400MPa～1000MPa;
Inner turbidity (5) is preferably below 50%, more preferably below 40%.
Under the situation of compsn (X1i), be preferably (1)～at least more than one rerum natura in (5) satisfies preferable range, and more preferably preferable range is satisfied in (1) or (2); More preferably satisfy (1), (3), (4) simultaneously; Or satisfy (2), (3), (4) simultaneously, or satisfy any situation of (3), (4), (5) simultaneously, further be preferably and satisfy (1), (3), (4), (5) simultaneously; Or satisfy (2), (3), (4), (5) simultaneously, be preferably (1), (2), (3), (4), (5) especially and all satisfy.
And under the situation of compsn (X1ii); Be preferably syndiotactic propene polymer (AA) more than 10 weight parts, be lower than 50 weight parts; More preferably 10 weight parts above, below 49 weight parts, further be preferably 15 weight parts above, below 45 weight parts, propylene-alpha-olefin copolymers (B2) be preferably be higher than 50 weight %, below 90 weight parts; More preferably 51～90 weight parts further are preferably 55～85 weight parts.
In the case, the terminal olefin (not comprising propylene) as the carbonatoms 2～20 of propylene-alpha-olefin copolymers (B2) is preferably ethene, or the combination of ethene and HAO comonomer, is preferably ethene especially.And the formation unit that more preferably is derived from terminal olefin is preferably 10 moles of %～45 mole %, further is preferably 15～35 moles of %, and is preferably 15～30 moles of % especially.In the time of in this scope, can form especially thermotolerance, the transparency, flexibility and the excellent compsn of anti-impaired property.
Under the situation of compsn (X1ii), the hypocrystalline time (1) is preferably below the 1000sec, more preferably below 500sec;
Pin go into temperature (2) be preferably more than 145 ℃, more preferably more than 147 ℃;
Izod shock strength (3) is preferably above, the 200J/m more preferably of 100J/m;
Modulus in tension (4) preferably in the scope of 1MPa～400MPa, more preferably in the scope of 1MPa～200MPa, further is preferably the scope of 1MPa～100MPa;
Inner turbidity (5) is preferably below 30, more preferably below 25.
Under the situation of compsn (X1ii), at least more than one the rerum natura that is preferably in (1), (2), (4), (5) satisfies preferable range, and more preferably preferable range is satisfied in (1) or (2); More preferably satisfy simultaneously (1) and (4); Or (2) and (4) satisfy simultaneously, or (4) and (5) any situation in satisfying simultaneously, further is preferably satisfied simultaneously (1), (4), (5); Or satisfy (2), (4), (5) simultaneously, be preferably (1), (2), (4), (5) especially and all satisfy.
In addition, under the situation of compsn (X1ii), the residual strain after 200% stretching is preferably below 50 (%), more preferably below 40 (%).The glossiness velocity of variation of learning vibration damage test front and back is preferably below 40 (%), more preferably below 30 (%).As long as in this scope, can form especially thermotolerance, the transparency, flexibility, anti-impaired property and the excellent compsn of caoutchouc elasticity.
The present invention's (4) propylene polymer composition (Y) contains 99.7～70 moles of % in formation unit that are derived from propylene; With 0.3～30 mole of % in formation unit of the terminal olefin that is derived from carbonatoms 2～20 (not comprising propylene) (wherein, the formation unit with the terminal olefin (comprising propylene) that is derived from carbonatoms 2～20 is 100 moles of %);
(2) pin go into temperature above at 145 degree, be preferably 147 spend more than;
(3) the Izod shock strength more than 50J/m, be preferably 100J/m;
(4) modulus in tension be 100MPa～2000MPa scope, be preferably the scope of 200MPa～1500MPa;
(5) inner turbidity value below 50%, be preferably below 40%.
" compsn " in this propylene polymer composition (Y) is meant; At least there are part that dissolves in 23 ℃ of decane and the part that is insoluble to 23 ℃ of decane; The part that dissolves in 23 ℃ of decane exists more than 2 weight parts, below 98 weight parts, is insoluble to 23 ℃ of decane and partly exists more than 2 weight parts, below 98 weight parts.
Wherein, under the situation of compsn (Y), dissolve in decane part scope, preferably in the scope of 5～50 weight parts at 5～55 weight parts.In addition, the syndiotactic five unit composition ratio (rrrr branch rate) of part that are insoluble to decane are more than 85%, and the fusing point (Tm) of being tried to achieve by DSC is more than 145 ℃.
The mensuration that dissolves in n-decane amount partly is through adding about 3g said composition in the 450ml n-decane to; After dissolving under 145 ℃; Cool to room temperature utilizes to remove by filter the part that is insoluble to n-decane, and recovery dissolves in the part of n-decane and carries out from filtrating.
The formation unit that is derived from propylene is 99.7～75 moles of %, formation unit 0.3～25 mole of % more preferably of being derived from terminal olefin more preferably.
As terminal olefin, more preferably contain ethene at least, further preferably be merely ethene.
Said composition can be through will be for example in the aforesaid propylene based polymer composition (X1), and the composition that can form compsn (X1i) and so on is mixed with each other and makes.
And the present invention's (4) another kind of propylene polymer composition (Z) is for containing 95～55 moles of % in formation unit of being derived from propylene, being preferably 95～60 moles of %; With 5～45 moles of % in formation unit of the terminal olefin that is derived from carbonatoms 2～20 (not comprising propylene), be preferably 5～40 moles of % (wherein; Formation unit with the terminal olefin (comprising propylene) that is derived from carbonatoms 2～20 is 100 moles of %)
(2) pin go into temperature above at 145 degree, be preferably 147 spend more than;
(3) modulus in tension is 1～400MPa, is preferably 1～200MPa;
(5) inner turbidity value below 40%, be preferably below 30%.
" compsn " in this propylene polymer composition (Z) is meant; At least there are part that dissolves in 23 ℃ of decane and the part that is insoluble to 23 ℃ of decane; The part that dissolves in 23 ℃ of decane exists more than 2 weight parts, below 98 weight parts, and the part that is insoluble to 23 ℃ of decane exists more than 2 weight parts, below 98 weight parts.
Wherein, under the situation of compsn (Z), dissolve in the scope of the part of decane, preferably in the scope of 50～90 weight parts at 50～95 weight parts.In addition, the syndiotactic five unit composition ratio (rrrr branch rate) of part that are insoluble to decane are more than 85%, and the fusing point (Tm) of being tried to achieve by DSC is more than 145 ℃.
Said composition can be passed through for example with in the aforesaid propylene based polymer composition (X1), and the composition that can form compsn (X1ii) and so on is mixed with each other and makes.
Graft modification
The present invention's (4) propylene polymer composition (X1), propylene polymer composition (Y), propylene polymer composition (Z) and wherein any, polar monomer all capable of using is at least a portion in the aforesaid acrylic polymer or all carry out graft modification.
Under the situation of aforesaid propylene based polymer composition (X1); For example both can be (AA) composition a part or all by graft modification; Also can be the part of (B2) composition or all by graft modification, can also be respectively to (AA) composition, (B2) composition separately a part or all carry out graft modification.
As this polar monomer, can enumerate the ethene property unsaturated compound that contains hydroxyl, the ethene property unsaturated compound that contains amino, the ethene property unsaturated compound that contains epoxy group(ing), aromatic ethenyl compound, unsaturated carboxylic acid or derivatives thereof, vinyl ester compound, vinylchlorid, carbodiimide compound etc.
As polar monomer, be preferably the unsaturated carboxylic acid or derivatives thereof especially especially.As the unsaturated carboxylic acid or derivatives thereof, can enumerate ester that the unsaturated compound with 1 above carboxylic acid group, the compound with carboxylic acid group and alkyl alcohol form, have 1 above acid anhydride's unsaturated compound etc.; As unsaturated group, can enumerate vinyl, vinylidene, unsaturated cyclic hydrocarbon radical etc.
As concrete compound; For example can enumerate vinylformic acid, toxilic acid, fumaric acid, tetrahydrophthalic acid, methylene-succinic acid, citraconic acid, butenoic acid, methylacrylic acid, Nadic acid (trade mark) unsaturated carboxylic acids such as (internally-oriented cis-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylicacid); Or derivatives thereof, for example acid halide (acid halide), acid amides, imide, acid anhydride, ester etc.As the concrete example of these verivates, can enumerate for example Malaysia acyl chlorides, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, toxilic acid glycidyl ester etc.
These unsaturated carboxylic acids and/or its verivate can use a kind of separately, also can two or more combinations use.Wherein, be fit to use unsaturated dicarboxylic acid or its acid anhydrides, especially preferably use toxilic acid, Nadic acid (trade mark) or their acid anhydrides.
Modification obtains through making be modified body and polar monomer graft polymerization.When be modified body and aforesaid polar monomer carried out graft polymerization, with respect to the 100 weight parts body that is modified, polar monomer used 1～100 weight part usually, preferably uses 5～80 weight parts.This graft polymerization is carried out in the presence of radical initiator usually.
As radical initiator, can use organo-peroxide or azo cpd etc.
Radical initiator can directly mix the back be modified body and polar monomer to be used, and also may be dissolved in a spot of organic solvent and uses afterwards.As this organic solvent,, remove this not special qualification so long as the organic solvent of solubilized radical initiator can use.
In addition, when being modified body and polar monomer graft polymerization, also can use reducing substances.When using reducing substances, can improve the grafting amount of polar monomer.
The body that is modified utilizes the graft modification of polar monomer to implement according to existing known method; For example; Can be dissolved in the organic solvent through the body that will be modified, then, polar monomer and radical initiator etc. added in the solution; 70～200 ℃, be preferably under 80～190 ℃ the temperature, react 0.5～15 hour, be preferably 1～10 hour and carry out.
And, also can use forcing machine etc., make be modified body and polar monomer reaction, make the modified propylene based polymer composition.This reaction is preferably usually more than the fusing point of body that is modified, particularly, (B2) composition is being carried out under the situation of modification, for example 120～300 ℃, be preferably under 120 ℃～250 ℃ the temperature, implemented usually 0.5～10 minute.And the body that is modified that contains (AA) composition is being carried out under the situation of modification, for example 160～300 ℃, be preferably under 180 ℃～250 ℃ the temperature, implemented usually 0.5～10 minute.
Be under the situation of 100 weight % with the modification body, the modification amount of the modification body that obtains like this (the grafting amount of polar monomer) is generally 0.1～50 weight %, is preferably 0.2～30 weight %, 0.2～10 weight % more preferably.
In the present invention (4); Use these modification bodies; And as required; Be selected from (AA) composition and more than one unmodified bodies in (B2) composition and carry out mixingly, at least a portion that can obtain the present invention (4) connects by the propylene polymer composition of branch modification (X1), propylene polymer composition (Y), propylene polymer composition (Z).
For example; Can be with the pellet modification of the propylene polymer composition (W) or the propylene polymer composition (W) of the present invention (4); The unmodified polymer of this modification body and other necessary amount (be selected from (AA) composition, (B2) composition more than one) fusion is mixed, make acrylic polymer (X1), (Y) or (Z).
And; Under the situation of any at propylene polymer composition (X1), (Y) and (Z); At least a portion that is obtained by aforesaid method with respect to 100 weight % is by the propylene polymer composition of polar monomer graft modification, the content of polar monomer is generally 0.001～50 weight %, is preferably 0.001～10 weight %, more preferably 0.001～5 weight %, further be preferably 0.01～3 weight %.The control of polar monomer content can easily be carried out through for example suitably selecting the grafting condition.
Under the situation of at least a portion by the polar monomer graft modification of the present invention's (4) propylene polymer composition, excellent with binding property, the intermiscibility of other resin, and can improve the wellability on the molding surface that obtains by propylene polymer composition sometimes.
In addition; At least a portion through making compsn forms the graft modification monomer; Not only have performances such as the transparency that the present invention's (4) propylene polymer composition has, low-temperature impact resistance, mechanical properties (rigidity or flexibility), thermotolerance, and can also increase intermiscibility or binding property with other material sometimes.
In addition; Through making polar monomer; For example the content of unsaturated carboxylic acid and/or its verivate makes the present invention's (4) propylene system: compositions demonstrate high bond strength with respect to the resin that contains polar group (for example polyester, Z 150PH, ethylene-vinyl alcohol copolymer, polymeric amide, PMMA, polycarbonate etc.) in above-mentioned scope.
In addition, at least a portion of the present invention (4) by the propylene polymer composition of graft modification in the scope of the characteristic that this modifier had, can with other polymkeric substance, for example cooperation such as thermoplastic resin, elastomerics.These cooperation both can mix in the graft modification stage, also can after modification, mix.
As long as the present invention's (4) propylene polymer composition is in the scope of the object of the invention; As required, also can cooperate additives such as weather-proof stablizer, heat-resisting stabilizing agent, static inhibitor, slipproofing agent, antiblocking agent, antifogging agent, nucleator, lubricant, pigment, dyestuff, softening agent, inhibitor, hydrochloric acid absorbent, inhibitor.
The present invention's (4) propylene polymer composition also can contain other polymkeric substance such as elastomerics, resin in the scope of the present invention's (4) purpose.
In addition, being the plasticity of the prolylene polymer composition that further improves the present invention (4), that is, is to improve Tc, accelerate crystallization velocity, can also contain the nucleator of specific any composition.In the case; Nucleator can be that for example biphenyl fork Sorbitol Powder is that nucleator, phosphate ester salt are that nucleator, rosin series nucleator, TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. metal-salt are nucleator, fluorinated polyethylene, 2; 2-methylene-bis (4, the 6-di-tert-butyl-phenyl) sodium phosphate, pimelic acid and salt, 2 thereof, 6-naphthoic acid dicarboxylicacid two Cyclohexamides etc.; The not special restriction of use level is about 0.1～1 weight part but be preferably with respect to propylene polymer composition.Not special restriction on cooperation opportunity can be between polymerization period, after the polymerization or be shaped to add and add man-hour.
The method of manufacture of propylene polymer composition (X1)
Aforesaid propylene polymer composition can be through adopting various known method with each composition in aforesaid scope; For example can adopt continous way or the multistage polymeric method of batch-type of utilizing slurry phase, solution phase or gas phase; Use method of mixing such as Henschel mixing roll, V-type mixing roll, ribbon blender (ribbon blender), drum tumbler; Or after mixing; Behind melting mixings such as single screw extrusion machine, twin screw extruder, kneader, Banbury, carry out the method manufacturing of granulation or pulverizing.
The present invention's (4) pellet is made up of propylene polymer composition (W), and this propylene polymer composition (W) contains:
Syndiotactic propene polymer (AA1) 1～65 weight part,
Propylene-alpha-olefin copolymers (B21) 99～35 weight parts (wherein, with (AA1) and (B21) add up to 100 weight parts),
And this polymkeric substance (AA1) fully satisfies following condition (a1), and this multipolymer (B21) fully satisfies following condition (b1),
(a1): the syndiotactic five unit composition ratio (rrrr divides rate) that adopt 13C-NMR mensuration are more than 85%; And utilize fusing point (Tm) that DSC tries to achieve more than 145 ℃; Contain the unitary amount of the formation that is derived from propylene and surpass 90 moles of % (wherein; With the unitary total amount of formation in this polymkeric substance (AA1) is 100 moles of %)
(b1): the unitary content of formation that is derived from propylene be 55～90 moles of % (wherein; With the unitary total amount of formation in this polymkeric substance (B21) is 100 moles of %); The unitary content of formation that is derived from least a alkene in the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20 is 10～45 moles of %; With JIS K-6721 is standard; 230 ℃, 2.16kg load down the MFR of mensuration be 0.01～100g/10 minute scope, and satisfy following condition (b1-1) or (b1-2) in any more than;
(b1-1): the syndiotactic triad branch rate (rr divides rate) that adopts 13C-NMR mensuration is more than 60%;
(b1-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] (dL/g) satisfies following relational expression with above-mentioned MFR (g/10 minute, 230 ℃, 2.16kg load):
1.50×MFR(-0.20)≤[η]≤2.65×MFR(-0.20)。
As used (AA1) syndiotactic propene polymer of the present invention's (4) pellet, can enumerate the acrylic polymer identical material used with aforesaid propylene based polymer composition (X1).Its combining form, to be derived from the syndiotactic propene polymer (AA) that preferred implementation that the unitary kind of the formation that is derived from terminal olefin, amount, rule five a unit composition ratio, Tm, Δ H, [η] beyond the formation unit of propylene wait, method of manufacture etc. are also complete and aforesaid propylene based polymer composition (X1) is used identical.
Used (B21) propylene-alpha-olefin copolymers of the present invention's (4) pellet can be enumerated propylene-alpha-olefin copolymers (B2) the identical material used with aforesaid propylene based polymer composition (X1).
In the present invention (4), the preferred implementation of the unitary kind of the formation of multipolymer, ratio, rr value, rr1 value, [η], percent crystallinity, Tg, Mw/Mn etc., method of manufacture etc. are also fully identical with the used propylene-alpha-olefin copolymers (B2) of aforesaid propylene based polymer composition (X1).
The present invention's (4) pellet is 1～65 weight part, is preferably 1～40 weight part by (AA1) composition; (B21) composition be 99～35 weight parts, be preferably 99～60 weight parts (wherein, with (AA1) and (B21) add up to 100 weight parts) propylene polymer composition (W) constitute.
As the pellet shape of propylene polymer composition (W), can enumerate examples such as spherical, cylindric, lensing, cubic.These pellets can be according to known prilling process manufacturing, for example, with (AA1) composition and (B21) the even melting mixing of composition, after extruding with forcing machine, through hot machining or wire cutting (strand cut), can obtain spherical, cylindric, lentiform pellet.In the case, cutting can be in water, implement under the arbitrary environment in the air-flow such as air.And when using under the situation with the forcing machine that can make the device that strand skin of material and internal layer be made up of different polymer; Being made into outer through cutting is the double-deck strand of material of (B21) composition for (AA1) composition, internal layer; Can further control mutual binding property, better effects if.The pellet of cubic can be through for example behind uniform mixing, is configured as sheet with roller etc., uses the sheet material dicing machine to obtain.The longest length partly that its specification is preferably pellet is below the 3cm.Under the situation of the pellet that surpasses this specification, cause error at measurment to increase sometimes.
The pellet of propylene polymer composition (W) can be on the surface of this pellet, pounce on add in lime carbonate, permanent white, silica, talcum, Triple Pressed Stearic Acid and the polyolefin powder any or two or more.Can further control in this case bonded to each other, or bridge formation (bridge) phenomenon of pellet when suppressing from barrel etc., to take out, therefore preferably.The face powder amount is corresponding with size, the shape of pellet, adds necessary amount and gets final product, and usually with respect to the resin combination pellet, adds 0.05～3 weight part.
In the scope of the present invention's (4) goal of the invention; As required, also can cooperate additives such as weathering resistance stablizer, heat-resisting stabilizing agent, static inhibitor, slipproofing agent, antiblocking agent, antifogging agent, nucleator, lubricant, pigment, dyestuff, softening agent, inhibitor, hydrochloric acid absorbent, inhibitor.In the propylene polymer composition of the present invention (4), in the scope of the present invention's (4) purpose, can also contain other polymkeric substance (except (AA1) acrylic polymer with (B21) the propylene-alpha-olefin copolymers).
As the preferred method that obtains propylene polymer composition (W) pellet; Can enumerate more than the climax temperature (Tm) in the differential scanning calorimeter (DSC) of (AA1) composition; And under the temperature below 280 ℃ for example, with (AA1) composition and (B21) the mixing method of composition.
The pellet of the present invention's (4) propylene polymer composition (W) can be used as thermoplastic polymer with properties-correcting agent, preferably can use properties-correcting agent as the polyolefin polymkeric substance.
As the polymkeric substance of modification, not special restriction is preferably the polyolefin polymkeric substance.As polyolefin-based resins, can enumerate for example high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), LLDPE (straight chain shape new LDPE (film grade)), polypropylene-based polymkeric substance, poly(4-methyl-1-pentene) etc.Be preferably polypropylene-based resin.Polypropylene-based polymkeric substance under this situation is the crystalline polypropylene based polymer, is the random or segmented copolymer of alfon or propylene and a spot of terminal olefin and/or ethene.
The Tm that is measured by DSC of the polypropylene-based polymkeric substance under this situation is preferably more than 120 ℃, below 170 ℃.And polypropylene-based polymkeric substance can be enumerated and the identical material of above-mentioned (AA) composition.Its combining form, the preferred implementation that is derived from the unitary kind of the formation that is derived from terminal olefin beyond the formation unit of propylene, amount, rule five a unit composition ratio, Tm, Δ H etc., method of manufacture etc. are also identical with the used acrylic polymer (AA) of aforesaid propylene based polymer composition (X1) fully.
Contained (AA1) composition and the polymkeric substance of modification can be the materials with same nature in the present invention's (4) the pellet.
For obtaining the polymer compsn of modification, can be with the polymkeric substance that needs modification, polyolefin polymkeric substance for example is with the present invention's (4) polyolefin properties-correcting agent and mixing according to propylene polymer composition (X1) described additive as required.As compounding process, be preferably pellet and the mixing method of polymer melt that needs modification with the present invention (4).The use level of properties-correcting agent is 3～95 weight %, be preferably 10～80 weight %, 30～70 weight % more preferably.This use level is in above-mentioned scope the time, and it is abundant then can to obtain modified effect, mobile might as well, shaping processability, intensity are also excellent, the polymer compsn of the modification of excellent heat resistance.
Because the resistance to blocking of the present invention's (4) pellet is excellent, therefore can carry out modification to other polymkeric substance with high productivity.Moreover, owing to can obtain the polymer compsn of the transparency, low-temperature impact resistance, mechanical properties (flexibility or rigidity etc.) excellence and excellent heat resistance, therefore useful with properties-correcting agent as polymkeric substance.Modified effect to used (AA) acrylic polymer of aforesaid propylene based polymer composition (X1) is big especially.
Therefore; Compsn (X1) through with the present invention (4) carries out melting mixing with the present invention's (4) pellet (thermoplastic polymer is with material modified), (AA) composition and other polymkeric substance as required (except (AA) acrylic polymer with (B2) the propylene-alpha-olefin copolymers), the additive of necessary amount, also can obtain.
<Propylene polymer composition (X2)>
Below, the present invention (5) of one of preferred implementation of the compsn that contains syndiotactic propene polymer (AA) is elaborated.
The present invention's (5) propylene polymer composition (X2) contains above-mentioned specific (AA) syndiotactic propene polymer, specific (B2) propylene-alpha-olefin copolymers, (C0) ethene-alpha-olefin copolymer.
Above-mentioned syndiotactic propene polymer (AA) and propylene-alpha-olefin copolymers (B2) specify as stated.
Ethene-alpha-olefin random copolymers (C0)
As the used ethene-alpha-olefin random copolymers (C0) of the present invention (5); Be preferably and contain the formation unit 50～99mol% that is derived from ethene, contain the ethene-alpha-olefin copolymer of 1～50 mole of % in formation unit (with the 100 moles of % that add up to of ethene and terminal olefin) of the terminal olefin that is derived from the carbonatoms 3～20 beyond the ethene.
The formation unit that is derived from ethene that preferably contains 60～95mol% contains the formation unit (with the 100 moles of % that add up to of ethene and terminal olefin) of the terminal olefin that is derived from the carbonatoms 3～20 beyond the ethene of 5～40 moles of %, and density is 910～850kg/m 3, according to JIS K-6721, the MFR that under 190 ℃, the load of 2.16kg, measures is in 0.01～100g/10 minute scope.
The formation unit that is derived from ethene that more preferably contains 80～95mol% contains the formation unit (with the 100 moles of % that add up to of ethene and terminal olefin) of the terminal olefin that is derived from the carbonatoms 3～20 beyond the ethene of 5～20 moles of %, and density is 900～860kg/m 3, according to JIS K-6721, the MFR that under 190 ℃, the load of 2.16kg, measures is in 0.05～50g/10 minute scope.
With the terminal olefin of ethylene copolymer be the terminal olefin of carbonatoms 3～20, specifically can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene, cetene, 1-vaccenic acid, 1-19 carbenes, 1-eicosylene, 4-methyl-1-pentene etc.Wherein, be preferably the terminal olefin of carbonatoms 3～10.Be preferably propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene especially.These terminal olefins can use separately, also can two or more combinations use.
In addition, ethene-alpha-olefin random copolymers (C0) in the scope of the object of the invention, also can contain the unit that is derived from other polymerizable monomer except said units.
As these other polymerizable monomer, can enumerate for example vinyl compound classes such as vinylbenzene, vinyl cyclopentenes, vinyl cyclohexane, vinyl norbornene alkane; Vinyl esters such as vinyl-acetic ester; Unsaturated organic acid or derivatives thereofs such as maleic anhydride; Divinyl, isoprene, pentadiene, 2,3-dimethylbutadiene equiconjugate dienes; 1; 4-hexadiene, 1; 6-octadiene, 2-methyl isophthalic acid; 5-hexadiene, 6-methyl isophthalic acid, 5-heptadiene, 7-methyl isophthalic acid, 6-octadiene, Dicyclopentadiene (DCPD), cyclohexadiene, two cyclooctadiene, methene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornylene, 6-chloromethyl-5-isopropenyl-2-nirbornene, 2; 3-diisopropylidene-5-norbornylene, 2-ethylidene-3-isopropylidene-5-norbornylene, 2-propenyl-2, unconjugated polyene classes such as 2-norbornadiene etc.Wherein, the polymerizable monomer that does not contain non-conjugated diene, unconjugated polyene also is one of preferred implementation.
Ethene-alpha-olefin random copolymers (C0) also can contain below the 10 moles of % in unit that are derived from other such polymerizable monomer, is preferably below 5 moles of %, more preferably 3 moles below the %.
As ethene-alpha-olefin random copolymers (C0), specifically can enumerate ethylene-propylene random copolymer, ethene-1-butylene random copolymers, ethylene-propylene-1-butylene random copolymers, ethylene-propylene-ethylidene norbornene random copolymers, ethene-1-butylene-1-octene random copolymers, ethene-4-methyl-1-pentene random copolymers, ethene-1-hexene random copolymers, ethene-1-octene random copolymers etc.Wherein, especially preferably use ethylene-propylene random copolymer, ethene-1-butylene random copolymers, ethene-1-butylene-1-octene random copolymers, ethene-1-hexene random copolymers, ethene-1-octene random copolymers etc.These multipolymers also can two or more and usefulness.
The percent crystallinity that the employing X-ray diffraction method of the ethene-alpha-olefin random copolymers (C0) that the present invention in addition, (5) is used is measured usually below 40%, be preferably 0～39%, more preferably 0～35%.And the limiting viscosity [η] that the used ethene-alpha-olefin random copolymers (C0) of the present invention (5) is measured in 135 ℃ of naphthane is generally 0.1～10dL/g, more preferably 0.5～5dL/g.
In the present invention (5),, especially can improve the balance of the shock resistance and the transparency through using (C0) composition.
Aforesaid ethene-alpha-olefin random copolymers can use vanadium series catalyst, Titanium series catalyst or metallocene catalyst etc., according to existing known method manufacturing.As ethene-alpha-olefin random copolymers (C0), can use for example commercially available article, for example can use Mitsui Chemicals system commodity to be called " TAFMER TM" etc.
Propylene polymer composition (X2)
The present invention's (5) propylene polymer composition (X2) is characterised in that, contains
(AA) above-mentioned syndiotactic propene polymer 100～25 weight parts,
(B2) aforesaid propylene-alpha-olefin copolymer 0～75 weight part (wherein, with (AA) and (B2) add up to 100 weight parts), and,
With respect to (AA) and 100 weight parts of total (B2), also contain (C0) above-mentioned ethene-alpha-olefin copolymer 1～100 weight part.
When in this scope, owing to can form especially plasticity and excellent heat resistance, and the transparency, flexibility, the excellent propylene polymer composition of low-temperature impact resistance, therefore preferably.
In addition, good in the needs flexibility, under the situation of the material that low-temperature impact resistance is excellent, be preferably and contain:
(AA) above-mentioned syndiotactic propene polymer 98～40 weight parts,
(B2) aforesaid propylene-alpha-olefin copolymer 2～60 weight parts (wherein, with (AA) and (B2) add up to 100 weight parts),
And,, also contain the compsn (also being called compsn (X2i) sometimes) of (C0) above-mentioned ethene-alpha-olefin copolymer 1～100 weight part with respect to (AA) and 100 weight parts of total (B2).
Needing excellent heat resistance, rigidity to compare under the situation of the good material of high and low temperature shock resistance, be preferably and contain:
(AA) above-mentioned syndiotactic propene polymer 100 weight parts,
(B2) aforesaid propylene-alpha-olefin copolymer 0 weight part and
(C0) compsn of above-mentioned ethene-alpha-olefin copolymer 1～100 weight part (also being called compsn (X2ii) sometimes).
In addition, plasticity, the excellent heat resistance of the present invention's (5) compsn, and the transparency, flexibility and low-temperature impact resistance is harmonious excellent.Wherein, the low-temperature impact resistance excellence is meant, for example under the material situation relatively of same elastic modulus, low temperature impact strength is higher, the perhaps material of for example same low temperature impact strength, and modulus in tension is higher.
In addition, here having excellent formability is meant, implement injection, inflation, blowing, extrude or situation that compacting etc. is shaped under, short from molten state to solidifying the required time.Under the good situation of plasticity, excellences such as forming period property, shape stability, long-term production property.
Particularly, the time till extremely solidifying, the hypocrystalline time (t during 110 ℃ the isothermal crystal that uses differential scanning calorimeter (DSC) to try to achieve is measured 1/2) be preferably below the 1000sec, more preferably below the 500sec.In addition, the hypocrystalline time (t during 110 ℃ the isothermal crystal that uses differential scanning calorimeter (DSC) to try to achieve is measured 1/2) be meant rerum natura (1).The present invention's (5) compsn is because of containing specific (AA) composition, (B2) composition, t 1/2Compared with prior art, tremendous raising is arranged, for example, can adopt with common used same moulding methodes such as isotactic Vestolen PP 7052 and have no to be shaped difficultly.
Utilize isothermal crystal to measure the hypocrystalline time (t that tries to achieve 1/2) be being under the situation of total heat with DSC heat curve in the isothermal crystal process and the area between the baseline, reach the time of 50% heat.Specifically can be with reference to new polymer experiment lecture 8 high molecular rerum naturas professional books such as (the upright altogether Co., Ltd. that publishes).Hypocrystalline time (t 1/2) mensuration be described below and carry out.5.00mg left and right sides sample is filled in the special-purpose aluminium dish; Use PerkinElmer corporate system DSCPyris1 or DSC7; According to being warmed up to 200 ℃ by 30 ℃ with 320 ℃/min; After keeping 5 minutes under 200 ℃, cool to 110 ℃ of isothermal crystal temperature by 200 ℃ with 320 ℃/min, temperature remains on the DSC curve that obtains under 110 ℃ and obtains.Wherein, hypocrystalline time (t 1/2) be to try to achieve in that 110 ℃ of isothermal crystal process time openings (moment when reaching 110 ℃ by 200 ℃) are made as t=0.In the compsn of the present invention (5), can try to achieve t as stated 1 / 2, under 110 ℃ of non crystallized situation, measure through under the isothermal crystal temperature below 110 ℃, getting a plurality of points easily, ask for hypocrystalline time (t by its extrapolated value 1/2).
And to the pin that aforesaid propylene based polymer composition (X2) is measured go into temperature (measure the softening temperature of trying to achieve according to TMA, hereinafter is also referred to as rerum natura (2)) be preferably more than 145 ℃, more preferably more than 150 ℃.
The softening temperature that utilizes TMA mensuration to try to achieve can be described below and measure.
Use system SS-120 of Jinggong Co., Ltd or TA Instrument corporate system Q-400, the compacting sheet material test film of used thickness 1mm with the heat-up rate of 5 ℃/min, applies 2kgf/cm on the pressure head of the plane of Φ 1.8mm 2Pressure, by the TMA curve try to achieve pin go into temperature (℃).
In addition, the measuring method of Izod shock strength (also being called as rerum natura (3)), modulus in tension (also being called as rerum natura (4)), turbidity (also being called as rerum natura (5)) is as follows.
The Izod shock strength strikes out the test film of 12.7mm (wide) * 3.2mm (thick) * 64mm (length) by the thick compacting sheet material of 3mm, introduces the breach of mechanical workout, measures down at 0 ℃, adopts the MV of three mensuration.
As modulus in tension, by the thick compacting sheet material of 1mm,, use the JIS3 dumb-bell test piece with O dumbbell punching press according to JIS K6301, be used to estimate sample.When measuring, for example, use Instron corporate system tensile testing machine Inston 1123, under distance between bench marks: 30mm, draw speed 30mm/min, measure modulus in tension down at 23 ℃, adopt the MV of measuring for three times.
As turbidity, the compacting test film of used thickness 1mm is measured inner turbidity with Japanese electric look Industrial Co., Ltd's system numeral turbidometer " NDH-20D ", adopts the MV of twice mensuration.
In addition, in above-mentioned each test, use pressing make-up machine at 200 ℃ down behind 5 minutes～10 minutes waste heats; Add at 10MPa and to depress, after being shaped with 1～2 minute, under 20 ℃; Depress cooling in adding of 10MPa, make the sheet material of specific thickness thus, obtain test film.
In addition, the present invention's (5) propylene polymer composition (X2) preferably satisfies
(2) pin go into temperature above at 145 degree, be preferably 147 spend more than;
(3) the Izod shock strength more than 50J/m, be preferably 100J/m;
(4) modulus in tension be 1MPa～2000MPa scope, be preferably the scope of 1MPa～1500MPa;
(5) inner turbidity value below 50%, be preferably below 40%.
Under the situation of compsn (X2i), be ethene as the terminal olefin of propylene-alpha-olefin copolymers (B2), be preferably ethene and the monomeric combination of above-mentioned HAO, be preferably ethene especially.And the formation unit that more preferably is derived from terminal olefin is preferably 10 moles of %～40 mole %, is preferably 15～35 moles of % especially.In this scope, can form the especially compsn of thermotolerance, the transparency, flexibility, shock resistance excellence.
Under the situation of compsn (X2i), the hypocrystalline time (1) is preferably below 1000sec, more preferably below 500sec;
Pin is gone into temperature (2) preferably more than 145 ℃, more preferably more than 147 ℃, further preferably more than 150 ℃;
Izod shock strength (3) is preferably more than the 50J/m, more preferably more than 100J/m;
Modulus in tension (4) preferably the scope of 1MPa～2000MPa, more preferably in the scope of 1MPa～1000MPa, further preferably in the scope of 1MPa～800MPa;
Inner turbidity value (5) is preferably below 50%, more preferably below 40%.
Under the situation of compsn (X2i); The rerum natura of at least more than one in preferably (1)～(5) satisfies preferable range; More preferably satisfy or (2), (3), any situation that (4) satisfy simultaneously or satisfy simultaneously (3), (4), (5) simultaneously (1), (3), (4); More preferably satisfy or satisfy simultaneously (2), (3), (4), (5) simultaneously (1), (3), (4), (5), is preferably (1), (2), (3), (4), (5) especially and all satisfies.
And under the situation of compsn (X2ii),, be preferably 1-butylene, 1-octene especially as the terminal olefin of ethene-alpha-olefin copolymer (C0).And the formation unit that more preferably is derived from terminal olefin is preferably 5 moles of %～40 mole %, and more preferably 5～30 moles of % are preferably 5～20 moles of % especially.In the time of in this scope, can form the especially compsn of thermotolerance, the transparency, low-temperature impact resistance, excellent rigidity.
Under the situation of compsn (X2ii), the hypocrystalline time (1) is preferably below 1000sec, more preferably below 500sec;
Pin is gone into temperature (2) preferably more than 145 ℃, more preferably more than 147 ℃, further preferably more than 150 ℃;
Izod shock strength (3) preferably more than 100J/m, more preferably 200J/m;
Modulus in tension (4) preferably the scope of 100MPa～2000MPa, more preferably in the scope of 100MPa～1000MPa, further preferably in the scope of 100MPa～800MPa;
Inner turbidity value (5) is preferably below 50%, more preferably below 40%.
Under the situation of compsn (X2ii); At least more than one the rerum natura that is preferably in (1), (2), (3), (4), (5) satisfies preferable range; More preferably satisfy or (2), (3), any situation that (4) satisfy simultaneously or satisfy simultaneously (3), (4), (5) simultaneously (1), (3), (4); More preferably satisfy or satisfy simultaneously (2), (3), (4), (5) simultaneously (1), (3), (4), (5), is preferably (1), (2), (3), (4), (5) especially and all satisfies.
The present invention's (5) propylene polymer composition (X2) is preferably and contains 99.0～35.0 moles of % in formation unit that are derived from propylene in the said composition; Be derived from 1.0～65 moles of % in formation unit (wherein, the formation unit with the terminal olefin (comprising propylene) that is derived from carbonatoms 2～20 is 100 moles of %) of the terminal olefin (not comprising propylene) of carbonatoms 2～20.In addition, the terminal olefin of carbonatoms 2～20 (not comprising propylene) more preferably contains ethene.
In the propylene polymer composition (X2) of the present invention (5); In the scope of goal of the invention, also can cooperate additives such as weather-proof stablizer, heat-resisting stabilizing agent, static inhibitor, slipproofing agent, antiblocking agent, antifogging agent, nucleator, lubricant, pigment, dyestuff, softening agent, inhibitor, hydrochloric acid absorbent, inhibitor as required.
The present invention's (5) propylene polymer composition (X2) also can contain other polymkeric substance such as elastomerics, resin in the scope of the present invention's (5) purpose.
Graft modification
At least a portion in the present invention's (5) the propylene polymer composition (X2) or whole, polar monomer capable of using carries out graft modification.
For example can be (AA) composition a part or all by graft modification; Also can be (B2) composition a part or all by graft modification; (C0) composition a part or all by graft modification; Can also be (AA) composition, (B2) composition separately a part or all by graft modification; (B2) composition, (C0) composition separately a part or all by graft modification, (AA) composition, (C0) composition separately a part or all by graft modification, (AA) composition, (B2) composition, (C0) composition separately a part or all by graft modification.
As this polar monomer, can enumerate the ethene property unsaturated compound that contains hydroxyl, the ethene property unsaturated compound that contains amino, the ethene property unsaturated compound that contains epoxy group(ing), aromatic ethenyl compound, unsaturated carboxylic acid or derivatives thereof, vinyl ester compound, vinylchlorid, carbodiimide compound etc.
As polar monomer, be preferably the unsaturated carboxylic acid or derivatives thereof especially especially.As the unsaturated carboxylic acid or derivatives thereof; Can enumerate ester that the unsaturated compound with 1 above carboxylic acid group, the compound with carboxylic acid group and alkyl alcohol form, have 1 above acid anhydride's unsaturated compound etc.; As unsaturated group, can enumerate vinyl, vinylidene, unsaturated cyclic hydrocarbon radical etc.
As concrete compound; For example can enumerate vinylformic acid, toxilic acid, fumaric acid, tetrahydrophthalic acid, methylene-succinic acid, citraconic acid, butenoic acid, methylacrylic acid, Nadic acid (trade mark) unsaturated carboxylic acids such as (internally-oriented cis-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylicacid); Or derivatives thereof, for example acid halide (acid halide), acid amides, imide, acid anhydride, ester etc.As the concrete example of these verivates, can enumerate for example Malaysia acyl chlorides, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, toxilic acid glycidyl ester etc.
These unsaturated carboxylic acids and/or its verivate can use a kind of separately, also can two or more combinations use.Wherein, be fit to use unsaturated dicarboxylic acid or its acid anhydrides, especially preferably use toxilic acid, Nadic acid or their acid anhydrides.
Modification obtains through making be modified body and polar monomer graft polymerization.When being modified body and aforesaid polar monomer graft polymerization, the consumption of polar monomer does, with respect to the 100 weight parts body that is modified, uses 1～100 weight part usually, preferably uses the amount of 5～80 weight parts.This graft polymerization is carried out in the presence of radical initiator usually.
As radical initiator, can use organo-peroxide or azo cpd etc.
Radical initiator can and use the direct mixing of be modified body and polar monomer, also may be dissolved in a spot of organic solvent and uses afterwards.As this organic solvent,, remove this not special qualification so long as the organic solvent of solubilized radical initiator can use.
And when being modified body and polar monomer graft polymerization, also can use reducing substances.When using reducing substances, can improve the grafting amount of polar monomer.
The body that is modified utilizes the graft modification of polar monomer to implement according to existing known method; For example; Can be dissolved in the organic solvent through the body that will be modified, then, polar monomer and radical initiator etc. added in the solution; 70～200 ℃, be preferably under 80～190 ℃ the temperature, react 0.5～15 hour, be preferably 1～10 hour and carry out.
And, also can use forcing machine etc., make be modified body and polar monomer reaction, make the modified propylene based polymer composition.This reaction is preferably usually to be carried out more than the fusing point of body that is modified, particularly, (B2) composition is being carried out under the situation of modification, for example 120～300 ℃, be preferably under 120 ℃～250 ℃ the temperature, implemented usually 0.5～10 minute.And the body that is modified that contains (AA) composition is being carried out under the situation of modification, be preferably for example 160～300 ℃, be preferably under 180 ℃～250 ℃ the temperature, implemented usually 0.5～10 minute.
Be under the situation of 100 weight % with the modification body, the modification amount of the modification body that obtains like this (the grafting amount of polar monomer) is generally 0.1～50 weight %, is preferably 0.2～30 weight %, 0.2～10 weight % more preferably.
In the present invention (5), use these modification bodies, and as required, and be selected from the mixing more than a kind of unmodified body in (AA) composition, (B2) composition and (C0) composition, can access the propylene polymer composition (X2) of the present invention (5).
For example; Can with after state the pellet modification of the propylene polymer composition (V) or the propylene polymer composition (V) of the present invention (5); Modulation modification body; With the unmodified polymer of this modification body and other necessary amount (be selected from (AA) composition, (B2) composition or (C0) in the composition more than a kind) fusion mixes, and makes acrylic polymer (X2).
And; At least a portion with respect to 100 weight % are obtained by aforesaid method utilizes polar monomer by the propylene polymer composition of graft modification (X2), the content of polar monomer is generally 0.001～50 weight %, is preferably 0.001～10 weight %, more preferably 0.001～5 weight %, further be preferably 0.01～3 weight %.The control of polar monomer content can easily be carried out through for example suitably selecting the grafting condition.
At least a portion of the present invention's (5) propylene polymer composition by polar monomer by the situation of graft modification under; Excellent with binding property, the intermiscibility of other resin, and can improve the wellability on the molding surface that obtains by propylene polymer composition sometimes.
In addition; At least a portion through forming compsn is by the compsn of graft modification; Not only can keep the present invention's (5) performance such as the transparency that propylene polymer composition had, low-temperature impact resistance, mechanical properties (rigidity or flexibility), thermotolerance, and can also add intermiscibility or binding property with other material sometimes.
In addition; Content through making polar monomer, for example unsaturated carboxylic acid and/or its verivate makes the present invention's (5) polyolefin compositions demonstrate high bond strength with respect to the resin that contains polar group (for example polyester, Z 150PH, ethylene-vinyl alcohol copolymer, polymeric amide, PMMA, polycarbonate etc.) in above-mentioned scope.
In addition, at least a portion of the present invention (5) by the propylene polymer composition of graft modification in the scope of the characteristic that this modifier had, can with other polymkeric substance, for example cooperation such as thermoplastic resin, elastomerics.These both cooperated and can mix in the graft modification stage, also can after modification, mix.
In addition, being the plasticity of the prolylene polymer composition that further improves the present invention (5), that is, is to improve Tc, accelerate crystallization velocity, can also contain the nucleator of specific any composition.In this case; Nucleator can be that for example biphenyl fork Sorbitol Powder is that nucleator, phosphate ester salt are that nucleator, rosin series nucleator, TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. metal-salt are nucleator, fluorinated polyethylene, 2; 2-methylene-bis (4, the 6-di-tert-butyl-phenyl) sodium phosphate, pimelic acid and salt, 2 thereof, 6-naphthoic acid dicarboxylicacid two Cyclohexamides etc.; The not special restriction of use level is about 0.1～1 weight part but be preferably with respect to propylene polymer composition.Not special restriction on cooperation opportunity can be between polymerization period, after the polymerization or be shaped to add and add man-hour.
The method of manufacture of propylene polymer composition (X2)
Aforesaid propylene polymer composition can adopt various known method through making each composition in aforesaid scope; For example can adopt utilize slurry phase, solution mutually or gas phase with continous way or the multistage polymeric method of batch-type; Use Henschel mixing roll, V-type mixing roll, ribbon blender (ribbon blender), drum tumbler to carry out method of mixing; Or after mixing; Behind melting mixings such as single screw extrusion machine, twin screw extruder, kneader, Banbury, carry out the method for granulation or pulverizing and make.
When making the present invention's (5) propylene polymer composition (X2), for example, can use the pellet that contains propylene polymer composition (V) that is described below as raw material.This propylene polymer composition (V) contains:
Syndiotactic propene polymer (AA1) 1～65 weight part,
Propylene-alpha-olefin copolymers (B21) 99～35 weight parts (wherein, with (AA1) and (B21) add up to 100 weight parts),
And this polymkeric substance (AA1) fully satisfies following condition (a1), and this multipolymer (B21) fully satisfies following condition (b '),
(a1): adopt 13The syndiotactic five unit composition ratio (rrrr divides rate) that C-NMR measures are more than 85%; And utilize fusing point (Tm) that DSC tries to achieve more than 145 ℃; The unitary content of formation that is derived from propylene surpasses 90 moles of % (being 100 moles of % with the formation unit total amount in this polymkeric substance (AA1) wherein)
(b1): the unitary content of formation that is derived from propylene is 55～90 moles of %; The unitary content of formation that is derived from least a alkene in the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20 be 10～45 moles of % (wherein; Add up to 100 moles of % so that the formation unit that is derived from propylene and the formation of the terminal olefin (not comprising propylene) that is derived from carbonatoms 2～20 are unitary); With JIS K-6721 is standard; 230 ℃, 2.16kg load down the MFR of mensuration be 0.01～100g/10 minute scope, and satisfy following condition (b1-1) and (b1-2) in any more than;
(b1-1): adopt 13The syndiotactic triad branch rate (rr divides rate) that the C-NMR method is measured is more than 60%;
(b1-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] (dL/g) satisfies following relational expression with above-mentioned MFR (g/10 minute, 230 ℃, 2.16kg load):
1.50×MFR (-0.20)≤[η]≤2.65×MFR (-0.20)。
As used (AA1) syndiotactic propene polymer of above-mentioned pellet, can enumerate the acrylic polymer identical material used with aforesaid propylene based polymer composition (X2).Its combining form, to be derived from the syndiotactic propene polymer (AA) that preferred implementation that the unitary kind of the formation that is derived from terminal olefin, amount, rule five a unit composition ratio, Tm, Δ H, [η] beyond the formation unit of propylene wait, method of manufacture etc. are also complete and aforesaid propylene based polymer composition (X2) is used identical.
As used (B21) propylene-alpha-olefin copolymers of the present invention's (5) pellet, can enumerate propylene-alpha-olefin copolymers (B2) the identical material used with aforesaid propylene based polymer composition (X2).
In the present invention (5), the preferred implementation of the unitary kind of the formation of multipolymer, ratio, rr value, rr1 value, [η], percent crystallinity, Tg, Mw/Mn etc., method of manufacture etc. are also fully identical with the used propylene-alpha-olefin copolymers (B2) of aforesaid propylene based polymer composition (X2).
It is 1～65 weight part that above-mentioned pellet contains (AA1) composition, be preferably 1～40 weight part; (B21) composition is 99～35 weight parts, is preferably the propylene polymer composition (V) of 99～60 weight parts 100 weight parts that add up to of (AA1) composition and (B21) composition (wherein, with).
As the shape of the pellet that constitutes by propylene polymer composition (V), can enumerate spherical, cylindric, lensing, cubic etc.These pellets can be according to known prilling process manufacturing, for example, with (AA1) composition and (B21) the even melting mixing of composition, after extruding with forcing machine, through hot machining or wire cutting, can obtain spherical, cylindric, lentiform pellet.In the case, cutting can be in water, implement under the arbitrary environment in the air-flow such as air.And when using under the situation with the forcing machine that can make the device that strand skin of material and internal layer be made up of different polymer; Being made into outer through cutting is the double-deck strand of material of (B21) composition for (AA1) composition, internal layer; Can further control mutual binding property, better effects if.The pellet of cubic can be through for example behind uniform mixing, is configured as sheet with roller etc., uses the sheet material dicing machine to obtain.The longest length partly that its specification is preferably pellet is below the 3cm.Under the situation of the pellet that surpasses this specification, cause error at measurment to increase sometimes.
By the pellet that propylene polymer composition (V) constitutes, can pounce on the surface of this pellet and add in lime carbonate, permanent white, silica, talcum, Triple Pressed Stearic Acid and the polyolefin powder one or more.In this case, can further suppress bonded to each other, or the adhesion phenomenon of pellet when suppressing from barrel etc. discharging, therefore preferably.The face powder amount gets final product with the corresponding interpolation necessary amount of size, the shape of pellet, usually with respect to the resin combination pellet, adds 0.05～3 weight part.
In the scope of the present invention's (5) goal of the invention; As required, also can cooperate additives such as weathering resistance stablizer, heat-resisting stabilizing agent, static inhibitor, slipproofing agent, antiblocking agent, antifogging agent, nucleator, lubricant, pigment, dyestuff, softening agent, inhibitor, hydrochloric acid absorbent, inhibitor.In the propylene polymer composition (V) of the present invention (5); In the scope of the present invention's (5) purpose, can also contain other polymkeric substance (except (AA1) acrylic polymer, (B21) propylene-alpha-olefin copolymers with the ethene-alpha-olefin copolymer (C0)).
As the preferred method that obtains propylene polymer composition (V) pellet; Can enumerate more than the climax temperature (Tm) in the differential scanning calorimeter (DSC) of (AA1) composition, and under the temperature below 280 ℃ for example mixing (AA1) composition and (B21) method of composition.
In order to obtain propylene polymer composition (X2) by propylene polymer composition (V); Can be with the polymkeric substance that needs modification, polyolefin polymkeric substance and the present invention's (5) polyolefin properties-correcting agent and carry out mixing according to propylene polymer composition (X2) described additive as required for example.As compounding process, preferably with the present invention's (5) pellet with need the polymer melt of modification mixing.The use level of properties-correcting agent is 3～95 weight %, be preferably 10～80 weight %, 30～70 weight % more preferably.This use level is in above-mentioned scope the time, and it is abundant then can to obtain modified effect, good fluidity, shaping processability, excellent strength, the polymer compsn that is modified of excellent heat resistance.
Because the resistance to blocking of above-mentioned pellet is excellent, therefore can carry out modification to other polymkeric substance with high productivity.
Therefore; Mixing through (C0) ethene-alpha-olefin copolymer of (AA) composition of above-mentioned pellet, necessary amount, necessary amount and other polymkeric substance as required (except the alpha-olefin copolymer of terminal olefin (wherein the not comprising propylene) multipolymer of (AA) syndiotactic propene polymer, (B2) propylene-carbonatoms 2～20, (C0) ethene-carbonatoms 3～20) and above-mentioned additive are as required cooperated, can access the compsn (X2) of the present invention (5).
<Propylene polymer composition (X3)>
Specify the present invention (6) below.
The present invention's (6) propylene polymer composition (X3) contains specific (AA) syndiotactic propene polymer and specific (B3) propylene-alpha-olefin copolymers.
Above-mentioned syndiotactic propene polymer (AA) specifically as stated.
Propylene-alpha-olefin copolymers (B3)
It is the amount of 30～90 moles of % that propylene-alpha-olefin copolymers (B3) contains the formation unit that is derived from propylene; Contain the formation unit that is derived from least a alkene in the terminal olefin (not comprising propylene) that is selected from carbonatoms 2～20 and be 10～70 moles of % (wherein; Add up to 100 moles of % so that the formation unit that is derived from propylene and the formation of the terminal olefin (wherein not comprising propylene) that is derived from carbonatoms 2～20 are unitary) amount; According to JIS K-6721 standard; 230 ℃, 2.16kg load down the MFR of mensuration be 0.01～100g/10 minute scope, and satisfy following condition (b-1) and (b-2) in any more than
(b-1): adopt 13The syndiotactic triad branch rate (rr divides rate) that the C-NMR method is measured is more than 60%,
(b-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] is (dL/g) with according to JIS K-6721 standard, 230 ℃, 2.16kgf load down the MFR (g/10 minute) of mensuration satisfy following relational expression:
1.50×MFR (-0.20)≤[η]≤2.65×MFR (-0.20)。
In the present invention (6), the not special restriction of the propylene-alpha-olefin copolymers (B3) of each rerum natura in above-mentioned scope, as this propylene-alpha-olefin copolymers (B3),
Consider from vibration damping property, anti-impaired property, wear resistance aspect; The unitary content of formation that is derived from propylene is 30～90 moles of %, be preferably 40～90 moles of %, more preferably 50～90 moles of %, further be preferably 51～90 moles of %; The formation unit that is derived from ethene and the formation of the terminal olefin that is derived from carbonatoms 4～20 be unitary to add up to 10～70 moles of % (wherein, unitaryly adding up to 100 moles of % with the formation unit that is derived from propylene, the formation unit and the formation of the terminal olefin that is derived from carbonatoms 4～20 that are derived from ethene), be preferably 10～60 moles of %, more preferably 10～50 moles of %, the multipolymer (B3) that further is preferably 10～49 moles of % are one of preferred implementation.
In addition, propylene-alpha-olefin copolymers (B3) be propylene-ethylene-carbonatoms 4～20 alpha-olefin copolymer, and will be made as P from the unitary ratio of the formation of ethene E(mole %) will be made as P from the unitary ratio of formation of the terminal olefin of carbonatoms 4～20 HAOSituation under, P more preferably E≤P HAOMultipolymer.More specifically, preferred P E/ P HAOBe 0.01～1.00, be preferably 0.05～0.80, more preferably 0.06～0.60, further be preferably 0.10～0.50.
Propylene polymer composition (X3) in the present invention (6) is total 100 weight parts with respect to above-mentioned syndiotactic propene polymer (AA) and aforesaid propylene-alpha-olefin copolymer (B3); Also contain under the situation of compsn (compsn (X3i)) of hydrocarbon resin as follows (C1) 0.1～100 weight part, aforesaid propylene-alpha-olefin copolymer (B3) is preferably:
The unitary content of formation that is derived from propylene is 30～90 moles of %, be preferably 40～90 moles of %, more preferably 50～90 moles of %, further be preferably 51～90 moles of %,
The formation unit that is derived from ethene adds up to 10～70 moles of % (wherein with the formation of the terminal olefin that is derived from carbonatoms 4～20 is unitary; With the formation unit that is derived from propylene, be derived from the formation unit of ethene and be derived from that the formation of terminal olefin of carbonatoms 4～20 is unitary to add up to 100 moles of %), be preferably 10～60 moles of %, more preferably 10～50 moles of %, further be preferably 10～40 moles of %; And
Being P from the unitary ratio of the formation of ethene E(mole %) is P with the unitary ratio of formation from the terminal olefin of carbonatoms 4～20 HAOSituation under, P E≤P HAOThe alpha-olefin copolymer of propylene-ethylene-carbonatoms 4～20.
More specifically, be preferably P especially E/ P HAOBe 0.01～1.00, more preferably 0.05～0.80, further be preferably 0.06～0.60, further be preferably 0.10～0.50.
Propylene polymer composition (X3) in the present invention (6) is total 100 weight parts with respect to above-mentioned syndiotactic propene polymer (AA) and propylene-alpha-olefin copolymers (B3); Also contain under the situation of compsn (compsn (X3ii)) of noncrosslinking or crosslinked ethylene series thermoplastic elastomer (C2) 0.1～500 weight part, aforesaid propylene-alpha-olefin copolymer (B3) more preferably:
The unitary content of formation that is derived from propylene is 30～90 moles of %, be preferably 50～90 moles of %, more preferably 55～90 moles of %, further be preferably 60～90 moles of %,
The formation unit that is derived from ethene and the formation of the terminal olefin that is derived from carbonatoms 4～20 be unitary to add up to 10～70 moles of % (wherein, with the formation unit that is derived from propylene, be derived from the formation unit of ethene and be derived from that the formation of terminal olefin of carbonatoms 4～20 is unitary to add up to 100 moles of %), be preferably 10～50 moles of %, 10～40 moles of % more preferably.
In addition; As the terminal olefin (not comprising propylene) of carbonatoms 2～20, can enumerate ethene, 3-methyl-1-butene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.Be preferably ethene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene especially.
The employed propylene-alpha-olefin copolymers of the present invention (6) (B3) is according to JIS K-6721,230 ℃, 2.16kg load down the MFR of mensuration be preferably 0.01～100g/10 minute scope.
The employed propylene-alpha-olefin copolymers of the present invention (6) (B3), satisfy following condition (b-1) and (b-2) in any more than:
(b-1): the syndiotactic triad branch rate (rr divides rate, triad syndiotactic property) that adopts NMR method mensuration is more than 60%;
(b-2): the limiting viscosity of in 135 ℃ of naphthane, measuring [η] (dL/g) satisfies following relational expression with above-mentioned MFR (g/10 minute, 230 ℃, 2.16kg load):
1.50×MFR (-0.20)≤[η]≤2.65×MFR (-0.20)。
This condition (b-1) and (b-2) respectively with the used propylene-alpha-olefin copolymers (B2) in the invention described above (4) and (5) in condition (b-1) and (b-2) identical, the detailed content of this condition is as stated.
Aforesaid propylene-alpha-olefin copolymer (B3) is identical with aforesaid propylene-alpha-olefin copolymer (B2); Can be in the presence of catalyst for olefines polymerizing; Propylene is made with being selected from least a olefinic polymerization in the terminal olefin (not comprising propylene) of carbonatoms 2～20, and above-mentioned catalyst for olefines polymerizing contains:
Crosslinked metallocene compound (a-2) shown in the formula [1-2] and
(b) be selected from (b-1) above-mentioned Organoaluminoxy compound,
(b-2) with the right above-claimed cpd of above-mentioned crosslinked metallocene compound (a-2) reacting forming ion and
(b-3) above-claimed cpd more than at least a kind in the above-mentioned organo-aluminium compound.But as long as satisfy the condition as propylene-alpha-olefin copolymers (B3), then method of manufacture also is not limited thereto.
Figure GSA00000105371101291
In formula [1-2], R 1, R 2, R 3, R 4, R 5, R 8, R 9And R 12For being selected from Wasserstoffatoms, alkyl, containing atom or base in silica-based, separately can be identical also can be different;
R 6And R 11For being selected from Wasserstoffatoms, alkyl and containing same atom or the same base in silica-based;
R 7And R 10For being selected from Wasserstoffatoms, alkyl and containing same atom or the same base in silica-based;
R 6, R 7, R 10And R 11All be not Wasserstoffatoms simultaneously;
R 2And R 3Can interosculate and form ring;
R 5～R 12Middle adjacent group can interosculate each other and form ring;
R 13And R 14Be the aryl that is selected from carbonatoms 6～18, the alkyl of carbonatoms 1～40, the alkylaryl of carbonatoms 6～40, the fluoro aryl of carbonatoms 6～20, the fluoroalkyl aryl of carbonatoms 7～40, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40; Separately can be identical also can be different
R 13And R 14In at least one is the aryl that is selected from carbonatoms 7～18, the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40;
M is Ti, Zr or Hf;
Y is carbon or silicon;
Q is selected from neutrality, conjugation or non-conjugated diene below 10 of halogen, alkyl, carbonatoms, anion binding base and can be with the identical or different combination of lone-pair electron coordinate neutral dentate;
J is 1～4 integer.
As the concrete example of this crosslinked metallocene compound (a-2), can enumerate the crosslinked metallocene compound (a-2a) described in the explanation of the present invention (4).
In addition; Compound or " dichloride " that " zirconium " of above-mentioned illustrated compound (crosslinked metallocene compound (a-2a)) replaces with " hafnium " or " titanium " replace with " difluoride ", " dibromide ", " diiodide ", or " dichloride " to replace with the metallocene compound of " dimethyl-" or " methylethyl " etc. be the metallocene compound shown in the general formula [1-2] too.
Above-mentioned crosslinked metallocene compound (a-2) can be with reference to the known method manufacturing.As known method of manufacture, for example can enumerate the applicant in the method for manufacture described in the WO04/029062 communique.
Aforesaid metallocene compound can use a kind of separately, also can two or more combinations use.
The Organoaluminoxy compound (b-1) that uses in the manufacturing as propylene-alpha-olefin copolymers (B3) can use and the used identical compound of Organoaluminoxy compound (b-1) during above-mentioned syndiotactic propene polymer (AA) is made.
The compound (b-2) right with crosslinked metallocene compound (a-2) reacting forming ion that uses in the manufacturing as propylene-alpha-olefin copolymers (B3) can use and used compound (b-2) the identical compound right with crosslinked metallocene compound (a-2) reacting forming ion during above-mentioned syndiotactic propene polymer (AA) is made.
The organo-aluminium compound that uses in the manufacturing as propylene-alpha-olefin copolymers (B3) (b-3) can use and the used identical compound of organo-aluminium compound (b-3) during above-mentioned syndiotactic propene polymer (AA) is made.
Above-mentioned each composition (a-2, b-1, b-2 and b-3) as required, and is also capable of loading and carrying in upward use of above-mentioned granular carrier (c).
The method of manufacture of propylene-alpha-olefin copolymers (B3)
When propylene-alpha-olefin copolymers (B3) polymerization, can select method of use, the interpolation order of each composition arbitrarily, can enumerate the method that is described below.
Add composition (a-2) and composition (b) in the polymerizer method with random order.
In aforesaid method, also can make the contact in advance more than at least two of each catalyst component.
When using aforesaid catalyst for olefines polymerizing to carry out olefinic polymerization, the consumption of composition (a-2) is that per 1 liter of reaction volume is generally 10 -9～10 -1The mole, be preferably 10 -8～10 -2Mole.
The consumption of composition (b-1) does, makes the mol ratio [(b-1)/M] of all transition metal atoms (M) in composition (b-1) and the composition (a-2) be generally 0.01～5,000, be preferably 0.05～2,000.The consumption of composition (b-2) does, makes the mol ratio [(b-2)/M] of aluminium atom and all transition metal (M) in the composition (a-2) in the composition (b-2) be generally 1～1,000, be preferably 1～500.The consumption of composition (b-3) does, makes the mol ratio [(b-3)/M] of the transition metal atoms (M) in composition (b-3) and the composition (a-2) be generally 1～10,000, be preferably 1～5,000.
Propylene-alpha-olefin copolymers (B3) is in the presence of aforesaid catalyst for olefines polymerizing, makes propylene and at least a alkene that is selected from the terminal olefin (not comprising propylene) of carbonatoms 2～20, copolymerization under liquid phase usually.At this moment, generally use hydrocarbon solvent, but also can be with terminal olefin as solvent.As hydrocarbon solvent, specifically can enumerate hydrocarbon solvent same as described above.Copolymerization can adopt any method in batch process or the continuous processing to implement.
As can be used for the polymeric terminal olefin, can enumerate for example ethene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.Terminal olefin can use a kind of separately, also can two or more combinations use.
Use catalyst for olefines polymerizing, adopting batch process to implement under the situation of copolymerization, the concentration of the metallocene compound in the polymerization system is that per 1 liter polymerization volume, consumption are generally 0.00005～1 mmole, are preferably 0.0001～0.50 mmole.
And the reaction times (average retention time under the situation of copolymerization employing continuous processing enforcement) is different because of conditions such as catalyst concn, polymerization temperatures, is generally 5 minutes～3 hours, is preferably 10 minutes～1.5 hours.
Aforesaid propylene be selected from the terminal olefin (not comprising propylene) of carbonatoms 2～20 at least a alkene respectively with the amount of the propylene-alpha-olefin copolymers (B3) that can obtain aforesaid specific composition to the polymerization system charging.In addition, when copolymerization, can use hydrogen equimolecular quantity regulator.
With propylene during with at least a olefin-copolymerization that is selected from the terminal olefin (not comprising propylene) of carbonatoms 2～20, what propylene-alpha-olefin copolymers (B3) obtained usually is the polymeric solution that contains it as stated.Handle this polymeric solution with ordinary method, obtain propylene-alpha-olefin copolymers (B3).
This copolyreaction usually 40～200 ℃ of temperature, be preferably in 40 ℃～180 ℃, more preferably 50 ℃～150 ℃ the scope, pressure for greater than 0 smaller or equal to 10Mpa, be preferably 0.5～10Mpa, more preferably implement under the condition of the scope of 0.5～7Mpa.
[(C1) be selected from rosin series resin, terpenic series resin and the petroleum resin more than one Resin]
In used being selected from more than one the resin (C1) in rosin series resin, terpenic series resin and the petroleum resin of the present invention (6); As the rosin series resin, can enumerate natural rosin, polymerized rosin; Utilize the modified rosin of modifications such as toxilic acid, fumaric acid, (methyl) vinylformic acid, rosin derivative.And,, can enumerate carboxylate, phenol modifier and the carboxylate thereof etc. of above-mentioned natural rosin, polymerized rosin or modified rosin as this rosin derivative.In addition, also can enumerate the hydrogenate of these rosin series resins.
In addition; As the terpenic series resin; Can enumerate the resin that forms by α-Pai Xi, beta-pinene, PC 560, kautschin, terpene phenolic, terpenol, terpene aldehyde etc., also can enumerate terpenic series resin of α-Pai Xi, beta-pinene, PC 560, kautschin etc. and aromatic monomer polymeric aromatic series modifications such as vinylbenzene etc.In addition, also can enumerate their hydrogenate.
And as petroleum resin, for example can to enumerate C 5 fraction with the tar petroleum naphtha be the aliphatics through-stone oleo-resinous of main raw material, be the aromatic series through-stone oleo-resinous of main raw material and their copolymerized petroleum resin with the C9 cut.Promptly; Can enumerate C5 through-stone oleo-resinous (with petroleum naphtha decompose oil the C 5 fraction polymerization and resin), C9 through-stone oleo-resinous (with petroleum naphtha decompose oil the polymerization of C9 cut and resin), C5C9 copolymerized petroleum resin (C 5 fraction that petroleum naphtha is decomposed oil with the copolymerization of C9 cut and the resin that gets); Also can enumerate the styrenic of tar naphtha fraction; The indenes class, coumarone, the coumarone indene that contains other Dicyclopentadiene (DCPD) etc. is a resin; The condenses of p-tert-butylphenol and acetylene is the induced by alkyl hydroxybenzene resin of representative, the diformazan benzene series resin that o-Xylol, p-Xylol or m-xylene and formalin (formalin) reaction forms etc.
In addition, the present invention (6) is employed to be selected from more than one the resin (C1) in rosin series resin, terpenic series resin and the petroleum resin, considers from making the excellent angle of weathering resistance and discoloration-resistant, is preferably hydrogenated derivatives.The softening temperature that the ring and ball method of above-mentioned resin (C1) records is preferably 40～180 ℃ scope.In addition, number-average molecular weight (Mn) molecular weight that the GPC of above-mentioned resin (C1) records is preferably 100～10, about 000 scope.
More than one the resin (C1) that the present invention (6) is employed to be selected from rosin series resin, terpenic series resin and the petroleum resin also can use commercially available article.
[noncrosslinking or partial cross-linked ethylene series thermoplastic elastomer (C2)]
Below, specify the present invention (6) employed (C2) composition.
The employed noncrosslinking or partial cross-linked ethylene series thermoplastic elastomer (C2) of the present invention (6) is preferably the ethene-alpha-olefin random copolymers that contains Vestolen PP 7052 and contain non-conjugated diene; But be not limited to this; It also can be the noncrosslinking or partial cross-linked ethylene series thermoplastic elastomer that for example contains Vestolen PP 7052 and ethene-alpha-olefin random copolymers; As above-mentioned terminal olefin, be preferably propylene, butylene.
Above-mentioned noncrosslinking or partial cross-linked ethylene series thermoplastic elastomer (C2) 230 ℃, 10kg load down the MFR of mensuration be preferably 0.001～100, more preferably 0.01～80.
The fusing point (Tm) of being tried to achieve by dsc endothermic curve of above-mentioned noncrosslinking or partial cross-linked ethylene series thermoplastic elastomer (C2) is preferably 120～165 ℃, more preferably 130～160 ℃ scope.Above-mentioned noncrosslinking or partial cross-linked ethylene series thermoplastic elastomer (C2) is the composition for thermoplastic elastomer of non-crosslinked or partial cross-linked composition for thermoplastic elastomer, is preferably to contain crystalline polyolefin resin (C2-1) and terminal olefin based copolymer rubber (C2-2).
[crystalline polyolefin resin (C2-1)]
The used crystalline polyolefin resin (C2-1) of the present invention (6) is one or more monoolefine polymerization and the crystalline polymer amount solid resultant that obtains that adopts that the arbitrary method in high-pressure process or the low-pressure process obtains.As such resin, can enumerate for example isotactic and syndiotactic monoolefine polymer resin, these representative resins can be obtained by commercial sources.
As the suitable raw material olefin of above-mentioned crystalline polyolefin resin (C2-1), concrete example can be enumerated ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 2-methyl isophthalic acid-propylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 5-methyl isophthalic acid-hexene, 1-octene, 1-decene and with the mixed olefins of two or more these olefin.
As above-mentioned crystalline polyolefin resin (C2-1), being particularly suitable for using propylene content is that above, the preferred propylene content of 70 moles of % is the above isotactic Vestolen PP 7052 of 80 moles of %.
Polymerized form both can be a random, also can be block type, as long as can obtain the arborescens thing, adopted which kind of polymerized form all can.The MFR of crystalline polyolefin resin (C2-1) (A-1STMA-41238-65T, 230 ℃) is generally 0.01～100g/10 minute, is preferably 0.05～50g/10 minute scope especially.
And the fusing point (Tm) of being tried to achieve by dsc endothermic curve of the crystalline polyolefin resin (C2-1) that above-mentioned thermoplastic elastomer (C2) is used is preferably 120～165 ℃, more preferably 130 ℃～160 scope.And crystalline polyolefin resin (C2-1) both can be the Vestolen PP 7052 of enumerating as above-mentioned syndiotactic polypropylenes (AA), also can be above-mentioned (AA) crystalline polyolefin in addition.
Above-mentioned crystalline polyolefin resin (C2-1) possesses flowability and the stable on heating function that improves compsn.In the present invention (6), crystalline polyolefin resin (C2-1) is that the total of copolymer rubber (C2-2) is measured 100 weight parts with respect to crystalline polyolefin resin (C2-1) and terminal olefin, and usage ratio is 10～60 weight parts, be preferably 20～55 weight parts.
Use the crystalline polyolefin resin (C2-1) of aforesaid ratio, just can obtain not only caoutchouc elasticity excellence, and the also excellent composition for thermoplastic elastomer of shaping processability.
[terminal olefin is copolymer rubber (C2-2)]
The used terminal olefin based polymer rubber (C2-2) of the present invention (6) is carbonatoms 2～20, be preferably the terminal olefin of carbonatoms 2～12 and as required unconjugated polyene, for example the rubber that obtains of non-conjugated diene copolymerization.
As above-mentioned terminal olefin, specifically can enumerate ethene, propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, cetene, 1-heptadecene, 1-19 carbenes, 1-eicosylene, 9-methyl isophthalic acid-decene, 11-methyl isophthalic acid-dodecylene, 12-ethyl-tetradecene etc.
In the present invention (6), above-mentioned terminal olefin can use a kind of separately, also can use two or more mixtures.Using with mixture under the situation of 4-methyl-1-pentene and other terminal olefin, the mol ratio (other terminal olefin/4-methyl-1-pentene) of 4-methyl-1-pentene and other terminal olefin is preferably in 10/90～95/5 scope.
In the above-mentioned terminal olefin, especially preferably use ethene, propylene, 1-butylene.
As above-mentioned terminal olefin based copolymer rubber (C2-2); Can enumerate and for example contain from the formation unit of ethene with from the unitary multipolymer of formation of the terminal olefin of carbonatoms more than 3, its for from the formation unit of ethene with from the unitary ratio of formation of the terminal olefin of carbonatoms more than 3, be that the terminal olefin (mol ratio) of ethene/carbonatoms more than 3 is 40/60～95/5 multipolymer.
And as the unconjugated polyene that the present invention (6) uses as required, specifically can enumerate Dicyclopentadiene (DCPD), 1,4-hexadiene, cyclooctadiene, methene norbornene, ethylidene norbornene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 4-ethyl-1; 4-hexadiene, 5-methyl isophthalic acid, 4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl isophthalic acid, 5-heptadiene, 6-methyl isophthalic acid, 5-heptadiene, 5-ethyl-1; 5-heptadiene, 4-methyl isophthalic acid, 4-octadiene, 5-methyl isophthalic acid, 4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl isophthalic acid; 5-octadiene, 6-methyl isophthalic acid, 5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl isophthalic acid, 6-octadiene, 7-methyl isophthalic acid; 6-octadiene, 6-ethyl-1,6-octadiene, 4-methyl isophthalic acid, 4-nonadiene, 5-methyl isophthalic acid, 4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1; 4-nonadiene, 5-methyl isophthalic acid, 5-nonadiene, 6-methyl isophthalic acid, 5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1; 5-nonadiene, 6-methyl isophthalic acid, 6-nonadiene, 7-methyl isophthalic acid, 6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1; 6-nonadiene, 7-methyl isophthalic acid, 7-nonadiene, 8-methyl isophthalic acid, 7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl isophthalic acid; 4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl isophthalic acid, 5-decadiene, 6-methyl isophthalic acid, 5-decadiene, 5-ethyl-1; 5-decadiene, 6-methyl isophthalic acid, 5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl isophthalic acid; 6-decadiene, 7-methyl isophthalic acid, 6-decadiene, 6-ethyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl isophthalic acid; 7-decadiene, 8-methyl isophthalic acid, 7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl isophthalic acid; 8-decadiene, 9-methyl isophthalic acid, 8-decadiene, 8-ethyl-1,8-decadiene, 9-methyl isophthalic acid, 8-11 carbon diene etc.Wherein, be preferably 5-ethylidene-2-norbornene, 5-vinyl-2-norbornylene, Dicyclopentadiene (DCPD), 4 especially, 8-dimethyl--1,4,8-triolefin in the last of the ten Heavenly stems (DMDT), 4-ethylidene-8-methyl isophthalic acid, 7-nonadiene (EMND).
In the present invention (6), state in the use under the situation of unconjugated polyene, for example non-conjugated diene, can use a kind ofly separately, also can use two or more mixtures.In addition, except aforesaid unconjugated polyene,, also can use the monomer that other can copolymerization in the scope of the present invention's (6) purpose.
In above-mentioned terminal olefin based polymer rubber (C2-2); Under the situation of unconjugated polyene copolymerization; In the multipolymer from the unitary content of formation of wherein unconjugated polyene at 0.01～30 mole of %, be preferably 0.1～20 mole of %, be preferably in the scope of 0.1～10 mole of % especially (wherein, be in the copolymer rubber (C2-2) the unitary total amount of formation be 100 moles of %) with this terminal olefin.
And, be preferably the multipolymer of terminal olefin and unconjugated polyene as above-mentioned terminal olefin based copolymer rubber (C2-2).Especially preferably can enumerate ethene-carbonatoms 3 above alpha-olefin-nonconjugated polyene multipolymers; Wherein, The ratio of ethene and the terminal olefin of carbonatoms more than 3; Be that the terminal olefin (mol ratio) of ethene/carbonatoms more than 3 is 40/60～95/5, and contain 0.01～30 mole of % in formation unit from unconjugated polyene.
The limiting viscosity of in 135 ℃ of naphthane solvents, measuring [η] of above-mentioned terminal olefin based copolymer rubber (C2-2) is 1.0～10.0dl/g, be preferably the scope of 1.5～7dl/g.In addition, although not special restriction, the fusing point (Tm) of being tried to achieve by dsc endothermic curve of preferred above-mentioned terminal olefin based copolymer rubber (C2-2) does not exist or exists and is lower than 120 ℃.
In the present invention (6), terminal olefin based copolymer rubber (C2-2) is measured in 100 weight parts in the total of crystalline polyolefin resin (C2-1) and terminal olefin based copolymer rubber (C2-2), uses with 90～40 weight parts, the ratio that is preferably 80～45 weight parts.
Aforesaid terminal olefin based copolymer rubber (C2-2) can be according to following method manufacturing.Above-mentioned terminal olefin based copolymer rubber (C2-2) can obtain the terminal olefin of carbonatoms 2～20 and non-conjugated diene copolymerization as required in the presence of catalyst for olefines polymerizing.
In above-mentioned noncrosslinking or partial cross-linked ethylene series composition for thermoplastic elastomer (C2); Except crystalline polyolefin resin (C2-1) with the terminal olefin based copolymer rubber (C2-2), can also contain tenderizer (C2-3) and/or inorganic filler (C2-4) as any composition.
As above-mentioned tenderizer (C2-3), can use the employed tenderizer of common rubber, specifically can enumerate oil such as process oil, lubricating oil, paraffin, whiteruss, petroleum pitch, Vaseline is material; Coal tar such as coal tar, coal-tar pitch oils; Waxs such as Viscotrol C, Toenol 1140, rapeseed oil, VT 18, cocounut oil; Wax classes such as Tall oil, beeswax, POLISHING WAX-103, yolk; Lipid acid or its metal-salts such as ricinoleic acid, palmitinic acid, Triple Pressed Stearic Acid, barium stearate, calcium stearate; Synthetic macromolecule materials such as petroleum resin, coumarone indeneresin, isotactic Vestolen PP 7052; Esters such as DOP, Octyl adipate, dioctyl sebacate are softening agent; Other also has Microcrystalline Wax, rubber substitute (ointment), liquid polybutadiene, modification liquid polybutadiene, liquid polysulphide rubber (thiocol) etc.
In the present invention (6), tenderizer (C2-3) is measured 100 weight parts with respect to the total of crystalline polyolefin resin (C2-1) and terminal olefin based copolymer rubber (C2-2), usually according to below 200 weight parts, the ratio that is preferably 2～100 weight parts uses.
As above-mentioned inorganic filler (C2-4), specifically can enumerate lime carbonate, Calucium Silicate powder, clay, kaolin, talcum, silica, zeyssatite, mica powder, asbestos, aluminum oxide, permanent white, Tai-Ace S 150, calcium sulfate, magnesium basic carbonate, molybdenumdisulphide, graphite, spun glass, glass sphere, Shirasu ball etc.
In the present invention (6), inorganic filler (C2-4) is measured 100 weight parts with respect to the total of crystalline polyolefin resin (C2-1) and terminal olefin based copolymer rubber (C2-2), usually according to below 100 weight parts, the ratio that is preferably 2～50 weight parts uses.In the present invention (6), when the usage quantity of inorganic filler (C2-4) surpassed 100 weight parts, the caoutchouc elasticity of the composition for thermoplastic elastomer of gained, shaping processability might reduce.
In addition; Above-mentioned partial cross-linked ethylene series composition for thermoplastic elastomer be through with the mixture of above-mentioned crystalline polyolefin resin (C2-1), terminal olefin based copolymer rubber (C2-2), the tenderizer (C2-3) that cooperates as required and/or inorganic filler (C2-4) in the presence of the organo-peroxide that is described below; Implement dynamic thermal treatment, implementation part is crosslinked and obtain.
Wherein, " dynamically thermal treatment " be meant under molten state, carry out mixing.As organo-peroxide; Specifically can enumerate Di Cumyl Peroxide 99, di-t-butyl peroxide, 2,5-dimethyl--2,5-two (tert-butyl peroxide) hexane, 2; 5-dimethyl--2; 5-two (tert-butyl peroxide)-hexin-3,1, two (tert-butyl peroxide sec.-propyl) benzene, 1 of 3-, two (tert-butyl peroxide)-3 of 1-; 3; 5-trimethyl-cyclohexane, normal-butyl-4, two (tert-butyl peroxide) valerates of 4-, Lucidol (benzylperoxide), chloro benzoyl peroxide, peroxo-2,4 dichloro benzene formyl, tert-butyl peroxide benzoate, tert-butyl peroxide sec.-propyl carbonic ether, diacetyl peroxide, lauroyl peroxide, tert-butyl peroxide isopropyl benzene etc.
The consumption of such organo-peroxide is that whole with respect to object being treated, promptly the total of crystalline polyolefin resin (C2-1) and terminal olefin based copolymer rubber (C2-2) is measured 100 weight parts, is 0.02～3 weight part, is preferably 0.05～1 weight part.When this use level was less than above-mentioned scope, the degree of crosslinking of the composition for thermoplastic elastomer of gained was low, so deficiencies such as thermotolerance, tensile properties, elastic recovery and resilience elasticity.And when this use level during more than above-mentioned scope, the degree of crosslinking of the composition for thermoplastic elastomer of gained is too high, causes the reduction of plasticity sometimes.
In the present invention (6); When utilizing above-mentioned organo-peroxide to carry out partial cross-linked processing; Can also cooperate sulphur, p-benzoqui(o)none dioxime, p; P '-dibenzoyl quininie dioxime (p, p '-dibenzoylquinonedioxime), N-methyl-N, the peroxyde crosslinked auxiliary agent of N '-metaphenylene dimaleimide etc.; Or multi-functional methacrylate monomers such as Vinylstyrene, triallyl cyanurate, TGM 1, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, multi-functional vinyl monomers such as vinyl butyrate or stearic acid vinyl ester.
Through using compounds such as aforesaid crosslinking coagent, be expected to realize even and gentle crosslinking reaction.Compounds such as such crosslinking coagent or multi-functional vinyl monomer, with respect to the above-mentioned whole object being treateds of 100 weight parts, consumption is below 2 weight parts usually, more preferably 0.3～1 weight part.
In addition,, also can use triethylamine, Tributylamine, 2,4 in order to promote the decomposition of organo-peroxide, tertiary amines such as 6-three (dimethylamino) phenol, or the naphthenate of aluminium, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead, mercury etc. etc. decomposes promotor.
Dynamic thermal treatment among the present invention (6) is preferably carried out in non-opening device, and preferably under inactive gas environment such as nitrogen, dioxide gas, carries out.Its temperature does, the scope by crystalline polyolefin resin (C2-1) fusing point to 300 ℃ is generally 150～250 ℃, is preferably 170～225 ℃.Mixing time is generally 1～20 minute, is preferably 1～10 minute.In addition, the shearing force that is applied does, is 10～100 as velocity of shear, 000sec -1, be preferably 100～50,000sec -1
As kneading device, can use mixing roll, intensive mixer (for example Banbury, kneader), single screw rod or twin screw extruder etc., be preferably non-opening device.
Through above-mentioned dynamic thermal treatment, can obtain containing crystalline polyolefin resin (C2-1) and terminal olefin based copolymer rubber ethylene series composition for thermoplastic elastomer (C2-2) or partial cross-linked.
In addition, in the present invention (6), composition for thermoplastic elastomer is partial cross-linked be meant the gel content measured according to following method more than 20%, be preferably 20～99.5%, be preferably the situation in 45～98% scopes especially.The mensuration of gel content can be according to the sample 100mg that will take by weighing composition for thermoplastic elastomer; Be cut into the small pieces of 0.5mm * 0.5mm * 0.5mm, in encloses container, at 23 ℃; Be immersed in the hexanaphthene of 30ml after 48 hours; Obtain sample from filter paper, at room temperature dry more than 72 hours, implement until the mode of constant weight.
All that will deduct with the weight of this drying residue beyond the component of polymer are insoluble to the weight of the composition (bat wool, weighting agent, pigment etc.) of hexanaphthene, and the difference of the weight of the crystalline polyolefin resin (C2-1) in the sample before the hexanaphthene dipping is defined as " revising back final weight [y] ".
On the other hand, the weight of the terminal olefin based copolymer (C2-2) in the sample is defined as " revising back initial weight [x] ".Wherein, gel content is tried to achieve by following formula.
Gel content [wt%]=(revising back final weight [y]/correction back initial weight [x]) * 100.
Propylene polymer composition (X3)
The present invention's (6) propylene polymer composition (X3) contains:
(AA) above-mentioned syndiotactic propene polymer 10～95 weight parts are preferably 15～90 weight parts,
(B3) aforesaid propylene-alpha-olefin copolymer 90～5 weight parts, be preferably 85～10 weight parts (wherein, with (AA) and (B3) add up to 100 weight parts).
The plasticity and the excellent heat resistance of the compsn (X3) of the cooperation ratio of above-mentioned syndiotactic propene polymer (AA) and aforesaid propylene-alpha-olefin copolymer in above-mentioned scope, and flexibility, anti-impaired property, excellent in wear resistance, therefore preferred.
In addition, high as thermotolerance, the material of flexibility, wearability, anti-impaired property, vibration damping property, binding property excellence, preferably can enumerate the propylene polymer composition (X3) (compsn (X3i)) that contains following compositions:
(AA) above-mentioned syndiotactic propene polymer 10～95 weight parts, be preferably 15～90 weight parts and
(B3) aforesaid propylene-alpha-olefin copolymer 90～5 weight parts, be preferably 85～10 weight parts (wherein, with (AA) and (B3) add up to 100 weight parts),
And also contain more than one the resin (C1) that is selected from rosin series resin, terpenic series resin and the petroleum resin, add up to 0.1～100 weight part.
More than one resin (C1) preferable amount that is selected from rosin series resin, terpenic series resin and the petroleum resin is 1～90 weight part, and more preferably 1～80 weight part further is preferably 2～70 weight parts.When containing (C1) of above-mentioned scope, the binding property of propylene polymer composition (X3) is also excellent.In addition, compsn (X3i) also can be the excellent compsn of the transparency.
And high as thermotolerance, wearability, anti-impaired property, the excellent material of low-temperature impact resistance, preferably can enumerate the propylene polymer composition (X3) (compsn (X3ii)) that contains following compositions:
(AA) above-mentioned syndiotactic propene polymer 10～95 weight parts are preferably 15～90 weight parts,
(B3) aforesaid propylene-alpha-olefin copolymer 90～5 weight parts, be preferably 85～10 weight parts (wherein, with (AA) and (B3) add up to 100 weight parts),
And also contain noncrosslinking or crosslinked ethylene series thermoplastic elastomer (C2) 0.1～500 weight part.The content of above-mentioned thermoplastic elastomer (C2) is 1～500 weight part more preferably, further is preferably 50～400 weight parts.
The present invention's (6) compsn also can form especially plasticity and excellent heat resistance, and the material of flexibility, anti-impaired property, excellent in wear resistance.
Wherein, having excellent formability is meant, implement injection, inflation, blowing, extrude, foam or situation that compacting etc. is shaped under, from molten state to solidifying the required time.Under the good situation of plasticity, excellences such as forming period property, shape stability, permanent output.
Particularly, the time till extremely solidifying, the hypocrystalline time (t during 110 ℃ the isothermal crystal that uses differential scanning calorimeter (DSC) to try to achieve is measured 1/2) be preferably below the 1000sec, more preferably below the 500sec.In addition, the hypocrystalline time (t during 110 ℃ the isothermal crystal that uses differential scanning calorimeter (DSC) to try to achieve is measured 1/2) be meant rerum natura (1).The present invention's (6) compsn is because of containing specific (AA) composition and (B3) composition, compared with prior art, and t 1/2Tremendous raising is arranged, for example, can adopt with common used same moulding methodes such as isotactic Vestolen PP 7052 and have no to be shaped difficultly.
Utilize isothermal crystal to measure the hypocrystalline time (t that tries to achieve 1/2) be being under the situation of total heat with DSC heat curve in the isothermal crystal process and the area between the baseline, reach the time of 50% heat.Specifically can be with reference to new polymer experiment lecture 8 high molecular rerum naturas professional books such as (the upright altogether Co., Ltd. that publishes).
Hypocrystalline time (t 1/2) mensuration be described below and carry out.5.00mg left and right sides sample is filled in the special-purpose aluminium dish; The DSCPyris1 or the DSC7 that use PerkinElmer company to produce; According to being warmed up to 200 ℃ by 30 ℃ with 320 ℃/min; After keeping 5 minutes under 200 ℃, cool to 110 ℃ of isothermal crystal temperature by 200 ℃ with 320 ℃/min, temperature remains on the DSC curve that obtains under 110 ℃ and obtains.Wherein, hypocrystalline time (t 1/2) try to achieve through isothermal crystal process time opening (by 200 ℃ of moment that reach 110 ℃) of 110 ℃ is made as t=0.Can try to achieve the t of the present invention's (6) compsn as stated 1/2, under 110 ℃ of non crystallized situation, through under the isothermal crystal temperature below 110 ℃, get a plurality of points and measure easily, ask for hypocrystalline time (t by its extrapolated value 1/2).
The present invention's (6) propylene polymer composition (X3) preferably satisfies arbitrary condition in following (1), (2), and more preferably (1) and (2) is all in its preferable range separately.
(1) above-mentioned hypocrystalline time (t 1/2) be preferably below the 1000sec, more preferably below the 500sec.
(2) softening temperature of measuring according to the TMA method is preferably more than 110 ℃, more preferably more than 120 ℃, is preferably especially more than 130 ℃.
And the compsn (X3i) of the present invention's (6) preferred implementation preferably satisfy in following (i-1)～(i-3) at least any; More preferably satisfy (i-1) and (i-3); Or satisfy (i-2) with (i-3) in arbitrary combination, further preferred (i-1)～(i-3) is all satisfied.
(i-1) hypocrystalline time (t 1/2) preferably below the 1000sec, more preferably below 500sec.
(i-2) softening temperature of measuring according to the TMA method is preferably more than 110 ℃, more preferably more than 120 ℃, is preferably especially more than 130 ℃.
(i-3) be that the resilience spring rate of standard test is preferably below 40% with JISK6255, more preferably below 35%, further be preferably below 30%.
Above-mentioned compsn (X3i) more preferably also satisfies following (i-7).
(i-7) inner turbidity is preferably below 50%, more preferably below 30%.
And above-mentioned compsn (X3i) especially preferably satisfies following (i-6).
(i-6) modulus in tension 1MPa～1000MPa, preferably at 1～800MPa, more preferably in the scope of 10MPa～500MPa.
And the compsn (X3ii) of the present invention's (6) preferred implementation preferably satisfy among following (ii-1), (ii-2), (ii-4), (ii-5) more than one; More preferably satisfy (ii-1) and (ii-5); Or satisfy (ii-2) and (ii-5); Further preferred satisfy (ii-1), (ii-5) with (ii-4), or satisfy (ii-2), (ii-5) with (ii-4), further preferably (ii-1), (ii-2), (ii-4), (ii-5) are all satisfied.
(ii-1) hypocrystalline time (t 1/2) preferably below the 1000sec, more preferably below 500sec.
(ii-2) softening temperature of measuring according to the TMA method is preferably more than 145 ℃, more preferably more than 147 ℃.
(ii-4) the Izod shock strength preferably more than 50J/m, more preferably at 100J/m.
(ii-5) the glossiness velocity of variation before and after the test of vibration damage is preferably below 40 (%), more preferably below 30 (%).
And the present invention's (6) compsn (X3ii) more preferably satisfies following (ii-6).
(ii-6) modulus in tension is preferably in the scope of 1MPa～1000MPa, more preferably in the scope of 1MPa～500MPa, further preferably in the scope of 1MPa～200MPa.
According to the softening temperature that the TMA method is measured, (be also referred to as rerum natura (2) or pin sometimes and go into temperature) can be described below and measure.
Use the SS-120 of Jinggong Co., Ltd's production or the Q-400 that TA Instrument company produces, the compacting sheet material test film of used thickness 1mm with the heat-up rate of 5 ℃/min, applies 2Kgf/cm on the pressure head of the plane of Φ 1.8mm 2Pressure, by the TMA curve try to achieve pin go into temperature (℃).
In addition, the measuring method of resilience spring rate (being also referred to as rerum natura (3) sometimes), Izod shock strength (being also referred to as rerum natura (4) sometimes), glossiness velocity of variation (being also referred to as rerum natura (5) sometimes), modulus in tension (being also referred to as rerum natura (6) sometimes), turbidity (being also referred to as rerum natura (7) sometimes) etc. following shown in.
(3) resilience spring rate
The resilience spring rate of measuring according to JISK6255 is preferably below 40%, more preferably below 35%, particularly preferably in below 30%.
(4) Izod shock strength
Strike out the test film of 12.7mm (wide) * 3.2mm (thick) * 64mm (length) by the thick compacting sheet material of 3mm, introduce the breach of mechanical workout, measure down, obtain the MV of measuring for three times at 0 ℃.
(5) glossiness velocity of variation
The glossiness velocity of variation of learning vibration damage test front and back is preferably below 40 (%), more preferably below 30 (%).
(6) modulus in tension
By the thick compacting sheet material of 1mm, according to JIS K6301, use the JIS3 dumb-bell test piece to carry out punching press with O dumbbell, be used to estimate sample.When measuring, for example, the tensile testing machine Inston 1123 that uses Instron company to produce under distance between bench marks: 30mm, draw speed 30mm/min, measures under 23 ℃, obtains the MV of three mensuration.
(7) turbidity
The compacting test film of used thickness 1mm is measured inner turbidity with the digital turbidometer " NDH-20D " that Japanese electric look Industrial Co., Ltd produces, and asks the MV of twice mensuration.
In addition, in above-mentioned explanation, in each test, use pressing make-up machine following after carrying out waste heat in 5 minutes～10 minutes at 200 ℃; Add at 10MPa and to depress, after being shaped with 1～2 minute, under 20 ℃; Depress in adding of 10MPa and to cool off, make the sheet material of specific thickness thus, obtain test film.
Graft modification
At least a portion or whole in the present invention's (6) the propylene polymer composition (X3), polar monomer capable of using carries out graft modification.
For example, both can or all carry out graft modification, also can or all carry out graft modification, and can also be directed against the part separately of (AA) composition, (B3) composition respectively or all carry out graft modification a part of of (B3) composition to a part of of (AA) composition.
As this polar monomer, can enumerate the ethene property unsaturated compound that contains hydroxyl, the ethene property unsaturated compound that contains amino, the ethene property unsaturated compound that contains epoxy group(ing), aromatic ethenyl compound, unsaturated carboxylic acid or derivatives thereof, vinyl ester compound, vinylchlorid, carbodiimide compound etc.
As polar monomer, be preferably the unsaturated carboxylic acid or derivatives thereof especially especially.As the unsaturated carboxylic acid or derivatives thereof, can enumerate the unsaturated compound with 1 above carboxylic acid group, compound and alkyl alcohol with carboxylic acid group ester, have 1 above acid anhydride's unsaturated compound etc.; As unsaturated group, can enumerate vinyl, vinylidene, unsaturated cyclic hydrocarbon radical etc.
As concrete compound; For example can enumerate vinylformic acid, toxilic acid, fumaric acid, tetrahydrophthalic acid, methylene-succinic acid, citraconic acid, butenoic acid, methylacrylic acid, Nadic acid (trade mark) unsaturated carboxylic acids such as (internally-oriented cis-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylicacid); Or derivatives thereof, for example acid halide, acid amides, imide, acid anhydride, ester etc.As the concrete example of these verivates, can enumerate for example Malaysia acyl chlorides, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, toxilic acid glycidyl ester etc.
These unsaturated carboxylic acids and/or its verivate can use a kind of separately, also can two or more combinations use.Wherein, be fit to use unsaturated dicarboxylic acid or its acid anhydrides, especially preferably use, toxilic acid, Nadic acid or their acid anhydrides.
Modification obtains through making be modified body and polar monomer graft polymerization.When being modified body and aforesaid polar monomer graft polymerization, with respect to the 100 weight parts body that is modified, polar monomer uses 1～100 weight part usually, preferably uses 5～80 weight parts.This graft polymerization is carried out in the presence of radical initiator usually.
As radical initiator, can use organo-peroxide or azo cpd etc.
Radical initiator can directly mix the back be modified body and polar monomer to be used, and also may be dissolved in a spot of organic solvent to re-use.As this organic solvent,, remove this not special qualification so long as the organic solvent of solubilized radical initiator can use.
In addition, when being modified body and polar monomer graft polymerization, also can use reducing substances.When using reducing substances, can improve the grafting amount of polar monomer.
The body that is modified utilizes the graft modification of polar monomer to carry out according to existing known method; For example; Can be dissolved in the organic solvent through the body that will be modified, then, polar monomer and radical initiator etc. added in the solution; 70～200 ℃, be preferably under 80～190 ℃ the temperature, react 0.5～15 hour, be preferably 1～10 hour and carry out.
And, also can use forcing machine etc., make be modified body and polar monomer reaction, make the modified propylene based polymer composition.This reaction is preferably usually more than the fusing point of body that is modified, particularly, (B3) composition is being carried out under the situation of modification, for example 120～300 ℃, be preferably under 120 ℃～250 ℃ the temperature, carried out usually 0.5～10 minute.And the body that is modified that contains (AA) composition is being carried out under the situation of modification, for example 160～300 ℃, be preferably under 180 ℃～250 ℃ the temperature, carried out usually 0.5～10 minute.
The modification amount of the modification body that obtains like this (the grafting amount of polar monomer) is being under the situation of 100 weight % with the modification body, is generally 0.1～50 weight %, is preferably 0.2～30 weight %, 0.2～10 weight % more preferably.
In the present invention (6), use these modification bodies, and as required, and be selected from the mixing more than a kind of unmodified body in (AA) composition and (B3) composition, at least a portion that can obtain the present invention (6) is by the propylene polymer composition of graft modification (X3).
And, polar monomer with respect at least a portion that obtains by aforesaid method by the content of propylene polymer composition (X3) the 100 weight % of polar monomer graft modification be generally 0.001～50 weight %, be preferably 0.001～10 weight %, more preferably 0.001～5 weight %, further be preferably 0.01～3 weight %.The control of polar monomer content can easily be carried out through for example suitably selecting the grafting condition.
Under the situation of at least a portion by the polar monomer graft modification of the propylene polymer composition (X3) of the present invention (6); Excellent with binding property, the intermiscibility of other resin, and can improve the wellability on the molding surface that obtains by propylene polymer composition sometimes.
In addition; Through making at least a portion graft modification of compsn; Not only have performances such as low-temperature impact resistance that the propylene polymer composition (X3) of the present invention (6) had, mechanical properties (rigidity or flexibility), thermotolerance, and can also add intermiscibility or binding property with other material sometimes.
In addition; Through making polar monomer; For example the content of unsaturated carboxylic acid and/or its verivate makes the polyolefin compositions (X3) of the present invention (6) demonstrate high bond strength with respect to the resin that contains polar group (for example polyester, Z 150PH, ethylene-vinyl alcohol copolymer, polymeric amide, PMMA, polycarbonate etc.) in above-mentioned scope.
In addition, at least a portion of the present invention (6), can be cooperated with other polymkeric substance, for example thermoplastic resin, elastomerics etc. in the scope of the characteristic that this modifier had by the propylene polymer composition of graft modification (X3).These both cooperated and can mix in the graft modification stage, also can after modification, mix.
The present invention's (6) propylene polymer composition (X3) is as long as in the scope of the object of the invention; As required, also can cooperate additives such as weather-proof stablizer, heat-resisting stabilizing agent, static inhibitor, slipproofing agent, antiblocking agent, antifogging agent, nucleator, lubricant, pigment, dyestuff, softening agent, inhibitor, hydrochloric acid absorbent, inhibitor.
The present invention's (6) propylene polymer composition (X3) can contain Vilaterm, isotactic Vestolen PP 7052 or styrene series elastomer, and the situation that does not contain Vilaterm, isotactic Vestolen PP 7052 or styrene series elastomer also is one of embodiment.
In addition, being the plasticity of the prolylene polymer composition (X3) that further improves the present invention (6), that is, is to improve Tc, accelerate crystallization velocity, can also contain the nucleator of specific any composition.In the case; Nucleator can be that for example biphenyl fork Sorbitol Powder is that nucleator, phosphate ester salt are that nucleator, rosin series nucleator, TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. metal-salt are nucleator, fluorinated polyethylene, 2; 2-methylene-bis (4, the 6-di-tert-butyl-phenyl) sodium phosphate, pimelic acid and salt, 2 thereof, 6-naphthoic acid dicarboxylicacid two Cyclohexamides etc.; The not special restriction of use level is about 0.1～1 weight part but be preferably with respect to propylene polymer composition.Not special restriction on cooperation opportunity can be between polymerization period, after the polymerization or be shaped to add and add man-hour.
The method of manufacture of propylene polymer composition (X3)
Aforesaid propylene polymer composition (X3) can be through adopting various known method with each composition in aforesaid scope; For example can adopt utilize slurry phase, solution mutually or gas phase with continous way or the multistage polymeric method of batch-type; Use the method for Henschel mixing roll, V-type mixing roll, ribbon blender (ribbon blender or revolving blender), drum tumbler; Or after mixing; Behind melting mixings such as single screw extrusion machine, twin screw extruder, kneader, Banbury, carry out the method for granulation or pulverizing and make.
Use the shaping of the propylene polymer composition formation of the present invention (4), (5) or (6) Body
Because aforesaid the present invention's (4) propylene polymer composition and aforesaid the present invention's (5) propylene polymer composition can obtain plasticity, excellent heat resistance; And flexibility, the transparency, anti-impaired property be the molding of excellence also; On the other hand; Because aforesaid the present invention's (6) propylene polymer composition can obtain plasticity, excellent heat resistance; And flexibility, anti-impaired property, vibration damping property, low-temperature impact property be the molding of excellence also; Therefore; Can be widely used in respectively and use existing syndiotactic polypropylenes unapproachable existing known polyolefine purposes in practicality, especially can the propylene polymer composition of the present invention (4), the present invention's (5) propylene polymer composition or the present invention's (6) propylene polymer composition (hereinafter also is generically and collectively referred to as them " propylene polymer composition (X) ") be configured as sheet material for example, not stretching or oriented film, filament, other different shape molding and utilize.And; The molding that uses propylene polymer composition (X) to form; The part that both can be molding contains propylene polymer composition (X), and promptly the part of molding can be used propylene polymer composition (X), also can all use propylene polymer composition (X) by molding.Use the example of propylene polymer composition (X) as the part of molding, can enumerate multilayer laminate.As multilayer laminate; Particularly; Being one of them layer is the multilayer body of the layer that contains propylene polymer composition (X), the multilayer film multilayer body that can enumerate multilayer film and sheet material, laminated vessel, multilayered tube, contains as one of moity of water-borne coatings etc.
As molding; Particularly, can enumerate the molding that obtains through known thermo shaping methods such as extrusion molding, injection forming, inflation shaping, blow molding, extrusion-blown modling shaping, injection blow molding shaping, press forming, vacuum forming, calendaring molding, foaming and molding, slush moulding shapings.Enumerate following numerical example and be illustrated as body.
Molding of the present invention is for for example to be extruded under the situation of body; To its shape and the not special qualification of goods kind; For example sheet material, film (not stretching), conduit (pipe), flexible pipe, wire covering materials, pipe (tube) etc. be can enumerate, sheet material (skin-material), film, pipe (tube), catheter (catheter), single strand (non-woven fabrics) etc. are preferably especially.
During propylene polymer composition (X) extrusion molding; Can adopt existing known extrusion device and molding condition; For example; Can use single screw extrusion machine, mixing extruder, plunger-type extruder (ram extruder), gear forcing machine etc., fused prolylene polymer composition (X) is extruded by specific mould etc., be configured as the shape of expection.
Oriented film stretches according to known drawing process such as for example tentering method (vertically and horizontally stretching, horizontal vertical stretching), the method for two-way stretch simultaneously, unilateral stretching methods through extrusion sheet or extrusion film as stated (not stretching) and obtains.
Stretching ratio when sheet material or non-stretched film stretch is generally about 20～70 times, and under the situation of unilateral stretching, is generally about 2～10 times under the situation of two-way stretch.Preferably obtain the oriented film about thickness 5～200 μ m through stretching.
In addition, as the film like molding, can make inflation film.Inflation is not prone to contraction (draw down) when being shaped.
The sheet material and the film shaped body that use propylene polymer composition (X) to form are difficult for charged; Mechanical characteristics, thermotolerance, retractility, shock resistance, resistance to deterioration, the transparency, see-through, glossiness, rigidity, moistureproofness and gas barrier property (gas barrier) excellence can be widely used as packaging film etc.
In the case, the sheet material and the film shaped body that use propylene polymer composition (X) to form both can be the multilevel shaping bodies, also can process the multilayer laminate that contains one deck propylene polymer composition (X) at least and use.
In addition, the filament formed body can be extruded and make by spinneret (spinning yarn mouth gold) by the propylene polymer composition (X) that for example makes fusion.Particularly, be fit to adopt spun-bond process, meltblown.The fiber that obtains so also can stretch again.As long as this stretching can make filament at least one axially be the degree of molecular orientation, preferably carry out usually with about 5～10 times multiplying power.The filament that contains propylene polymer composition (X) is difficult for charged, and the transparency, flexibility, thermotolerance and shock resistance, retractility are excellent.
Being injected into body and can using existing known injection molding device for molding, adopt known condition, is the different shape manufacturing with propylene polymer composition (X) injection forming.The body that is injected into that uses aforesaid propylene based polymer composition (X) and get is difficult for charged; Excellences such as the transparency, rigidity, thermotolerance, shock resistance, surface gloss, resistance to chemical reagents, wearability, can be widely used in automobile interior trim with decorative material, automobile with the shell of decorative material, tame electrical article, container etc.
Be blow molded into body and can use existing known blow molding apparatus, adopt known condition, propylene polymer composition (X) blow molding is made.In the case, the body that is blow molded into that is made up of propylene polymer composition (X) both can be the multilevel shaping body, and also one deck contains propylene polymer composition (X) at least.
For example, in extrusion-blown modling was shaped, propylene polymer composition (X) was under the molten state of 100 ℃～300 ℃ of resin temperatures; (die) extrudes the formation tubular parison through die head; After remaining on this parison in the mould with anticipated shape then, be blown into air, under 130 ℃～300 ℃ of resin temperatures; Be assemblied on the mould, just can make the hollow forming body.(blowing) multiplying power that stretches is preferably on the transverse direction about 1.5～5 times.
In addition, during injection blow molding was shaped, propylene polymer composition (X) was under 100 ℃～300 ℃ of resin temperatures; Be expelled in the parison mould; Form parison, be blown into air after remaining on this parison in the mould of intended shape then, under 120 ℃～300 ℃ of resin temperatures; Be assemblied on the mould, just can make the hollow forming body.(blowing) multiplying power that stretches is preferably on the longitudinal direction on 1.1～1.8 times, transverse direction about 1.3～2.5 times.
Not only the transparency, rigidity or flexibility, thermotolerance and shock resistance are excellent for the body that is blow molded into that use propylene polymer composition (X) forms, and moistureproofness is also excellent.
As compression forming body, can enumerate mold punching press (mold stamping) molding, for example base material and skin-material while press forming makes both compound, and the base material when being configured as one (mold drawing) can adopt propylene polymer composition (X) to form.
Mold as such strikes out body, specifically can enumerate inner decoration material for vehicle such as door trim material, boot finishing material, backrest backboard, panel board.
The compression forming body that uses propylene polymer composition (X) to form is difficult for excellences such as charged, rigidity or flexibility, thermotolerance, the transparency, shock resistance, resistance to deterioration, surface gloss, resistance to chemical reagents, wearability.
The foam molding that uses propylene polymer composition (X) to form can reach high foamability, and has good injecting formability, and has the high rigidity and the strength of materials.
Propylene polymer composition (X) can be made interior trim skin-material equal vacuum moldinies such as the panel board, door trim material of automobile.This molding is difficult for charged, excellences such as flexibility, thermotolerance, shock resistance, resistance to deterioration, surface gloss, resistance to chemical reagents, wearability.
Propylene polymer composition (X) can be made slush moulding powder moldinies such as automobile component, tame electrical article, toy, general merchandise.This molding is difficult for charged, excellences such as flexibility, thermotolerance, shock resistance, resistance to deterioration, surface gloss, resistance to chemical reagents, wearability.
In addition, as molding of the present invention, can enumerate the multilayer body that has the layer that one deck is made up of acrylic polymer (X) at least.
Propylene polymer composition of the present invention (X) is applicable to for example container or non-woven fabrics.As said vesse, can enumerate for example food product containers such as freezer storage container, high-temperature retort bag, bottle container etc.In addition, also can enumerate medical container, infusion bag etc.
As stated, propylene polymer composition of the present invention (X) for example can be widely used in that infusion bag, medical container, automotive interior/exterior material, carafe, clothing case, food product pack, high temperature steaming container, PET substitute, conduit (pipe), transparency carrier, transparent sealant, porous membrane, mask, electric capacity are material modified with film, multilayer body (comprising glass), foam, reflectance coating, pelletizing film, electric wire, sound insulating member, shock absorber part, foam material, material of construction, automobile skin-material, encapsulating material for solar cell, anti-radioactive rays film, anti-gamma-rays film, current mark, non-woven fabrics, material modified, shape-memory material, laminated glass-use film, bullet resistant material, splinter-proof glass be with purposes such as film, protective film, tackiness agent, compatibility agent (for example can carry out processing such as graft modification), shrink films.
[embodiment]
Below, in [example I]～[example VI], further specify the present invention (1)～(6) respectively.
[example I]
Below, further specifying the present invention (1) according to synthetic example and embodiment, the present invention is not limited to these embodiment.And dibenzyl methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, dimethylated methylene base (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride, dibenzyl methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, phenylbenzene methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride synthesize according to the said method of following patent documentation.
TOHKEMY 2000-212194 communique
TOHKEMY 2004-168744 communique
TOHKEMY 2004-189666 communique
The structure of the compound that is obtained by synthetic example is used 270MHz 1H-NMR (GSH-270 of NEC), FD-mass analysis decisions such as (SX-102A of NEC).
[synthetic routine 1-1]
Dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) dichloride Synthesizing of zirconium
(i) 2,7-two bromo-3,6-di-t-butyl-fluorenes synthetic
Under nitrogen environment, in the there-necked flask of 300mL, add according to Bull.Chem.Soc.Jpn. 59,97 (1986) described method synthetic 3,6-di-t-butyl-fluorenes 15.22g (54.7mmol) and Texacar PC 170ml, stirring.In this solution, add N-bromine succinimide 20.52g (115mmol), 80 ℃ of heated and stirred 5 hours.Naturally place cooling then, in 800mL water, add reaction soln, at room temperature stir 15 minutes after, the solid that filtering separation is separated out.The solid of gained is cleaned 5 times with ethanol 10mL.Then, add the mixing solutions of normal hexane and a spot of methylene dichloride, be heated to 60 ℃ fully after the dissolving, leave standstill a night at-20 ℃ to this solid.The crystallization of separating out is cleaned 3 times with hexane 5mL, obtains title product (receipts amount 21.16g, yield 76%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.60(s，tBu(Flu)，18H)，3.75(s，Flu-9H，2H)，7.73(s，Flu，2H)，7.81(s，Flu，2H).
MS(FD)：M/z?436(M +).
(ii) 2,7-phenylbenzene-3,6-di-t-butyl-fluorenes synthetic
Under nitrogen environment, in the there-necked flask of 300mL, to 2,7-two bromo-3,6-di-t-butyl-fluorenes 8.15g (18.7mmol), Pd (PPh 3) add among the 1.08g (0.93mmol) anhydrously 1,2-glycol dimethyl ether 120mL at room temperature stirred 20 minutes.The ethanol 20mL solution that in this solution, adds phenyl-boron dihydroxide 5.01g (41.1mmol) after at room temperature stirring 20 minutes, adds the aqueous sodium carbonate 37.4mL (74.8mmol) of 2.0mol/L.Then, reflux 18 hours after the placement cooling, under ice bath, is carried out chilling (quench) with Hydrogen chloride naturally.Add ether, extract soluble part, clean organic layer twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans twice with saturated aqueous common salt, uses dried over mgso then.Distillation removes and desolvates then, with the separating obtained solid of column chromatography, obtains title product (receipts amount 4.36g, yield 54%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.29(s，tBu(Flu)，18H)，3.78(s，Flu-9H，2H)，7.16(s，Flu，2H)，7.34(br，PhFlu，10H)，7.97(s，Flu，2H).
MS(FD)：M/z?430(M +).
(iii) 6,6-dibenzo fulvene synthetic
Under nitrogen environment, in the there-necked flask of 500mL, add cyclopentadiene 8.0g (121mmol) and anhydrous tetrahydro furan 100mL, stirring.With this mixing solutions of ice bath cooling, add the hexane solution 80mL (125.6mmol) of the n-Butyl Lithium of concentration 1.57mol/L.Then, at room temperature stirred 3 hours, after the white slurry with ice bath cooling gained, add 1,3-phenylbenzene-2-acetone 25.0g (118mmol) is dissolved in the solution that anhydrous tetrahydro furan 50mL forms.Then, at room temperature stirred 12 hours, with the yellow solution of saturated aqueous ammonium chloride chilling gained.Add normal hexane 100mL, extract soluble part, water, saturated aqueous common salt clean after this organic phase, use dried over mgso.Distillation removes and desolvates, and with the refining residue of column chromatography, obtains the title product (receipts amount 3.7g, yield 12%) of yellow solid shape.The identification and utilization of title product 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?3.69(s，PhCH 2，4H)，6.60-6.72(m，Cp，4H)，7.13-7.32(m，PhCH 2，10H).
(iv) dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-tert-butyl-fluorene) is synthetic
Under nitrogen environment,, add anhydrous tetrahydro furan mL and stirring in the 7-phenylbenzene-3,6-di-tert-butyl-fluorene 1.60g (3.71mmol) 2.With this solution of ice bath cooling, add the hexane solution 2.65mL (4.13mmol) of the n-Butyl Lithium of 1.56mol/L.At room temperature stirred 2 hours, the red solution that cools off gained with dry ice-methanol bath dripped 6, the THF 20mL solution of 6-dibenzo fulvene 1.06g (4.10mmol) to-78 ℃ with 20 minutes.Then, slowly be warmed up to room temperature, and stirred 18 hours.In the dark red solution of gained, add 1N hydrochloric acid 60mL, termination reaction.Add diethyl ether 80mL and carry out separatory, extract soluble part.Clean this organic layer twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso then.Distillation removes and desolvates, and is refining with silica gel chromatography, obtains the pulverous title product of yellow-white (receipts amount 0.59g, yield 23%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.25 (s, tBu (Flu), 18H), 2.66 (br, CpH, 1H), 3.22 (br, CH 2Ph, 4H), 4.41 (br, Flu-9H, 1H), 5.85-6.51 (m, Cp, 4H), 6.82-7.40 (m, Ph (Flu) and CH 2Ph and Flu, 22H), 7.67 (s, Flu, 2H).
MS(FD)：M/z?688(M +).
(v) dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100mL pipe, add dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl-fluorenes) 0.59g (0.855mmol), anhydrous diethyl ether 40mL, stirring.With this mixed slurry solution of ice bath cooling, add the hexane solution 1.21mL (1.88mmol) of the n-Butyl Lithium of concentration 1.56mol/L, slowly be warmed up to room temperature, and stirred 45 hours.Should be cooled to after-78 ℃ with dry ice/methanol bath by the redness reaction solution, add zirconium tetrachloride 0.200g (0.858mmol).Then, slowly be warmed up to room temperature, and stirred 42 hours, obtain orange red suspension liquid.Underpressure distillation under nitrogen, is dissolved in it in normal hexane after removing and desolvating, and through having filled diatomaceous glass filter, cleans with normal hexane, is not dissolved in the orange powder of normal hexane with dichloromethane extraction.The solvent of methylene dichloride dissolving part is removed in distillation, with diethyl ether/cold Skellysolve A cleaning-drying, forms orange powder, obtains title product (receipts amount 515mg, yield 71%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.30 (s, tBu (Flu), 18H), 3.82 (d, J=15.5Hz, CH 2Ph, 2H), 3.93 (d, J=15.5Hz, CH 2Ph, 2H), 5.80 (t, J=2.6Hz, Cp, 2H), 6.25 (t, J=2.6Hz, Cp, 2H), 6.97-7.34 (m, Ph (Flu) and CH 2Ph, 20H), 7.37 (s, Flu, 2H), 8.32 (s, Flu, 2H).
MS(FD)：M/z?848(M +).
[synthetic routine 1-2]
Two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) two Synthesizing of zirconium chloride
(i) 6,6-di-n-butyl fulvene synthetic
Under nitrogen environment, in the there-necked flask of 200mL, add methyl alcohol 15mL, tetramethyleneimine 11.8mL (146mmol).With the ice bath cooling, add butyl ketone 20.21g (144mmol), cyclopentadiene 11.0mL (146mmol), at room temperature stirred 22 hours.Add diethyl ether 100mL, water 100mL extracts soluble part, and water cleans this organic layer twice, cleans once with saturated aqueous common salt, uses dried over mgso.Distillation removes and desolvates, and with the refining residue of column chromatography, forms yellow oily, obtains title product (receipts amount 22.53g, yield 82%).The identification and utilization of title product 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.93(t，J＝7.3Hz，CH 2CH 2CH 2CH 3，6H)，1.38(sex，J＝7.3Hz，CH 2CH 2CH 2CH 3，4H)，1.53(quin，J＝7.3Hz，CH 2CH 2CH 2CH 3，4H)，2.53(t，J＝7.3Hz，CH 2CH 2CH 2CH 3，4H)，6.40-6.57(m，Cp，4H).
(ii) two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-tert-butyl-fluorene) is synthetic
Under nitrogen environment, at (ii) synthetic 2 of synthetic routine 1-1, add anhydrous tetrahydro furan 30mL in the 7-phenylbenzene-3,6-di-t-butyl-fluorenes 1.51g (3.51mmol) and stir.With this solution of ice bath cooling, add the hexane solution 2.50mL (3.90mmol) of the n-Butyl Lithium of 1.56mol/L.At room temperature stirred 2 hours, the dark red solution that cools off gained with dry ice-methanol bath dripped 6, the THF 15mL solution of 6-two (normal-butyl) fulvene 0.757g (3.98mmol) to-78 ℃ with 15 minutes.Then, slowly be warmed up to room temperature, stirred 18 hours.In the red solution of gained, add 1N hydrochloric acid 50mL, termination reaction.Add diethyl ether 100mL and carry out separatory, extract soluble part.Clean this organic layer twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso.Distillation removes and desolvates, and carries out recrystallization with hexane, forms white powder, obtains title product (receipts amount 1.54g, yield 70%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.72(t，J＝7.3Hz，CH 2CH 2CH 2CH 3，6H)，0.86-1.24(m，CH 2CH 2CH 2CH 3，8H)，1.26(s，tBu(Flu)，18H)，1.57-1.72(m，CH 2CH 2CH 2CH 3，4H)，2.68(br，CpH，1H)，3.97(br，Flu-9H，1H)，5.70-6.55(m，Cp，4H)，6.78(s，Flu，2H)，7.15-7.50(m，Ph(Flu)，10H)，7.81(s，Flu，2H).
MS(FD)：M/z?620(M +).
(iii) two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100mL pipe, add two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-tert-butyl-fluorene) 0.71g (1.15mmol), anhydrous diethyl ether 30mL, stirring.With this mixed slurry solution of ice bath cooling, add the hexane solution 1.62mL (2.53mmol) of the n-Butyl Lithium of 1.56mol/L, slowly be warmed up to room temperature, stirred 47 hours.Should be cooled to after-78 ℃ with dry ice/methanol bath by orange red reaction solution, add zirconium tetrachloride 0.265g (1.14mmol).Then, slowly be warmed up to room temperature, stirred 42 hours, obtain red suspension liquid.Underpressure distillation under nitrogen, is dissolved in it in normal hexane after removing and desolvating, and through having filled diatomaceous glass filter, cleans with normal hexane, is not dissolved in the red powder of normal hexane with dichloromethane extraction.The solvent that methylene dichloride dissolving part is removed in distillation carries out recrystallization with methylene dichloride/normal hexane, obtains the title product (receipts amount 217mg, yield 24%) of orange powder shape.The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 0.82 (t, J=7.3Hz, CH 2CH 2CH 2CH 3, 6H), 1.12-1.70 (m, CH 2CH 2CH 2CH 3, 8H), 1.24 (s, tBu (Flu), 18H), 2.30-2.60 (m, CH 2CH 2CH 2CH 3, 4H), 5.53 (t, J=2.6Hz, Cp, 2H), 6.26 (t, J=2.6Hz, Cp, 2H), 7.15-7.40 (m, Ph (Flu) and Flu, 12H), 8.19 (s, Flu, 2H).
MS(FD)：M/z?780(M +).
[synthetic routine 1-3]
Two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) two Synthesizing of zirconium chloride
(i) 2,7-dimethyl--3,6-di-t-butyl-fluorenes synthetic
Under nitrogen environment, to synthetic routine 1-1 (i) synthetic 2,7-two bromo-3,6-di-t-butyl-fluorenes 5.03g (11.5mmol), PdCl 2(dppf) CH 2Cl 20.196g add dry tert-butylmethyl ether 100mL, stirring (0.24mmol).With this solution of ice bath cooling, with the diethyl ether solution 19.2mL (57.6mmol) that dripped the methyl-magnesium-bromide of concentration 3mol/L in 15 minutes.Implement 5 days reflux.Naturally after placing cooling, under ice bath, drip 1N hydrochloric acid, termination reaction.Add diethyl ether and carry out separatory, clean organic layer twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso.Distillation removes and desolvates, and implements to separate with silica gel chromatography, forms white powder, obtains title product (receipts amount 2.07g, yield 63%).The identification and utilization of title product 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.50(s，tBu(Flu)，18H)，2.60(s，Me(Flu)，6H)，7.26(s，Flu，2H)，7.75(s，Flu，2H).
(ii) two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-tert-butyl-fluorene) is synthetic
Under nitrogen environment,, add anhydrous tetrahydro furan and stirring in the 7-dimethyl--3,6-di-t-butyl-fluorenes 0.783g (2.55mmol) 2.With this solution of ice bath cooling, add the hexane solution 1.85mL (2.85mmol) of the n-Butyl Lithium of 1.54mol/L.At room temperature stirred 2 hours, the orange solution that cools off gained with dry ice-methanol bath is to-78 ℃, and with synthetic routine 1-2 (i) synthetic 6 of dropping in 20 minutes, the anhydrous tetrahydro furan 15mL solution of 6-two (normal-butyl) fulvene 0.571g (3.00mmol) stirred 2 hours.In the orange solution of gained, add 1N hydrochloric acid 100mL, termination reaction.Add diethyl ether 100mL and carry out separatory, extract soluble part.Clean this organic layer twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso then.Distillation removes and desolvates, and carries out recrystallization with diethyl ether/methyl alcohol, forms white powder, obtains title product (receipts amount 0.63g, yield 50%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.76(t，J＝7.3Hz，CH 2CH 2CH 2CH 3，6H)，0.80-1.90(m，CH 2CH 2CH 2CH 3，10H)，1.46(s，tBu(Flu)，18H)，2.50(s，Me(Flu)，6H)，3.00(br，CpH，1H)，4.01(br，Flu-9H，1H)，5.85-6.70(m，Cp，4H)，6.93(s，Flu，2H)，7.60(s，Flu，2H).
MS(FD)：M/z?496(M +).
(iii) two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100mL pipe, add two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-tert-butyl-fluorene) 0.614g (1.24mmol), anhydrous diethyl ether 30mL, stirring.With this mixed slurry solution of ice bath cooling, add the hexane solution 1.78mL (2.74mmol) of the n-Butyl Lithium of 1.54mol/L, slowly be warmed up to room temperature, and stirred 16 hours.Should be cooled to after-78 ℃ with dry ice/methanol bath by orange red reaction solution, add zirconium tetrachloride 0.239g (1.02mmol).Then, slowly be warmed up to room temperature, and stirred 22 hours, obtain the sorrel suspension liquid.Underpressure distillation under nitrogen, is dissolved in it in normal hexane after removing and desolvating, and through having filled diatomaceous glass filter, cleans with normal hexane, is not dissolved in the red powder of normal hexane with dichloromethane extraction.The solvent of methylene dichloride dissolving part is removed in distillation, with methylene dichloride/normal hexane recrystallization, obtains the title product (receipts amount 286mg, yield 41%) of orange powder shape.The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.99(t，J＝7.3Hz，CH 2CH 2CH 2CH 3，6H)，1.30-1.78(m，CH 2CH 2CH 2CH 3，8H)，1.46(s，tBu(Flu)，18H)，2.53(s，Me(Flu)，2.60-2.80(m，CH 2CH 2CH 2CH 3，4H)，5.60(t，J＝2.6Hz，Cp，2H)，6.21(t，J＝2.6Hz，Cp，2H)，7.38(s，Flu，2H)，7.95(s，Flu，2H).
MS(FD)：M/z 656(M +).
[synthetic routine 1-4]
Two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) Synthesizing of zirconium dichloride
(i) 6,6-two (rubigan) fulvene synthetic
Under nitrogen environment; In the reaction vessel that addition funnel has been installed, add anhydrous tetrahydro furan 40mL and cyclopentadiene 2.15mL (25.89mmol); This solution is cooled to 0 ℃, and slowly drips the hexane solution 18mL (28.47mmol) and the stirring of the n-Butyl Lithium of 1.58mol/L.In addition funnel, add then be dissolved with 4,4 '-the THF 30mL solution of dichloro benzophenone 5.00g (19.91mmol), slowly drip, directly be returned to room temperature, stirred one day.Extract this reaction solution with diethyl ether, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, use dried over mgso, underpressure distillation removes and desolvates, and makes with extra care with silicagel column, obtains title product (receipts amount 3.37g, yield 57%).The identification and utilization of title product 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?6.21-6.24(m，2H)，6.60-6.63(m，2H)，7.23(d，2H，J＝8.1Hz)，7.37(d，2H，J＝8.6Hz).
(ii) two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-tert-butyl-fluorene) is synthetic
Under nitrogen environment, in the there-necked flask of 200mL, add (ii) synthetic 2 of synthetic routine 1-1,7-phenylbenzene-3,6-di-tert-butyl-fluorene 3.5g (8.1mmol) and anhydrous tetrahydro furan 100mL also stir.To-78 ℃, drip the hexane solution 5.7mL (8.87mmol) of the n-Butyl Lithium of 1.56mol/L with dry ice-this solution of methanol bath cooling.Then, at room temperature stirred 3 hours, the solution of gained is cooled to-40 ℃ once more, drip 6, the tetrahydrofuran solution of 6-two (rubigan) fulvene 2.22g (7.39mmol) at room temperature stirred 5 hours.Then, use the diluted hydrochloric acid aqueous solution chilling.In reaction solution, add normal hexane 100mL, extract soluble part, clean this organic layer, use dried over mgso with saturated sodium bicarbonate aqueous solution, water, saturated aqueous common salt.Then, after solvent concentrated,, obtain title product (receipts amount 3.2g, yield 54%) with normal hexane, washed with methanol.The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.2(s，18H)，2.9(s，2H)，5.2(s，1H)，6.0(d，1H)，6.2(d，1H)，6.3(s，1H)，6.6(s，2H)，6.9(s，10H)，7.2-7.4(m+s，8H)，7.6(s，2H)，
MS(FD)：M/z?729(M +)
(iii) two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl-fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100mL pipe, add two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl-fluorenes) 1.0g (1.4mmol) and anhydrous diethyl ether 60mL, stirring.After-78 ℃, drip the hexane solution 1.8mL (2.88mmol) of the n-Butyl Lithium of 1.56mol/L with this solution of dry ice/methanol bath cooling, at room temperature stirred 20 hours.Then, be cooled to after-60 ℃, add zirconium tetrachloride 0.37g (1.59mmol), at room temperature stirred 20 hours with dry ice/methanol bath.Underpressure distillation under nitrogen, with normal hexane and dichloromethane extraction residue, is carried out the recrystallization from each solution after removing and desolvating, and obtains title product (receipts amount 0.47g, yield 38%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.2(s，18H)，5.4(m，2H)，5.8(s，2H)，6.3(m，2H)，7-7.2(s+m+m，6H)，7.5-7.7(m，12H)，8.3(s，2H)
MS(FD)：M/z?888(M +)
[synthetic routine 1-5]
Two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl-fluorenyl) Synthesizing of zirconium dichloride
(i) two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl-fluorenes) is synthetic
Under nitrogen environment, in the there-necked flask of 200mL, add synthetic routine 1-3 (i) synthetic 2,7-dimethyl--3,6-di-t-butyl-fluorenes 2.6g (8.48mmol) and anhydrous tetrahydro furan 100mL also stir.,, at room temperature stirred 3 hours behind the hexane solution 5.7mL (8.9mmol) of the n-Butyl Lithium of dropping concentration 1.56mol/L to-78 ℃ with this mixing solutions of ice bath cooling; Then, the solution of gained is cooled to-40 ℃ once more with dry ice/methanol bath, drips and dissolved synthetic routine 1-4 (i) synthetic 6; The tetrahydrofuran solution 60mL of 6-two (rubigan) fulvene 2.78g (9.33mmol); Then, slowly be warmed up to room temperature, stirred 1 hour.In reaction soln, add 1N hydrochloric acid 100mL, add normal hexane 100mL, extract soluble part, after water, saturated aqueous common salt clean this organic layer, use dried over mgso.Then, distillation removes desolvates, will be from normal hexane the recrystallization residue, obtain title product (receipts amount 4.4g, yield 86%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.3(s，18H)，2.3(s，6H)，3.0(s，2H)，5.2(s，2H)，6.1-6.3(s，4H)，6.7(s，2H)，7.0(s，6H)，7.4(s，2H)
MS(FD)：M/z?604(M +)
(ii) two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl-fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100mL pipe, add two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl-fluorenes) 1.0g (1.65mmol) and anhydrous diethyl ether 50mL, stirring.After-40 ℃, add the hexane solution 2.2mL (3.38mmol) of the n-Butyl Lithium of concentration 1.56mol/L with this mixed slurry solution of dry ice/methanol bath cooling, slowly be warmed up to room temperature, and stirred 22 hours.With dry ice/methanol bath this reaction solution is cooled to after-78 ℃, adds zirconium tetrachloride 0.38g (1.65mmol), slowly be warmed up to room temperature then, and stirred 20 hours.After underpressure distillation removes and desolvates, under nitrogen, add the about 30mL of normal hexane, after the stirring, remove insolubles with diatomite filtration.And then, remove insolubles with diatomite filtration with this insolubles of methylene dichloride dissolving.After will using the solution concentration of normal hexane extraction, clean the solid of separating out, obtain title product (receipts amount 0.122g, yield 10%) with normal hexane, Skellysolve A.The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.5(s，18H)，2.3(s，6H)，5.6(m，2H)，6.0(m，2H)，6.3(m，2H)，7.3(dd，2H)，7.4(dd，2H)，7.7(dd，2H)，7.8(dd，2H)，8.1(s，2H)
MS(FD)：M/z?764(M +)
[synthetic routine 1-6]
Two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-two uncle's fourths The base fluorenyl) zirconium dichloride is synthetic
(i) 6,6-two (m-trifluoromethylphenyl) fulvene synthetic
Under nitrogen environment, in anhydrous tetrahydro furan 70mL, add cyclopentadiene 2.08mL (25.14mmol), stir.This solution is cooled to 0 ℃, drips the hexane solution 16.3mL (25.77mmol) of the n-Butyl Lithium of concentration 1.58mol/L.After at room temperature stirring 20 hours, once more solution is cooled to 0 ℃, with 3,3 '-two (trifluoromethyl) the UVNUL MS-40 4.08g (12.6mmol) among 15 minutes dropping anhydrous tetrahydro furan 30mL.At room temperature stirred 2.5 hours, with 1N hydrochloric acid termination reaction.Carry out separatory, extract water layer twice,, after saturated sodium bicarbonate aqueous solution, water, saturated aqueous common salt cleaning, use dried over mgso with organic layer merging before with diethyl ether.Distillation removes and desolvates, and separates with silica gel chromatography, obtains title product (receipts amount 1.2g, yield 26%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?6.17-6.21(m，2H)，6.64-6.66(m，2H)，7.44-7.58(m，6H)，7.68(d，2H).
MS(FD)：m/z?366(M +).
(ii) two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-tert-butyl-fluorene) is synthetic
Under nitrogen environment, in the there-necked flask of 300mL, add (ii) synthetic 2 of synthetic routine 1-1,7-phenylbenzene-3,6-di-t-butyl-fluorenes 2.1g (6.85mmol) and anhydrous tetrahydro furan 60mL also stir.This solution is cooled to 0 ℃, adds the hexane solution 4.83mL (7.5mmol) of the n-Butyl Lithium of concentration 1.56mol/L.Then, at room temperature stir 2 hours.The solution of gained is cooled to-78 ℃ with dry ice/methanol bath, dripped with 15 minutes and be dissolved in 6 among the anhydrous tetrahydro furan 50mL, 6-two (m-trifluoromethylphenyl) fulvene 2.39g (6.52mmol).Stirred 10 minutes, and in reaction soln, added 1N hydrochloric acid, termination reaction.Implement oily water separation, water layer is extracted twice,, after saturated sodium bicarbonate aqueous solution, water, saturated aqueous common salt cleaning, use dried over mgso with organic layer merging before with diethyl ether 50mL.Distillation removes and desolvates, and residue 4.8g is dissolved among the methylene dichloride 15mL, drips methyl alcohol 300mL.Methanol solution is cooled to 0 ℃, and the crystallization of filtering separation gained obtains title product (receipts amount 2.3g, yield 50%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.37(s，18H)，2.35(s，6H)，3.16(s，1H)，5.30(s，1H)，6.38-6.52(m，2H)，6.86(m，2H)，7.06-7.28(m，12H).
MS(FD)：m/z?673(M +).
(iii) two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100mL pipe, add two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-tert-butyl-fluorene) 0.672g (1mmol) and anhydrous diethyl ether 40mL, stirring.To-78 ℃, add the hexane solution 1.3mL (2.05mmol) of the n-Butyl Lithium of concentration 1.56mol/L with this solution of dry ice/methanol bath cooling, at room temperature stirred 19 hours, up to making white casse solution be orange transparent.This reaction solution is cooled to after-78 ℃ with dry ice/methanol bath once more, adds zirconium tetrachloride 0.23g (1mmol).Then, slowly be warmed up to room temperature, and stirred 23 hours.Underpressure distillation removes and desolvates, and under nitrogen, adds the about 50mL of normal hexane, removes insolubles with diatomite filtration.The hexane solution of gained is concentrated to about 5mL, left standstill 24 hours at-18 ℃.The solid that filtration is separated out cleans with normal hexane, Skellysolve A, forms orange powder, obtains title product (receipts amount 0.2g, yield 24%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.44(s，18H)，2.20(s，6H)，5.59(d，2H)，5.80(m，2H)，6.31(m，2H)，7.19-8.14(m，10H).
MS(FD)：m/z?833(M +).
[synthetic routine 1-7]
Cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride Synthetic
(i) cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-tert-butyl-fluorene) is synthetic
Under nitrogen environment,, add anhydrous tetrahydro furan 30mL in the 7-phenylbenzene-3,6-di-t-butyl-fluorenes 1.14g (2.65mmol) and stir to (ii) synthetic 2 of synthetic routine 1-1.With this solution of ice bath cooling, add the hexane solution 1.90mL (2.96mmol) of the n-Butyl Lithium of 1.56mol/L.At room temperature stirred 2 hours.Be cooled to after-78 ℃ with the dark red solution of dry ice-methanol bath, with the tetrahydrofuran solution 20mL of dropping in 15 minutes according to the said method synthetic of japanese kokai publication hei 2000-26490 cyclohexyl fulvene 0.49g (3.35mmol) with gained.Slowly be warmed up to room temperature then, and stirred 19 hours.In the dark red solution of gained, add 1N hydrochloric acid 30mL, termination reaction.Add diethyl ether 100mL and carry out separatory, extract soluble part.Clean organic layer twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso then.Distillation removes and desolvates, and utilizes diethyl ether and methyl alcohol to carry out recrystallization, forms buff powder, obtains title product (receipts amount 0.98g, yield 64%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.26(s，tBu(Flu)，18H)，0.90-1.85(m，C6，10H)，2.75(br，CpH，1H)，3.79(br，Flu-9H，1H)，5.80-6.52(m，Cp，4H)，6.73(s，Flu，2H)，7.20～7.60(m，Ph(Flu)，10H)，7.82(s，Flu，2H).
MS(FD)：M/z?577(M +).
(ii) cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100mL pipe, add cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-tert-butyl-fluorene) 0.98g (1.70mmol), anhydrous diethyl ether 40mL, stirring.With this mixed slurry solution to 0 of ice bath cooling ℃, add the hexane solution 2.40mL (3.74mmol) of the n-Butyl Lithium of 1.56mol/L, slowly be warmed up to room temperature, and stirred 23 hours.Should be cooled to after-78 ℃ with dry ice/methanol bath by the redness reaction solution, add zirconium tetrachloride 0.391g (1.68mmol).Then, slowly be warmed up to room temperature, and stirred 22 hours, obtain orange suspension liquid.,, under nitrogen, it is dissolved in the normal hexane except that after desolvating through underpressure distillation,, cleans, be not dissolved in the red powder of normal hexane with dichloromethane extraction with normal hexane through having filled diatomaceous glass filter.The solvent of methylene dichloride dissolving part is removed in distillation, cleans with cold diethyl ether/cold normal hexane, obtains orange solids shape title product (receipts amount 0.71g, yield 57%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.25 (s, tBu (Flu), 18H), 1.45-1.90 (m, C6,6H); 2.10-2.35 (m, C6,2H), 2.85-3.00 (m, C6,2H), 5.55 (t; J=2.6Hz, Cp, 2H), 6.29 (t, J=2.6Hz, Cp, 2H); 7.15-7.45 (m, Ph (Flu) and Flu, 12H), 8.22 (s, Flu, 2H).
MS(FD)：M/z?736(M +).
[synthetic routine 1-8]
Dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [2-naphthyl]-3,6-di-t-butyl fluorenyl) dichloro Change the synthetic of zirconium
(i) 2,7-two (2-naphthyl)-3,6-di-t-butyl-fluorenes synthetic
Under nitrogen environment, to synthetic routine 1-1 (i) synthetic 2, add anhydrously 1 in 7-two bromo-3,6-di-t-butyl-fluorenes 3.02g (6.92mmol), Pd (PPh3) 0.40g (0.35mmol), 2-glycol dimethyl ether 45mL at room temperature stirred 20 minutes.Add the ethanol 15mL solution of 2-naphthalene boronic acids 2.62g (15.2mmol) to this solution.After at room temperature stirring 20 minutes, add the aqueous sodium carbonate 13.8mL (27.7mmol) of 2.0mol/L.Reflux 21 hours.Naturally after placing cooling, under ice bath, with 1N hydrochloric acid termination reaction.Add methylene dichloride and carry out separatory, water layer is extracted twice, with organic layer merging before with diethyl ether.Clean twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso.Distillation removes and desolvates, and separates with silica gel chromatography.In the yellow-white powder of gained, add the mixing solutions of normal hexane and a spot of methylene dichloride, be heated to 65 ℃ of dissolvings fully.At room temperature leave standstill after the night, clean the crystallization separate out three times, form white powder, obtain title product (receipts amount 2.71g, yield 74%) with normal hexane 10mL.The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.32(s，tBu(Flu)，18H)，3.81(s，Flu-9H，2H)，7.22(s，Flu，2H)，7.46-7.52(m，NapFlu，6H)，7.77-7.90(m，NapFlu，8H)，8.03(s，Flu，2H).
MS(FD)：M/z?530(M +).
(ii) dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [2-naphthyl]-3,6-di-tert-butyl-fluorene) is synthetic
Under nitrogen environment,, add dry tert-butylmethyl ether 80mL and stirring among the 7-two (2-naphthyl)-3,6-di-t-butyl-fluorenes 0.82g (1.54mmol) 2.With this solution of ice bath cooling, add the hexane solution 1.10mL (1.76mmol) of the n-Butyl Lithium of 1.60mol/L.At room temperature stirred 22 hours, and in the yellow suspension liquid of gained, added (iii) synthetic 6 of synthetic routine 1-1,6-dibenzo fulvene 0.44g (1.70mmol).Reflux 19 hours.In the greenish orange brown solution of gained, add 1N hydrochloric acid 30mL termination reaction.Add diethyl ether 100mL and carry out separatory, extract soluble part.Clean this organic layer twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso then.Distillation removes and desolvates, and with the refining residue of column chromatography, obtains faint yellow solid title product (receipts amount 0.64g, yield 53%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.28 (s, tBu (Flu), 18H), 2.65 (br, CpH, 1H), 3.28 (br, CH 2Ph, 4H), 4.46 (br, Flu-9H, 1H), 5.85-6.48 (m, Cp, 4H), 6.80-7.92 (m, Nap (Flu) and CH 2Ph and Flu, 26H).
MS(FD)：M/z?788(M +).
(iii) dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100mL pipe, add dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [2-naphthyl]-3,6-di-tert-butyl-fluorene) 0.64g (0.811mmol), anhydrous diethyl ether 40mL, stirring.With this mixed slurry solution of ice bath cooling, add the hexane solution 1.14mL (1.82mmol) of the n-Butyl Lithium of 1.60mol/L, slowly be warmed up to room temperature, and stirred 42 hours.Should be cooled to after-78 ℃ with dry ice/methanol bath by the redness reaction solution, add zirconium tetrachloride 0.180g (0.772mmol).Then, slowly be warmed up to room temperature, and stirred 47 hours, obtain orange suspension liquid.,, under nitrogen, it is dissolved in the normal hexane except that after desolvating through underpressure distillation,, cleans, be not dissolved in the red powder of normal hexane with dichloromethane extraction with normal hexane through having filled diatomaceous glass filter.The solvent that methylene dichloride dissolving part is removed in distillation cleans with diethyl ether/normal hexane, obtains orange red Powdered title product (receipts amount 379mg, yield 49%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.35 (s, tBu (Flu), 18H), 3.72-4.00 (m, CH 2Ph, 4H), 5.83 (br, Cp, 2H), 6.52 (br, Cp, 2H), 6.95-7.90 (m, Nap (Flu) and CH 2Ph, 26H), 8.40 (s, Flu, 2H).
MS(FD)：M/z?948(M +).
[synthetic routine 1-9]
Dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [p-methylphenyl]-3,6-di-t-butyl fluorenyl) Synthesizing of zirconium dichloride
(i) 2,7-two [p-methylphenyl]-3,6-di-t-butyl-fluorenes synthetic
Under nitrogen environment, at synthetic routine 1-1 (i) synthetic 2,7-two bromo-3,6-di-t-butyl-fluorenes 8.00g (18.3mmol), Pd (PPh 3) add among the 1.05g (0.909mmol) anhydrously 1,2-glycol dimethyl ether 120mL at room temperature stirred 20 minutes.In this solution, add the ethanol 20mL solution of 4-aminomethyl phenyl boric acid 5.50g (40.5mmol).After at room temperature stirring 20 minutes, add the aqueous sodium carbonate 36.8mL (73.6mmol) of 2.0mol/L.Reflux 21 hours.Naturally after placing cooling, under ice bath, add 1N hydrochloric acid, termination reaction.Add methylene dichloride and carry out separatory, extract water layer twice, with organic layer merging before with diethyl ether.Clean twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso.Distillation removes and desolvates, and separates with silica gel chromatography.In the white yellow powder of gained, add a small amount of normal hexane and alcoholic acid mixing solutions, be heated to 65 ℃, at room temperature leave standstill one hour after; Clean the crystallization of separating out 10 times with cold ethanol 2mL; Clean 20 times with cold normal hexane 1mL, obtain white powder title product (receipts amount 6.95g, yield 83%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.29 (s, tBu (Flu), 18H), 2.41 (s, MePhFlu, 6H), 3.76 (s, Flu-9H, 2H), 7.12～7.26 (m, Flu and MePhFlu, 10H), 7.95 (s, Flu, 2H).
MS(FD)：M/z?458(M +).
(ii) dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [p-methylphenyl]-3,6-di-tert-butyl-fluorene) is synthetic
Under nitrogen environment,, add dry tert-butylmethyl ether 100mL and stirring among the 7-two [p-methylphenyl]-3,6-di-t-butyl-fluorenes 1.30g (2.84mmol) 2.With this solution of ice bath cooling, add the hexane solution 2.10mL (3.36mmol) of the n-Butyl Lithium of 1.60mol/L.At room temperature stirred 21 hours.In the blackyellow suspension liquid of gained, add (iii) synthetic 6 of synthetic routine 1-1,6-dibenzo fulvene 0.808g (3.12mmol).Carry out 19 hours reflux.In the gained red tan solution, add 1N hydrochloric acid 30mL, termination reaction.Add diethyl ether 100mL and carry out separatory, extract soluble part.Clean this organic layer twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso.Distillation removes and desolvates, with chromatographic column separating residual thing.Clean the white yellow powder 1 time of gained with cold hexane 10mL, clean 3 times,, obtain white powder title product (receipts amount 1.04g, yield 51%) with cold hexane 2mL cleaning 3 times with cold ethanol 5mL.The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.25 (s, tBu (Flu), 18H), 2.38 (s, MePhFlu, 6H), 2.69 (br, CpH, 1H), 3.27 (br, CH 2Ph, 4H), 4.40 (br, Flu-9H, 1H), 5.80-6.48 (m, Cp, 4H), 6.80-7.30 (m, MePh (Flu) and CH 2Ph and Flu, 20H), 7.66 (s, Flu, 2H).
MS(FD)：M/z?717(M +).
(iii) dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [p-methylphenyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100mL pipe, add dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [p-methylphenyl]-3,6-di-tert-butyl-fluorene) 1.04g (1.45mmol), anhydrous diethyl ether 60mL, stirring.With this mixed slurry solution of ice bath cooling, add the hexane solution 2.00mL (3.20mmol) of the n-Butyl Lithium of 1.60mol/L, slowly be warmed up to room temperature, and stirred 51 hours.Should be cooled to after-78 ℃ with dry ice/methanol bath by orange red reaction solution, add zirconium tetrachloride 0.363g (1.60mmol).Then, slowly be warmed up to room temperature, and stirred 43 hours, obtain orange suspension liquid.,, under nitrogen, it is dissolved in the normal hexane except that after desolvating through underpressure distillation,, cleans, be not dissolved in the orange powder of normal hexane with dichloromethane extraction with normal hexane through having filled diatomaceous glass filter.The solvent that methylene dichloride dissolving part is removed in distillation cleans with diethyl ether/normal hexane, obtains orange powder shape title product (receipts amount 744mg, yield 58%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.32 (s, tBu (Flu), 18H), 2.37 (s, MePhFlu, 6H), 3.86 (d, J=15.5Hz, CH 2Ph, 2H), 3.94 (d, J=15.5Hz, CH 2Ph, 2H), 5.81 (t, J=2.6Hz, Cp, 2H), 6.46 (t, J=2.6Hz, Cp, 2H), 6.90-7.40 (m, MePh (Flu) and CH 2Ph and Flu, 20H), 8.32 (s, Flu, 2H).
MS(FD)：M/z?876(M +).
[synthetic routine 1-10]
Dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [o-tolyl]-3,6-di-t-butyl fluorenyl) Synthesizing of zirconium dichloride
(i) 2,7-two [p-methylphenyl]-3,6-di-t-butyl-fluorenes synthetic
Under nitrogen environment, at synthetic routine 1-1 (i) synthetic 2,7-two bromo-3,6-di-t-butyl-fluorenes 3.50g (8.02mmol), Pd 2(dba) 30.186g (0.20mmol), P (tBu) 30.115g (0.57mmol), add anhydrous tetrahydro furan 50mL among the Tripotassium phosphate 6.81g (32.1mmol), at room temperature stirred 20 minutes.In this solution, add the anhydrous tetrahydro furan 15mL solution of o-tolyl boric acid 2.73g (20.0mmol).Reflux is 72 hours then.Naturally after placing cooling, under ice bath, add 1N hydrochloric acid, termination reaction.Add diethyl ether and carry out separatory, extract water layer twice, with organic layer merging before with diethyl ether.Clean twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso.Distillation removes and desolvates, and separates with silica gel chromatography.Obtain white powder title product (receipts amount 0.532g, yield 14%).The identification and utilization of title product 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.27(s，tBu(Flu)，18H)，2.07(s，Me(o-tolyl)，6H)，3.79(s，Flu-9H，2H)，7.07(s，Flu，2H)，7.19-7.25(m，o-tolylFlu，10H)，8.00(s，Flu，2H).
(ii) dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [o-tolyl]-3,6-di-tert-butyl-fluorene) is synthetic
Under nitrogen environment,, add dry tert-butylmethyl ether 40mL and stirring among the 7-two [p-methylphenyl]-3,6-di-t-butyl-fluorenes 0.92g (2.00mmol) 2.With this solution of ice bath cooling, add the hexane solution 1.45mL (2.20mmol) of the n-Butyl Lithium of 1.52mol/L.At room temperature stirred 4 hours.With the red solution of ice bath cooling gained, synthesize (iii) synthetic 6 of routine 1-1, the THF solution 20mL of 6-dibenzo fulvene 0.58g (2.24mmol) with dropping in 25 minutes.Slowly be warmed up to room temperature, and stirred 18 hours, reflux is 3 hours then.After the dark red solution of gained placed cooling naturally, interpolation 1N hydrochloric acid under ice bath, termination reaction.Add diethyl ether and carry out separatory, extract water layer twice, with organic layer merging before with diethyl ether.Clean twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso.Distillation removes and desolvates, and separates with silica gel chromatography, obtains yellow powder.In this yellow powder, add hexane and ethanol mixed solvent, be heated to 60 ℃ of dissolvings fully.Under-20 ℃, leave standstill an evening.Clean the crystallization of separating out with ethanol, obtain pale yellow powder shape title product (receipts amount 0.57g, yield 40%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.21-1.23 (m, tBu (Flu), 18H), 1.96-1.99 (m, CH 3(o-tolyl), 3H), 2.14-2.19 (m, CH 3(o-tolyl), 3H), 2.66 (br, CpH, 1H), 3.06-3.34 (br, CH 2Ph, 4H), 4.45 (br, Flu-9H, 1H), 5.80-6.48 (br, Cp, 4H), 6.75-7.20 (m, o-tolyl (Flu) and CH 2Ph and Flu, 20H), 7.64-7.79 (m, Flu, 2H).
MS(FD)：M/z?716(M +).
(iii) dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [o-tolyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 50mL pipe, add dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-two [o-tolyl]-3,6-di-tert-butyl-fluorene) 0.36g (0.50mmol), anhydrous diethyl ether 25mL, stirring.With this mixed slurry solution of ice bath cooling, add the hexane solution 0.72mL (1.09mmol) of the n-Butyl Lithium of concentration 1.52mol/L, slowly be warmed up to room temperature, stirred 40 hours.Should be cooled to after-78 ℃ with dry ice/methanol bath by the redness reaction solution, add zirconium tetrachloride 0.251g (1.08mmol).Then, slowly be warmed up to room temperature, and stirred 17 hours, obtain orange red suspension liquid.After the drying under reduced pressure solvent, under nitrogen, it is dissolved in the normal hexane, through having filled diatomaceous glass filter, clean with normal hexane, be not dissolved in the orange powder of normal hexane with dichloromethane extraction.The solvent of methylene dichloride dissolving part is removed in distillation, cleans with diethyl ether/cold normal hexane, and drying obtains the Powdered title product of dark peachiness (receipts amount 167mg, yield 38%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.28-1.33 (m, tBu (Flu), 18H), 1.68,1.87,2.16 (s, s, s, CH 3(o-tolyl), 6H), 3.34-4.30 (m, CH 2Ph, 4H), 5.73-5.82 (m, Cp, 2H), 6.45-6.48 (m, Cp, 2H), 6.95-7.30 (m, o-tolyl (Flu) and CH 2Ph, 18H), 7.48 (s, Flu, 2H), 8.37-8.41 (m, Flu, 2H).
MS(FD)：M/z?876(M +).
[synthetic routine 1-11]
Two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) two Synthesizing of zirconium chloride
(i) two (4-benzyl chloride base) ketone is synthetic
Under nitrogen environment, in the there-necked flask of 500mL, add dicyclohexyl carbodiimide 15.12g (73.3mmol) and dimethyl aminopyridine 2.24g (18.3mmol), add anhydrous methylene chloride 150mL then, at room temperature stir.In this solution, drip and be dissolved in the 4-chlorophenylacetic acid 12.50g (73.3mmol) among the anhydrous methylene chloride 120mL.After at room temperature stirring 3, filter the white crystals of separating out with paulownia mountain funnel.To filtrate concentrates, and with silica gel chromatography separating residual thing, obtains the mixture of white crystals/yellow oil.In this mixture, add ethanol, be heated to 50 ℃, after the dissolving, at room temperature leave standstill an evening fully.Clean the crystallization of separating out with small amount of ethanol, obtain white powder title product (receipts amount 5.52g, yield 54%).The identification and utilization of title product 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?3.69(s，4-Cl-PhCH 2，4H)，7.05(d，4-Cl-PhCH 2，4H)，7.28(d，4-Cl-PhCH 2，4H).
(ii) 6,6-two (4-benzyl chloride base) fulvene synthetic
Under nitrogen environment, in the there-necked flask of 100mL, add cyclopentadiene lithium 0.66g (9.22mmol), anhydrous THF 10mL, stirring.With dry ice/methanol bath cooling (78 ℃) this solution, drip two (4-benzyl chloride base) the ketone 2.50g (8.96mmol) that are dissolved among the anhydrous THF 15mL.Slowly be warmed up to room temperature, and stirred 17 hours, in the black dark brown solution of gained, add 1N hydrochloric acid, termination reaction.Add hexane and carry out separatory, with hexane extraction water layer twice, with organic layer merging before.With saturated sodium bicarbonate aqueous solution clean twice, water clean twice, clean once with saturated aqueous common salt, use dried over mgso.Distillation removes and desolvates, and with the refining residue of column chromatography, obtains yellow powder shape title product (receipts amount 0.65g, yield 22%).The identification and utilization of title product 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?3.65(s，PhCH 2，4H)，6.64(s，Cp，4H)，7.02(d，4-Cl-PhCH 2，4H)，7.23(d，4-Cl-PhCH 2，4H).
(iii) two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-tert-butyl-fluorene) is synthetic
Under nitrogen gas stream,, add anhydrous THF15mL in the 7-phenylbenzene-3,6-di-t-butyl-fluorenes 0.69g (1.60mmol) and stir to (ii) synthetic 2 of synthetic routine 1-1.This solution with dry ice/methanol bath cooling (78 ℃), is added the hexane solution 1.26mL (1.92mmol) of the n-Butyl Lithium of 1.52mol/L.Slowly be warmed up to room temperature, and stirred 19 hours.The dark red solution of gained is cooled off (78 ℃) with dry ice-methanol bath, dripped with 20 minutes and be dissolved in 6 among the THF10mL, 6-two (4-benzyl chloride base) fulvene 0.62g (1.88mmol).Stirred 30 minutes, and in the dark red solution of gained, added 1N hydrochloric acid, termination reaction.Add hexane and carry out separatory, water layer is extracted twice, with organic layer merging before with hexane.Clean twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans once with saturated aqueous common salt, uses dried over mgso.Distillation removes and desolvates, and obtains the yellow-white powder.Clean this yellow-white powder with hexane and ethanol mixed solvent, obtain white powder title product (receipts amount 0.80g, yield 66%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.27 (s, tBu (Flu), 18H), 2.70 (br, CpH, 1H), 3.12 (br, 4-Cl-PhCH 2, 4H), 4.34 (s, Flu-9H, 1H), 5.87-6.62 (m, Cp, 4H), 6.70-7.30 (m, Ph (Flu) and 4-Cl-PhCH 2And Flu, 20H), 7.67 (br, Flu, 2H).
MS(FD)：M/z?756(M +).
(iv) two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 50mL pipe, add two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-tert-butyl-fluorene) 0.79g (1.01mmol) and anhydrous diethyl ether 40mL, stirring.With dry ice/methanol bath cooling this mixed slurry solution (78 ℃), add the hexane solution 1.45mL (2.20mmol) of the n-Butyl Lithium of 1.52mol/L, slowly be warmed up to room temperature, and stirred 18 hours.Should the redness reaction solution with after the dry ice/methanol bath cooling (78 ℃), add zirconium tetrachloride 0.32g (1.37mmol).Then, slowly be warmed up to room temperature, and stirred 22 hours, obtain orange suspension liquid.Behind the drying under reduced pressure solvent, under nitrogen, filter through having filled diatomaceous glass filter, clean with a small amount of diethyl ether, concentrated filtrate obtains orange solids.Extract with diethyl ether/hexane/pentane mixed solvent, the solvent of dissolving part is removed in distillation, and drying obtains the Powdered title product of dark peachiness (receipts amount 366mg, yield 40%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR (270MHz, CDCl 3, TMS): δ/ppm 1.32 (s, tBu (Flu), 18H), 3.70 (d, J=15.5Hz, 4-Cl-PhCH 2, 2H), 3.86 (d, J=15.5Hz, 4-Cl-PhCH 2, 2H), 5.79 (t, J=2.6Hz, Cp, 2H), 6.48 (t, J=2.6Hz, Cp, 2H), 6.92-7.33 (m, Ph (Flu) and 4-Cl-PhCH 2And Flu, 20H), 8.35 (s, Flu, 2H).
MS(FD)：M/z?916(M +).
[embodiment 1-1]
-propylene polymerization-
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 250ml, propylene is passed through, kept 20 minutes down at 25 ℃ with 150 liters/hour amounts.On the other hand; In the flask of the band branch road that has fully carried out nitrogen metathetical internal volume 30ml, adding magnetic agitation, is that the amount of 5.00mmol is to the toluene solution that wherein adds MAO (Al=1.53mol/l), then according to being converted into the aluminium atom again; According to being converted into the amount adding dibenzyl methylene radical (cyclopentadienyl moiety) (2 that zirconium atom is 5.0 μ mol; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) toluene solution of zirconium dichloride stirred 20 minutes.This solution is added in the toluene that makes the glass autoclave that flow of propylene passes through in advance the beginning polymerization.Supply with propylene gas continuously with 150 liters/hour amounts, under normal pressure, after carrying out 10 minutes polymerization under 25 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 6.32g.Polymerization activity is 7.58kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.54dl/g, Tm 1=157.0 ℃, Tm 2=162.0 ℃, rrrr=95.3%.
[embodiment 1-2]
-propylene polymerization-
Except before the polyreaction with polyreaction in autoclave in temperature remain on 50 ℃, polymerization time is beyond 15 minutes, carries out equally with embodiment 1-1.Resulting polymers is 12.74g, and polymerization activity is 10.19kg-PP/mmol-Zrhr, and [η] of polymkeric substance is 1.64dl/g, Tm 1=142.9 ℃, Tm 2=150.1 ℃.
[embodiment 1-3]
-propylene polymerization-
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 250ml, make the propylene circulation, kept 20 minutes down at 25 ℃ with 150 liters/hour amounts.On the other hand; In the flask of the band branch road that has fully carried out nitrogen metathetical internal volume 30ml, adding magnetic agitation, is that the amount of 5.00mmol is to the toluene solution that wherein adds MAO (Al=1.53mol/l), then according to being converted into the aluminium atom again; According to being converted into amount adding two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2 that zirconium atom is 5.0 μ mol; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) toluene solution of zirconium dichloride stirred 20 minutes.This solution is added in the toluene that makes the glass autoclave that flow of propylene passes through in advance the beginning polymerization.Supply with propylene gas continuously with 150 liters/hour amounts, under normal pressure, after carrying out 25 minutes polymerization under 25 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 7.35g.Polymerization activity is 3.53kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.43dl/g, Tm 1=154.9 ℃, Tm 2=160.0 ℃, rrrr=95.2%.
[embodiment 1-4]
-propylene polymerization-
Before polyreaction with polyreaction in autoclave in temperature remain on 50 ℃, implement equally with embodiment 1-3.Resulting polymers is 11.00g, and polymerization activity is 5.28kg-PP/mmol-Zrhr, and [η] of polymkeric substance is 1.54dl/g, Tm 1=138.6 ℃, Tm 2=146.2 ℃.
[embodiment 1-5]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-1; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 40 minutes, and according to the operation same with embodiment 1-1, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 3.31g.Polymerization activity is 0.99kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.52dl/g, Tm 1=142.6 ℃, Tm 2=151.8 ℃.
[embodiment 1-6]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-1; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 30 minutes, and according to the operation same with embodiment 1-1, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 8.35g.Polymerization activity is 3.34kg-PP/mmol-Zrhr, and [η] of resulting polymers is 5.98dl/g, Tm 2=153.3 ℃.
[embodiment 1-7]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 40 minutes, and according to the operation same with embodiment 1-2, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 2.90g.Polymerization activity is 0.87kg-PP/mmol-Zrhr, and [η] of resulting polymers is 3.22dl/g, Tm 1=139.1 ℃, Tm 2=143.8 ℃.
[embodiment 1-8]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-1; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 60 minutes, and according to the operation same with embodiment 1-1, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 7.30g.Polymerization activity is 1.46kg-PP/mmol-Zrhr, and [η] of resulting polymers is 5.96dl/g, Tm 1=142.6 ℃, Tm 2=149.0 ℃.
[embodiment 1-9]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-1; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 60 minutes, and according to the operation same with embodiment 1-1, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 2.90g.Polymerization activity is 0.58kg-PP/mmol-Zrhr, and [η] of resulting polymers is 4.64dl/g, Tm 1=135.7 ℃, Tm 2=141.9 ℃.
[embodiment 1-10]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-1; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 15 minutes, and according to the operation same with embodiment 1-1, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 6.55g.Polymerization activity is 5.24kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.17dl/g, Tm 1=153.7 ℃, Tm 2=157.7 ℃.
[embodiment 1-11]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-1; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 15 minutes, and according to the operation same with embodiment 1-2, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 5.64g.Polymerization activity is 4.51kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.42dl/g, Tm 1=136.9 ℃, Tm 2=145.8 ℃.
[embodiment 1-12]
-propylene polymerization-
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 250ml, make the propylene circulation, kept 20 minutes down at 25 ℃ with 150 liters/hour flows; Then according to being converted into 1.0 mmoles/ml toluene solution that the aluminium atom is the amount adding triisobutyl aluminium of 2.0 mmoles; Be the toluene solution that 5.0 μ mol add dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride according to being converted into zirconium atom again; At last; Add 0.020 mmole/liter N, the toluene solution of accelerine four (pentafluorophenyl group) boric acid ester, the beginning polymerization.Supply with propylene gas continuously with 150 liters/hour amounts, under normal pressure, after carrying out 20 minutes polymerization under 25 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 10.56g.Polymerization activity is 6.34kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.25dl/g, Tm 1=144.9 ℃, Tm 2=151.8 ℃.
[comparative example 1-1]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-1; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with dibenzyl methylene radical (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride, and polymerization time was changed to beyond 15 minutes; According to the operation same with embodiment 1-1, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 8.94g.Polymerization activity is 7.15kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.12dl/g, Tm 1=150.2 ℃, Tm 2=155.2 ℃, rrrr=94.1%.
[comparative example 1-2]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with dibenzyl methylene radical (cyclopentadienyl moiety) (3; 6-di-t-butyl fluorenyl) beyond the zirconium dichloride, according to the operation same with embodiment 1-2, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 8.23g.Polymerization activity is 6.58kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.23dl/g, Tm 1=132.2 ℃, Tm 2=142.1 ℃.
[comparative example 1-3]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-1; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with cyclohexylidene (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 60 minutes, and according to the operation same with embodiment 1-1, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 0.06g.Polymerization activity is 0.02kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.61dl/g, Tm 1=149.1 ℃, Tm 2=153.7 ℃.
[comparative example 1-4]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-1; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with dimethylated methylene base (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride, and polymerization time was changed to beyond 30 minutes; According to the operation same with embodiment 1-1, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 1.70g.Polymerization activity is 0.68kg-PP/mmol-Zrhr, the Tm of resulting polymers 2=150.1 ℃.
[comparative example 1-5]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with dimethylated methylene base (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride, and polymerization time was changed to beyond 60 minutes; According to the operation same with embodiment 1-2, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 2.65g.Polymerization activity is 0.53kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.22dl/g, Tm 2=131.0 ℃.
[comparative example 1-6]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-1; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with dibenzyl methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 45 minutes, and according to the operation same with embodiment 1-1, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 2.38g.Polymerization activity is 0.63kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.15dl/g, Tm 1=150.1 ℃, Tm 2=155.4 ℃, rrrr=94.2%.
[comparative example 1-7]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with dibenzyl methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 45 minutes, and according to the operation same with embodiment 1-2, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 2.14g.Polymerization activity is 0.57kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.32dl/g, Tm 1=125.4 ℃, Tm 2=136.1 ℃.
[comparative example 1-8]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-2; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with phenylbenzene methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 60 minutes, and according to the operation same with embodiment 1-2, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 0.75g.Polymerization activity is 0.15kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.85dl/g, Tm 1=98.0 ℃, Tm 2=104.0 ℃.
[embodiment 1-13]
-vinyl polymerization-
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 400ml, make the ethene circulation, kept 10 minutes down at 75 ℃ with 100 liters/hour amounts.Then; According to being converted into the aluminium atom is that the amount of 1.30mmol is to the toluene solution that wherein adds MAO (Al=1.21mol/l); Then, according to be converted into zirconium atom be the amount of 2.0 μ mol add dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) toluene solution of zirconium dichloride, the beginning polymerization.Supply with ethylene gas continuously with 100 liters/hour amounts, under normal pressure, after carrying out 6 minutes polymerization under 75 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 4.59g.Polymerization activity is 23.0kg-PE/mmol-Zrhr, and [η] of resulting polymers is 3.69dl/g.
[embodiment 1-14]
-vinyl polymerization-
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 400ml, make the ethene circulation, kept 10 minutes down at 75 ℃ with 100 liters/hour amounts.Then; According to being converted into the aluminium atom is that the amount of 0.52mmol is to the toluene solution that wherein adds MAO (Al=1.21mol/l); Then, according to be converted into zirconium atom be the amount of 0.8 μ mol add two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) toluene solution of zirconium dichloride, the beginning polymerization.Supply with ethylene gas continuously with 100 liters/hour amounts, under normal pressure, after carrying out 3 minutes polymerization under 75 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 2.70g.Polymerization activity is 67.5kg-PE/mmol-Zrhr, and [η] of resulting polymers is 4.32dl/g.
[embodiment 1-15]
-vinyl polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-14; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) beyond the zirconium dichloride; According to the operation same with embodiment 1-14, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 4.72g.Polymerization activity is 118.0kg-PE/mmol-Zrhr, and [η] of resulting polymers is 3.53dl/g.
[embodiment 1-16]
-vinyl polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-14; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) beyond the zirconium dichloride; According to the operation same with embodiment 1-14, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 3.68g.Polymerization activity is 92.0kg-PE/mmol-Zrhr, and [η] of resulting polymers is 7.32dl/g.
[embodiment 1-17]
-vinyl polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-14; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 2 minutes, and according to the operation same with embodiment 1-14, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 4.24g.Polymerization activity is 159.0kg-PE/mmol-Zrhr, and [η] of resulting polymers is 7.61dl/g.
[embodiment 1-18]
-vinyl polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-13; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time changed to beyond 4 minutes, and according to the operation same with embodiment 1-13, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 4.07g.Polymerization activity is 30.5kg-PE/mmol-Zrhr, and [η] of resulting polymers is 4.05dl/g.
[comparative example 1-9]
-vinyl polymerization-
Except with dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-13; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with cyclohexylidene (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride; Polymerization time changed to beyond 2 minutes, and according to the operation same with embodiment 1-13, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 1.21g.Polymerization activity is 18.2kg-PE/mmol-Zrhr, and [η] of resulting polymers is 2.23dl/g.
[comparative example 1-10]
-vinyl polymerization-
Except with dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-13; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with dibenzyl methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride; Polymerization time changed to beyond 2.5 minutes, and according to the operation same with embodiment 1-13, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 1.76g.Polymerization activity is 21.1kg-PE/mmol-Zrhr, and [η] of resulting polymers is 2.62dl/g.
[comparative example 1-11]
-vinyl polymerization-
Except with dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-13; 7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with phenylbenzene methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride; Polymerization time changed to beyond 3 minutes, and according to the operation same with embodiment 1-13, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 4.15g.Polymerization activity is 41.5kg-PE/mmol-Zrhr.
[embodiment 1-19]
-carry the modulation hold catalyzer-
On the there-necked flask that has fully carried out nitrogen metathetical 100ml, assemble stirring rod, add silicon-dioxide then and carry and hold MAO (Al=16.1wt%) 0.501g.At room temperature add dry toluene 15ml then, under agitation add the toluene solution 10ml of dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride 10.2mg, stirred 1 hour.Filter the slurry of gained with strainer, with the powder on the 10ml dry toluene filter rinsed 1 time, then with 10ml anhydrous hexane cleaning 3 times.Powder after cleaning is implemented two hours drying under reduced pressure, obtain the 0.422g powder,, process the slurry of 10.0wt% the mineral oil of itself and 3.80g.
[embodiment 1-20]
-bulk propylene polymerization-
In the flask of the band branch road that has fully carried out nitrogen metathetical 50ml, add magnetic agitation; Add hexane solution (Al=1.0M) 1.0mmol and anhydrous hexane 5.0ml that the foregoing description 1-19 held catalyst pulp 0.596g, triisobutyl aluminium in synthetic year then, import in the SUS system autoclave that has fully carried out nitrogen metathetical internal volume 2000ml.Then, add propylene liquid 500g, after carrying out polymerization in 40 minutes under 70 ℃, the cooling autoclave, and remove propylene, stop polymerization.The gained syndiotactic polypropylenes is 38.7g, and polymerization activity is 45.8kg-PP/mmol-Zrhr.Polymers analysis results is [η]=0.99dl/g, Mw=72800, Mw/Mn=1.87, Tm 1=135.9 ℃, Tm 2=145.7 ℃.
[embodiment 1-21]
-bulk propylene polymerization-
Except using the foregoing description 1-19 to hold catalyst pulp 0.194g in synthetic year, add after the propylene liquid 500g, add beyond the hydrogen 0.3NL, according to carrying out polymerization with the same condition of the foregoing description 1-20.The syndiotactic polypropylenes of gained is 42.2g, and polymerization activity is 153.5kg-PP/mmol-Zrhr.Polymers analysis results is [η]=1.00dl/g, Mw=74200, Mw/Mn=1.99, Tm 1=134.6 ℃, Tm 2=145.8 ℃.
[comparative example 1-12]
-carry the modulation hold catalyzer-
On the there-necked flask that has fully carried out nitrogen metathetical 100ml, assemble stirring rod, add silicon-dioxide then and carry and hold MAO (Al=16.1wt%) 0.506g.At room temperature add dry toluene 15ml then, under agitation add the toluene solution 10ml of isopropylidene (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride 10.3mg, stirred 1 hour.Filter the slurry of gained with strainer, with the powder on the 10ml dry toluene filter rinsed 1 time, then with 10ml anhydrous hexane cleaning 3 times.Powder after cleaning is carried out two hours drying under reduced pressure, obtain the 0.410g powder,, process the slurry of 10.0wt% the mineral oil of itself and 3.69g.
[comparative example 1-13]
-bulk propylene polymerization-
In the flask of the band branch road that has fully carried out nitrogen metathetical 50ml, add magnetic agitation; Add hexane solution (Al=1.0M) 1.0mmol and anhydrous hexane 5.0ml that above-mentioned comparative example 1-12 held catalyst pulp 0.205g, triisobutyl aluminium in synthetic year then, import in the SUS system autoclave that has fully carried out nitrogen metathetical internal volume 2000ml.Then, add propylene liquid 500g, after carrying out polymerization in 40 minutes under 70 ℃, the cooling autoclave, and remove propylene, stop polymerization.Under 80 ℃, polymkeric substance carried out 10 hours drying under reduced pressure.The gained syndiotactic polypropylenes is 6.9g, and polymerization activity is 16.9kg-PP/mmol-Zrhr.Polymers analysis results is [η]=1.15dl/g, Mw=88200, Mw/Mn=1.76, Tm 1=126.9 ℃, Tm 2=136.9 ℃.
[comparative example 1-14]
-bulk propylene polymerization-
Except using above-mentioned comparative example 1-12 to hold catalyst pulp 0.198g in synthetic year, add after the propylene liquid 500g, add beyond the hydrogen 0.3NL, according to carrying out polymerization with the same condition of above-mentioned comparative example 1-13.The syndiotactic polypropylenes of gained is 168.9g, and polymerization activity is 429.7kg-PP/mmol-Zrhr.Polymers analysis results is [η]=1.07dl/g, Mw=84700, Mw/Mn=1.96, Tm 1=122.3 ℃, Tm 2=136.4 ℃.
[embodiment 1-22]
-propylene polymerization-
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add normal heptane 400ml, make the propylene circulation, kept 20 minutes down at 25 ℃ with 150 liters/hour amounts.On the other hand; In the flask of the band branch road that has fully carried out nitrogen metathetical internal volume 30ml, add magnetic agitation, again to the toluene solution that wherein adds MAO (Al=1.53mol/L) 5.00mmol, then; Add dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) the toluene solution 5.0 μ mol of zirconium dichloride stirred 20 minutes.This solution is added in the normal heptane that makes the glass autoclave that flow of propylene passes through in advance the beginning polymerization.Supply with propylene gas continuously with 150 liters/hour amounts, under normal pressure, after carrying out 7.5 minutes polymerization under 25 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 9.00g.Polymerization activity is 14.40kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.73dl/g, Tm 2=159.0 ℃.
[embodiment 1-23]
-propylene polymerization-
Except with before the polyreaction with polyreaction in autoclave in temperature remain on 50 ℃, polymerization time is beyond 31 minutes, carries out polymerization equally with embodiment 1-22.The polymkeric substance of gained is 19.60g, and polymerization activity is 7.59kg-PP/mmol-Zrhr, and [η] of polymkeric substance is 1.72dl/g, Tm 1=149.9 ℃, Tm 2=154.8 ℃.
[embodiment 1-24]
-propylene polymerization-
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 250ml, make the propylene circulation, kept 20 minutes down at 25 ℃ with 150 liters/hour amounts.On the other hand; In the flask of the band branch road that has fully carried out nitrogen metathetical internal volume 30ml, add magnetic agitation, again to the toluene solution that wherein adds MAO (Al=1.53mol/L) 5.00mmol, then; Add dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) the toluene solution 5.0 μ mol of zirconium dichloride stirred 20 minutes.This solution is added in the toluene of the glass autoclave that makes the propylene circulation in advance the beginning polymerization.Supply with propylene gas continuously with 150 liters/hour amounts, under normal pressure, after carrying out 15 minutes polymerization under 25 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 12.19g.Polymerization activity is 9.75kg-PP/mmol-Zrhr, and [η] of the polymkeric substance of gained is 2.27dl/g, Tm 1=156.5 ℃, Tm 2=161.0 ℃.
[embodiment 1-25]
-propylene polymerization-
Except before the polyreaction with polyreaction in autoclave in temperature remain on 50 ℃, polymerization time is beyond 20 minutes, carries out polymerization equally with embodiment 1-24.The polymkeric substance of gained is 12.30g, and polymerization activity is 7.38kg-PP/mmol-Zrhr, and [η] of polymkeric substance is 1.43dl/g, Tm 1=143.0 ℃, Tm 2=150.6 ℃.
[embodiment 1-26]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-23; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[2-naphthyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 15 minutes, and according to the operation same with embodiment 1-23, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 5.75g.Polymerization activity is 4.60kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.59dl/g, Tm 1=147.2 ℃, Tm 2=154.1 ℃.
[embodiment 1-27]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-24; 7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[p-methylphenyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 10 minutes, and according to the operation same with embodiment 1-24, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 29.81g.Polymerization activity is 35.77kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.00dl/g, Tm 1=155.1 ℃, Tm 2=160.0 ℃.
[embodiment 1-28]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-25; 7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[p-methylphenyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 15 minutes, and according to the operation same with embodiment 1-25, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 39.08g.Polymerization activity is 31.26kg-PP/mmol-Zrhr, and [η] of resulting polymers is 0.71dl/g, Tm 1=140.5 ℃, Tm 2=148.9 ℃.
[embodiment 1-29]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-23; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[p-methylphenyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 15 minutes, and according to the operation same with embodiment 1-23, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 7.42g.Polymerization activity is 5.94kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.87dl/g, Tm 1=147.2 ℃, Tm 2=153.6 ℃.
[embodiment 1-30]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-24; 7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[o-tolyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 5 minutes, and according to the operation same with embodiment 1-24, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 2.24g.Polymerization activity is 5.38kg-PP/mmol-Zrhr, and [η] of resulting polymers is 3.63dl/g, Tm 2=156.0 ℃.
[embodiment 1-31]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-25; 7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[o-tolyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 8 minutes, and according to the operation same with embodiment 1-25, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 3.98g.Polymerization activity is 5.97kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.46dl/g, Tm 1=138.4 ℃, Tm 2=145.8 ℃.
[embodiment 1-32]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-22; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[o-tolyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 9 minutes, and according to the operation same with embodiment 1-22, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 3.75g.Polymerization activity is 5.00kg-PP/mmol-Zrhr, and [η] of resulting polymers is 3.88dl/g, the Tm of resulting polymers 2=156.2 ℃.
[embodiment 1-33]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-23; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[o-tolyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 20 minutes, and according to the operation same with embodiment 1-23, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 6.66g.Polymerization activity is 4.00kg-PP/mmol-Zrhr, Tm 1=141.9 ℃, Tm 2=149.0 ℃.
[embodiment 1-34]
-vinyl polymerization-
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 400ml, make the ethene circulation, kept 10 minutes down at 75 ℃ with 100 liters/hour amounts.Add toluene solution (Al=1.21mol/l) 1.3mmol of MAO then, add the toluene solution 2.0 μ mol of dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride then, the beginning polymerization.Supply with ethylene gas continuously with 100 liters/hour amounts, under normal pressure, after carrying out 4 minutes polymerization under 75 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 3.76g.Polymerization activity is 28.2kg-PE/mmol-Zrhr, and [η] of resulting polymers is 3.74dl/g.
[embodiment 1-35]
-vinyl polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-34; 7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[p-methylphenyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 5 minutes, and according to the operation same with embodiment 1-34, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 6.00g.Polymerization activity is 36.0kg-PE/mmol-Zrhr, and [η] of resulting polymers is 4.58dl/g.
[embodiment 1-36]
-vinyl polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-34; 7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[o-tolyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 6 minutes, and according to the operation same with embodiment 1-34, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 4.41g.Polymerization activity is 22.1kg-PE/mmol-Zrhr, and [η] of resulting polymers is 6.37dl/g.
[embodiment 1-37]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-24; 7-[2-naphthyl]-3; 6-di-t-butyl fluorenyl) zirconium dichloride replaces with two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) beyond the zirconium dichloride; According to the operation same with embodiment 1-24, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 6.54g.Polymerization activity is 5.23kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.29dl/g, Tm 1=157.6 ℃, Tm 2=163.0 ℃.
[embodiment 1-38]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-25; 7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 15 minutes, and according to the operation same with embodiment 1-25, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 6.17g.Polymerization activity is 4.94kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.48dl/g, Tm 1=146.6 ℃, Tm 2=154.1 ℃.
[embodiment 1-39]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-22; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 8 minutes, and according to the operation same with embodiment 1-22, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 2.76g.Polymerization activity is 4.14kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.68dl/g, Tm 2=160.5 ℃.
[embodiment 1-40]
-propylene polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-23; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 10 minutes, and according to the operation same with embodiment 1-23, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 1.69g.Polymerization activity is 2.03kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.55dl/g, Tm 1=150.2 ℃, Tm 2=156.8 ℃.
[comparative example 1-15]
-propylene polymerization-
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add normal hexane 400ml, make the propylene circulation, kept 20 minutes down at 45 ℃ with 150 liters/hour amounts.On the other hand; In the flask of the band branch road that has fully carried out nitrogen metathetical internal volume 30ml, add magnetic agitation; To the toluene solution that wherein adds MAO (Al=1.53mol/L) 5.00mmol, then, add dibenzyl methylene radical (cyclopentadienyl moiety) (3 again; 6-di-t-butyl fluorenyl) the toluene solution 5.0 μ mol of zirconium dichloride stirred 20 minutes.This solution is added in the toluene that makes the glass autoclave that flow of propylene passes through in advance the beginning polymerization.Supply with propylene gas continuously with 150 liters/hour amounts, under normal pressure, after carrying out 30 minutes polymerization under 45 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 2.15g.Polymerization activity is 0.86kg-PP/mmol-Zrhr, and [η] of resulting polymers is 1.31dl/g, Tm 1=134.1 ℃, Tm 2=143.5 ℃.
[embodiment 1-41]
-vinyl polymerization-
Except with the dibenzyl methylene radical (cyclopentadienyl moiety) (2 among the embodiment 1-34; 7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride replace with two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) zirconium dichloride; Polymerization time was changed to beyond 6 minutes, and according to the operation same with embodiment 1-34, modulation catalyst solution also carries out polymerization.The result obtains polymkeric substance 2.00g.Polymerization activity is 10.0kg-PE/mmol-Zrhr, and [η] of resulting polymers is 3.36dl/g.
[embodiment 1-42]
-vinyl polymerization-
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 400ml, make the ethene circulation, kept 10 minutes down at 75 ℃ with 100 liters/hour amounts.Add toluene solution (Al=1.21mol/l) 0.52mmol of MAO then, add the toluene solution 0.8 μ mol of two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride then, the beginning polymerization.Supply with ethylene gas continuously with 100 liters/hour amounts, under normal pressure, after carrying out 6 minutes polymerization under 75 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 0.42g.Polymerization activity is 5.3kg-PE/mmol-Zrhr, and [η] of resulting polymers is 8.44dl/g.
About The above results; Sum up the result of embodiment 1-1～12 with comparative example 1-1～8 relevant with propylene polymerization at table 1-1; Sum up the result of embodiment 1-13～18 with comparative example 1-9～11 relevant with vinyl polymerization at table 1-2; 1-3 sums up embodiment 1-22～33,37～40 relevant with propylene polymerization, the result of comparative example 1-12 at table, and 1-4 sums up embodiment 1-34～36,41 relevant with vinyl polymerization, 42 result at table.
Figure GSA00000105371101861
Catalyzer a: dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer b: two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer c: two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer d: two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer e: two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer f: two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer g: cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer h: dibenzyl methylene radical (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer i: cyclohexylidene (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride
Catalyzer j: dimethylated methylene base (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer k: dibenzyl methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride
Catalyzer l: phenylbenzene methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride
Figure GSA00000105371101881
Catalyzer a: dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer b: two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer c: two (normal-butyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer e: two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer f: two (m-trifluoromethyl-phenyl) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer g: cyclohexylidene (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer i: cyclohexylidene (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride
Catalyzer k: dibenzyl methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride
Catalyzer l: phenylbenzene methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride
Figure GSA00000105371101901
Catalyzer a: dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer h: dibenzyl methylene radical (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer m: dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer n: dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[p-methylphenyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer o: dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[o-tolyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer p: two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Figure GSA00000105371101921
Catalyzer d: two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer m: dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[2-naphthyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer n: dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[p-methylphenyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer o: dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-[o-tolyl]-3,6-di-t-butyl fluorenyl) zirconium dichloride
Catalyzer p: two (4-benzyl chloride base) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride
[example II]
Below, further specifying the present invention (2) according to embodiment, the present invention does not receive any restriction of these embodiment.
The structure of metallocene compound and precursor thereof is used 270MHz 1H-NMR (GSH-270 of NEC), FD-mass analysis decisions such as (SX-102A of NEC).
Below, rerum natura test conditions etc. is described.
1. limiting viscosity [η] is measured in 135 ℃, naphthane.
Butene content and ethylene content by 13C-NMR composes decision.
[compound method of known metallocene compound]
In addition, synthetic as phenylbenzene methylene radical (cyclopentadienyl moiety) (fluorenyl) zirconium dichloride of the used known metallocene compound of comparative example according to the described method of japanese kokai publication hei 2-274703 communique.
[synthetic routine 2-1]
Two { (trifluoromethyl) phenyl } methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenes Base) zirconium dichloride is synthetic
(i) prestox octahydro dibenzo fluorenes is synthetic
Possess in the there-necked flask of 500ml of three pistons, tap funnel, magnetic agitation fully having carried out the nitrogen metathetical, at room temperature add fluorenes 9.72g (58.6mmol) and 2,5-dimethyl--2,5-pinakon 19.6g (134mmol).Add anhydrous methylene chloride 85ml, after stirring with magnetic agitation, be cooled to-8 ℃ with ice bath.After wherein adding the Aluminum chloride anhydrous 38.9g (292mmol) of pulverizing with 70 fens clockwise, stirred 2 hours down, remove ice bath again, at room temperature stirred 19 hours at 0 ℃.After adopting G.C. to confirm that fluorenes disappears, dark brown solution is injected frozen water 150ml carry out chilling.After extracting soluble part with diethyl ether 500ml,, wash with in the saturated sodium bicarbonate aqueous solution and organic layer.After the isolated organic phase of anhydrous magnesium sulfate drying, filter sal epsom, use the rotary evaporator underpressure distillation to remove the solvent of filtrating.Residue moves on the funnel of paulownia mountain, and after time cleaning of hexane 10ml * 6, drying under reduced pressure obtains title product (receipts amount 12.0g, yield 53%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.3(s，12H)，1.4(s，12H)，1.7(s，8H)，3.8(s，2H)，7.4(s，2H)，7.6(s，2H).
MS(FD)：M/z?386(M +).
(ii) 6,6-two [-(trifluoromethyl) phenyl] fulvene synthetic
In the reaction vessel of tap funnel is installed; Under nitrogen environment; Add anhydrous tetrahydro furan 80ml and cyclopentadiene 2.0ml (24.1mmol); This solution is cooled to 0 ℃, and slowly drips the hexane solution 17.0ml (26.5mmol) of the n-Butyl Lithium of 1.56mol/L, at room temperature stir an evening.Then, in tap funnel, add 3,3 '-(trifluoromethyl) UVNUL MS-40 8.43g (26.5mmol) is dissolved in the solution of anhydrous tetrahydro furan 50ml, is cooled to 0 ℃ and slowly drip, and keeps this state, is returned to room temperature, stirred one.Extract this reaction solution with diethyl ether, clean this organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, after the organic phase that obtains with anhydrous magnesium sulfate drying, filter sal epsom, the solvent of filtrating is removed in the underpressure distillation of use rotary evaporator.Make with extra care with silicagel column, obtain title product (receipts amount 4.14g, yield 47%).The evaluation of title product is adopted 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?6.17-6.21(m，2H)，6.64-6.66(m，2H)，7.44-7.58(m，6H)，7.68(d，2H，J＝7.56Hz).
(iii) two [-(trifluoromethyl) phenyl] cyclopentadienyl moiety (prestox octahydro dibenzo fluorenyl) methane is synthetic
In the reaction vessel of tap funnel is installed; Under nitrogen environment; Add anhydrous tetrahydro furan 30ml and prestox octahydro dibenzo fluorenes 0.82g (2.11mmol); This solution is cooled to 0 ℃, and slowly drips the hexane solution 1.50ml (2.32mmol) of the n-Butyl Lithium of 1.56mol/L, at room temperature stir an evening.Then, in tap funnel, add 6,6-two {-(trifluoromethyl) phenyl } fulvene 1.00g (2.32mmol) is dissolved in the solution of anhydrous tetrahydro furan 20ml, is cooled to-78 ℃ and slowly drip, and keeps this state, slowly gets back to room temperature, stirs one.Extract this reaction solution with diethyl ether, clean this organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, after the organic phase that obtains with anhydrous magnesium sulfate drying, filter sal epsom, the solvent of filtrating is removed in the underpressure distillation of use rotary evaporator.Make with extra care with silicagel column, obtain title product (receipts amount 0.74g, yield 47%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.94(b，5H)，1.14(s，6H)，1.21(s，7H)，1.26(s，7H)，1.62(s，8H)，3.14(b，2H)，5.46(s，1H)，6.48(m，2H)，7.06-7.28(m，12H).
MS(FD)：m/z?752(M +).
(iv) two [-(trifluoromethyl) phenyl] methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment; In anhydrous diethyl ether 30mL, add two [-(trifluoromethyl) phenyl] cyclopentadienyl moiety (prestox octahydro dibenzo fluorenyl) methane 0.79g (1.05mmol); This solution is cooled to 0 ℃; And slowly drip the hexane solution 1.39ml (2.20mmol) of the n-Butyl Lithium of 1.58mol/L, stir an evening.Then, be cooled to-78 ℃, and add zirconium tetrachloride-THF coordination compound (1: 2) 438mg (1.16mmol), stir an evening.After the volatile fraction of this slurry is removed in underpressure distillation, clean residue, filter scavenging solution with anhydrous hexane 40ml.Hexane dissolving partially concd with filtrating adds anhydrous pentane and carries out recrystallization in the solid of separating out, obtain title product (receipts amount 70mg, yield 7%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.827(s，6H)，0.93(s，6H)，1.42(s，6H)，1.49(s，6H)，1.60-1.69(m，8H)，5.52-5.56(m，2H)，6.042(s，1H)，6.088(s，1H)，6.32-6.38(m，2H)，7.56-7.66(m，4H)，8.09-8.12(m，4H)，8.16-8.25(m，2H).
MS(FD)：m/z?912(M +).
[synthetic routine 2-2]
Two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) dichloride Synthesizing of zirconium
(i) 6,6-two (rubigan) fulvene synthetic
In the reaction vessel of tap funnel is installed; Under nitrogen environment; Add anhydrous tetrahydro furan 40ml and cyclopentadiene 2.15ml (25.9mmol), this solution is cooled to 0 ℃, and slowly drips the hexane solution 18.0ml (28.5mmol) of the n-Butyl Lithium of 1.58mol/L.Then, in tap funnel, add 4,4 '-dichloro benzophenone 5.00g (19.9mmol) is dissolved in the solution of anhydrous tetrahydro furan 30ml, is cooled to 0 ℃ and slowly drip, and keeps this state, gets back to room temperature, stirred one.Extract this reaction solution with diethyl ether, clean this organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, after the organic phase that obtains with anhydrous magnesium sulfate drying, filter sal epsom, the solvent of filtrating is removed in the underpressure distillation of use rotary evaporator.Make with extra care with silicagel column, obtain title product (receipts amount 3.37g, yield 57%).The evaluation of title product is adopted 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?6.21-6.24(m，2H)，6.60-6.63(m，2H)，7.23(d，2H，J＝8.1Hz)，7.37(d，2H，J＝8.6Hz)
(ii) two (rubigan) cyclopentadienyl moiety (prestox octahydro dibenzo fluorenyl) methane is synthetic
In the reaction vessel of tap funnel is installed; Under nitrogen environment; Add anhydrous tetrahydro furan 40ml and the method synthetic prestox octahydro dibenzo fluorenes 2.35g (6.08mmol) described in (i) that synthesize routine 2-1; This solution is cooled to 0 ℃, slowly drips the hexane solution 4.62ml (7.30mmol) and the stirring of the n-Butyl Lithium of 1.58mol/L simultaneously.In this solution, add 1; 3-dimethyl--2-imidazolone 0.86ml (7.90mmol) stirred after 30 minutes, in tap funnel, added 6, and 6-two (rubigan) fulvene 2.00g (6.68mmol) is dissolved in the solution of anhydrous tetrahydro furan 30ml; Be cooled to-78 ℃ and slowly dropping; Keep this state, get back to room temperature, and stirred one.Extract this reaction solution with diethyl ether, clean this organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, after the organic phase that obtains with anhydrous magnesium sulfate drying, filter sal epsom, the solvent of filtrating is removed in the underpressure distillation of use rotary evaporator.After making with extra care with silicagel column, carry out recrystallization, obtain title product (receipts amount 0.714g, yield 17%) with toluene.The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.94(s，6H)，1.14(s，6H)，1.27(s，12H)，1.62(s，8H)，3.06(b，2H)，5.30(s，1H)，6.38-6.50(b，3H)，7.00-7.29(m，8H).
MS(FD)：m/z?684(M +).
(iii) two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment; In anhydrous diethyl ether 15mL, add two (rubigan) cyclopentadienyl moiety (prestox octahydro dibenzo fluorenyl) methane 428mg (0.62mmol); This solution is cooled to 0 ℃; And slowly drip the hexane solution 0.87ml (1.37mmol) of the n-Butyl Lithium of 1.58mol/L, stir an evening.Then, be cooled to-78 ℃, and add zirconium tetrachloride-THF coordination compound (1: 2) 224mg (0.59mmol), stir an evening.After the volatile component of this slurry is removed in underpressure distillation, clean residue, filter scavenging solution with anhydrous hexane 40ml.Hexane dissolving partially concd with filtrating adds anhydrous hexane and carries out recrystallization in the solid of separating out, obtain title product (receipts amount 90mg, yield 18%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.87(s，6H)，0.99(s，6H)，1.42(s，6H)，1.49(s，6H)，1.64-1.71(m，8H)，5.51-5.53(m，2H)，6.17(s，2H)，6.29-6.31(m，2H)，7.33(dd，2H，J＝2.16Hz，8.37Hz)，7.46(dd，2H，J＝1.89Hz，8.64Hz)，7.74(dd，2H，J＝2.43Hz，8.1Hz)，7.88(dd，2H，J＝2.16Hz，8.37Hz)，8.08(s，2H).
MS(FD)：m/z?844(M +).
[synthetic routine 2-3]
Two [chloro-phenyl-] methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) dichloride Zirconium
(i) two (m-chloro) UVNUL MS-40 is synthetic
Possess and add 1-chloro-3-iodobenzene 7.51g (31.5mmol) and anhydrous diethyl ether 40ml, stirring in the there-necked flask of 500ml of tap funnel, magnetic agitation fully having carried out the nitrogen metathetical.Be cooled to-78 ℃, wherein add the hexane solution 19.7ml (31.5mmol) of the n-Butyl Lithium of 1.60mol/L with 10 fens clockwise.Utilize gc to confirm to react and carry out, then with 30 minutes interpolation ethyl piperidine-1-carboxylicesters 1.98g (12.6mmol).After the dropping, stirred 30 minutes at-78 ℃.Add Hydrogen chloride, termination reaction.Add diethyl ether 50ml, obtain organic phase with separating funnel.Extract water with diethyl ether 30ml.Collect organic phase, clean twice, clean once, after the isolated organic phase of anhydrous magnesium sulfate drying, filter sal epsom, use the rotary evaporator underpressure distillation to remove the solvent of filtrating with saturated aqueous common salt 50ml with 50ml water.Make with extra care with column chromatography, obtain title product (receipts amount 3.70g, yield 82%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?7.4-7.8(m，Ph，8H).
MS(FD)：m/z?250(M +).
(ii) 6,6-two (m-chloro) phenyl fulvene synthetic
Possess and add two (m-chloro) UVNUL MS-40 3.80g (15.0mmol) and anhydrous tetrahydro furan 20ml, stirring in the there-necked flask of 500ml of tap funnel and magnetic agitation fully having carried out the nitrogen metathetical.In this solution, drip the tetrahydrofuran solution 11.25ml (22.5mmol) of 2.0mol/L cyclopentadiene sodium with tap funnel, after the dropping, stirred 30 minutes at 0 ℃.Add saturated aqueous ammonium chloride 50ml, ether 50ml obtains organic phase with separating funnel.Extract water with ether 30ml.Collect organic phase, clean twice, clean once, after the isolated organic phase of anhydrous magnesium sulfate drying, filter sal epsom, use the rotary evaporator underpressure distillation to remove the solvent of filtrating with saturated aqueous common salt 50ml with 50ml water.Make with extra care with column chromatography, obtain title product (receipts amount 3.70g, yield 82%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?6.2(m，Cp，2H)，6.6(m，Cp，2H)，7.1-7.4(m，Ph，10H).
MS(FD)：M/z?299(M +).
(iii) two (m-chloro) phenylmethylene (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) is synthetic
Possess in the there-necked flask of 200ml of three pistons and tap funnel, magnetic agitation fully having carried out the nitrogen metathetical; Interpolation is according to (i) described method synthetic prestox octahydro dibenzo fluorenes 2.13g (5.50mmol) and the anhydrous tetrahydro furan 80ml of synthetic routine 2-1; After the stirring of magnetic agitation, be cooled to 0 ℃.Behind the hexane solution 3.90ml of the n-Butyl Lithium that wherein adds 1.54mol/L (6.01mmol), remove ice bath then, at room temperature stirred 4 hours.After this slurry is cooled to-78 ℃, add 6 with 15 minutes, 6-two (m-chloro) phenyl fulvene 1.50g (5.00mmol) is dissolved in the solution among the anhydrous tetrahydro furan 10ml.Stirred this mixture 2 hours at-78 ℃.With 1N hydrochloric acid this solution is carried out chilling, extract soluble part with diethyl ether 50ml.After cleaning isolated organic phase with saturated aqueous common salt 100ml, carry out drying with anhydrous magnesium sulfate.Filter sal epsom, use the rotary evaporator underpressure distillation to remove the solvent of filtrating.With methylene chloride the thick refining thing of gained is carried out recrystallization, obtain title product (3.40g, yield 91%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.9-1.5(m，24H)，1.6(s+s，8H)，3.0(br，2H)，5.4(s+s，1H)，6.2-6.5(m(br)，3H)，7.0-7.4(br+s，12H).
MS(FD)：m/z?684(M +).
(iv) two (m-chloro) phenylmethylene (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride is synthetic
Possess in the schlenk pipe of 30ml of tap funnel and magnetic agitation and add two (m-chloro) phenylmethylene (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) 1.37g (2.00mmol) and anhydrous diethyl ether 15ml fully having carried out the nitrogen metathetical; After the stirring of magnetic agitation, be cooled to-78 ℃.Behind the hexane solution 2.90ml of the n-Butyl Lithium that wherein adds 1.54mol/L (4.47mmol), slowly heat up then, at room temperature stirred 22 hours.After this slurry is cooled to-78 ℃ once more, add zirconium tetrachloride-THF coordination compound (1: 2) 0.73g (1.94mmol), at room temperature stirred 19 hours.After the volatile component of this slurry is removed in underpressure distillation, clean residue, filter insolubles with anhydrous hexane 40ml.Use pentane to carry out recrystallization, obtain title product (0.40g, yield 24%) filtering gained solution.The evaluation of title product adopts the FD-MS spectrum to carry out.
MS(FD)：M/z?845(M +).
[synthetic routine 2-4]
Two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl-fluorenyl) Synthesizing of zirconium dichloride
(i) 2,7-two bromo-3,6-di-t-butyl-fluorenes synthetic
Under nitrogen gas stream, in the there-necked flask of 300ml, add 3,6-di-t-butyl-fluorenes 15.2g (54.7mmol) and Texacar PC 170ml, stirring.In this solution, add N-bromine succinimide 20.5g (115mmol), 80 ℃ of heated and stirred 5 hours.Naturally place cooling then, in 800ml water, add reaction soln, at room temperature stir 15 minutes after, the solid that filtering separation is separated out.The gained solid is cleaned 5 times with ethanol 10mL.Then, add the mixing solutions of hexane and a spot of methylene dichloride, be heated to 60 ℃ fully after the dissolving, leave standstill an evening at-20 ℃ to this solid.The crystallization of separating out is cleaned 3 times with hexane 5mL, obtains title product (receipts amount 21.2g, yield 76%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.5(s，18H)，3.7(s，2H)，7.7(s，2H)，7.8(s，2H).
MS(FD)：M/z?436(M +).
(ii) 2,7-phenylbenzene-3,6-di-t-butyl-fluorenes synthetic
Under nitrogen gas stream, in the there-necked flask of 300mL, to 2,7-two bromo-3,6-di-t-butyl-fluorenes 8.15g (18.7mmol), Pd (PPh 3) the middle adding 1 of 1.08g (0.93mmol), 2-glycol dimethyl ether 120ml at room temperature stirred 20 minutes.The ethanol 20ml solution that in this solution, adds phenyl-boron dihydroxide 5.01g (41.1mmol) after at room temperature stirring 20 minutes, adds the aqueous sodium carbonate 37.4ml (74.8mmol) of 2.0mol/L.Then, reflux 18 hours after the placement cooling, under ice bath, is carried out chilling with Hydrogen chloride naturally.Add ether, extract soluble part, clean organic layer 2 times with saturated sodium bicarbonate aqueous solution, water cleans 2 times, cleans 2 times with saturated aqueous common salt, uses dried over mgso then.Filter sal epsom, use the rotary evaporator underpressure distillation to remove the solvent of filtrating.Solid with the refining gained of column chromatography obtains title product (receipts amount 4.36g, yield 54%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.3(s，18H)，3.8(s，2H)，7.1(s，2H)，7.3(s，10H)，7.9(s，2H).
MS(FD)：M/z?430(M +).
(iii) two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl-fluorenyl) is synthetic
Under nitrogen environment, in the there-necked flask of 200ml, add 2,7-phenylbenzene-3,6-di-t-butyl-fluorenes 3.50g (8.14mmol) and anhydrous tetrahydro furan 100mL also stir.With this solution of ice bath cooling, drip the hexane solution 5.70ml (8.89mmol) of the n-Butyl Lithium of 1.56mol/L.At room temperature stirred then 3 hours, and once more gained solution was cooled to-40 ℃, drip the prescription synthetic 6 according to synthetic routine 2-2 (i), the anhydrous tetrahydrofuran solution of 6-two (rubigan) fulvene 2.22g (7.39mol) at room temperature stirred 5 hours.Then, carry out chilling with diluted hydrochloric acid aqueous solution.In reaction solution, add hexane 100ml and extract soluble part, clean this organic layer, use dried over mgso with saturated sodium bicarbonate aqueous solution, water, saturated aqueous common salt.Filter sal epsom, use the rotary evaporator underpressure distillation to remove the solvent of filtrating.Clean with hexane, methyl alcohol then, obtain title product (receipts amount 3.20g, yield 54%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.2(s，18H)，2.9(s，2H)，5.2(s，1H)，6.0(d，1H)，6.2(d，1H)，6.3(s，1H)，6.6(s，2H)，6.9(s，10H)，7.2-7.4(m+s，8H)，7.6(s，2H).
MS(FD)：M/z?729(M +).
(iv) two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl-fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100mL pipe, add two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl-fluorenyl) 1.00g (1.37mmol) and anhydrous diethyl ether 60ml, stirring.With this solution of dry ice/methanol bath cooling, drip the hexane solution 1.80ml (2.81mmol) of the n-Butyl Lithium of 1.56mol/L, at room temperature stirred 20 hours.After being cooled to-60 ℃ with dry ice/methanol bath then, add zirconium tetrachloride 0.37g (1.59mmol), at room temperature stirred 20 hours.After the organic solvent of this solution is removed in underpressure distillation, extract residue, carry out recrystallization, obtain title product (receipts amount 0.47g, yield 38%) from each solution with anhydrous hexane and anhydrous methylene chloride.The identification and utilization of title product 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.2(s，18H)，5.4(m，2H)，5.8(s，2H)，6.3(m，2H)，7-7.2(s+m+m，6H)，7.5-7.7(m，12H)，8.3(s，2H).
[synthetic routine 2-5]
Two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl-fluorenyl) Synthesizing of zirconium dichloride
(i) 2,7-dimethyl--3,6-di-t-butyl-fluorenes synthetic
Under nitrogen gas stream, in the there-necked flask of 300ml, to prescription synthetic 2 according to Synthetic 2-4 (i), 7-two bromo-3,6-di-t-butyl-fluorenes 5.03g (11.5mmol) and PdCl 2(dppf) CH 2Cl 20.196g add dry tert-butylmethyl ether 100mL (0.24mmol), at room temperature stirred 20 minutes.With this solution of the dry ice bath cooling, with the ethereal solution 19.2mL (57.6mmol) that dripped the methyl-magnesium-bromide of 3.0mol/L in 15 minutes.After the pulp solution that the reflux that will carry out 5 days then obtains is placed cooling naturally, use and carry out chilling with ice bath refrigerative 1N hydrochloric acid.Add ether then, extract soluble part, behind saturated sodium bicarbonate aqueous solution, water, this organic layer of saturated aqueous common salt cleaning, use dried over mgso.Filter sal epsom, use the rotary evaporator underpressure distillation to remove the solvent of filtrating.Make with extra care with column chromatography, obtain title product (receipts amount 2.07g, yield 63%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.5(s，18H)，2.5(s，6H)，3.7(s，2H)，7.2(d，2H)，7.7(s，2H).
MS(FD)：M/z?306(M +).
(ii) two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl-fluorenyl) is synthetic
Under nitrogen environment, in the there-necked flask of 200ml, add 2,7-dimethyl--3,6-di-t-butyl-fluorenyl 2.60g (8.49mmol) and anhydrous tetrahydro furan 100mL also stir.With this mixing solutions of ice bath cooling, behind the hexane solution 5.70ml (8.89mmol) of the n-Butyl Lithium of dropping 1.56mol/L, at room temperature stirred 3 hours.Then, gained solution is cooled to-40 ℃ with dry ice/methanol bath, drips prescription synthetic 6, the tetrahydrofuran solution 60ml of 6-two (rubigan) fulvene 2.78g (9.33mmol) according to synthetic routine 2-2 (i).Slowly be warmed up to stirring at room 1 hour then.In reaction soln, add 1N hydrochloric acid 100ml, add hexane 100ml, and extract soluble part, water, saturated aqueous common salt clean after this organic layer, use dried over mgso.Filter sal epsom, use the rotary evaporator underpressure distillation to remove the solvent of filtrating.Carry out the recrystallization of residue then by hexane, obtain title product (receipts amount 4.40g, yield 86%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.3(s，18H)，2.3(s，6H)，3.0(s，2H)，5.2(s，2H)，6.1-6.3(s，4H)，6.7(s，2H)，7.0(s，6H)，7.4(s，2H).
MS(FD)：M/z?604(M +).
(iii) two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl-fluorenyl) zirconium dichloride is synthetic
Under nitrogen environment, in the schlenk of 100ml pipe, add two (rubigan) methylene radical (cyclopentadienyl moiety) (2,7-dimethyl--3,6-di-t-butyl-fluorenyl) 1.00g (1.65mmol) and anhydrous diethyl ether 50ml, stirring.To-40 ℃, add the hexane solution 2.20ml (3.43mmol) of the n-Butyl Lithium of concentration 1.56mol/L with this mixed slurry solution of dry ice/methanol bath cooling, slowly be warmed up to room temperature, and stirred 22 hours.Behind this reaction solution of dry ice/methanol bath cooling, add zirconium tetrachloride 0.38g (1.65mmol).Slowly be warmed up to room temperature then, and stirred 20 hours.
After underpressure distillation removes and desolvates, add the anhydrous hexane of about 30ml, after the stirring, remove by filter insolubles.With this insolubles of anhydrous methylene chloride dissolving, remove by filter insolubles again.With hexane solution that filters gained and dichloromethane solution merge concentrate after, the powder of separating out with the anhydrous hexane filtration.At last, clean, obtain title product (receipts amount 0.122g, yield 10%) with anhydrous hexane, anhydrous pentane.The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.5(s，18H)，2.3(s，6H)5.6(m，2H)，6.0(m，2H)，6.3(m，2H)，7.3(dd，2H)，7.4(dd，2H)，7.7(dd，2H)7.8(dd，2H)，8.1(s，2H)
MS(FD)：M/z?764(M +)
[synthetic routine 2-6]
(chloro-phenyl-) (phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) two Synthesizing of zirconium chloride
(i) 6,6-(chloro-phenyl-) (phenyl) fulvene synthetic
Possess and add (chloro-phenyl-) (phenyl) ketone 6.48g (29.9mmol) and anhydrous tetrahydro furan 100ml, stirring in the there-necked flask of 500ml of tap funnel and magnetic agitation fully having carried out the nitrogen metathetical.In this solution, drip the tetrahydrofuran solution 22.5ml (45mmol) of 2.0M cyclopentadiene sodium with tap funnel.Under 0 ℃, stirred 4 hours.Use the Hydrogen chloride termination reaction, add diethyl ether 50ml, obtain organic phase with separating funnel.Extract water with diethyl ether 30ml.Collect organic phase, clean twice, clean 1 time with saturated aqueous common salt 50ml with saturated sodium bicarbonate aqueous solution 50ml.Use dried over mgso, filter sal epsom, use the rotary evaporator underpressure distillation to remove the solvent of filtrating.Make with extra care with column chromatography, obtain title product (receipts amount 4.85g, yield 61%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?6.2(m，Cp，2H)，6.6(m，Cp，2H)，7.1-7.4(m，Ph，9H).
MS(FD)：M/z?264(M +).
(iii) (chloro-phenyl-) (phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) is synthetic
Possess in the there-necked flask of 500ml of three pistons and tap funnel, magnetic agitation fully having carried out the nitrogen metathetical, add according to (i) said method synthetic prestox octahydro dibenzo fluorenes 6.73g (17.4mmol) of synthetic routine 2-1 and anhydrous tetrahydro furan 150ml, stirring.Be cooled to 0 ℃, behind the hexane solution 12.6ml (20.1mmol) of the n-Butyl Lithium of interpolation 1.60mol/L, at room temperature stirred 4 hours.Reaction solution is cooled to after-78 ℃, with 6,6-(chloro-phenyl-) (phenyl) fulvene 4.85g (18.4mmol) was dissolved in the solution of anhydrous tetrahydro furan 30ml with interpolation in 15 minutes.Stirred this mixture 2 hours at-78 ℃.With this solution of Hydrogen chloride water quick cooling, extract soluble part with diethyl ether 50ml.Collect organic phase, clean twice, clean once with saturated aqueous common salt 50ml with saturated sodium bicarbonate aqueous solution 50ml.Filter sal epsom, use the rotary evaporator underpressure distillation to remove the solvent of filtrating.Utilize column chromatography to obtain title product (receipts amount 3.10g, yield 26%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.9-1.5(m，24H)，1.6(s+s，8H)，3.0(br，2H)，5.4(s+s，1H)，6.2-6.5(m(br)，3H)，7.0-7.4(br+s，13H)
MS(FD)：M/z?650(M +)
(iii) (chloro-phenyl-) (phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride is synthetic
Possess in the schlenk pipe of 30ml of tap funnel and magnetic agitation and add two (m-chloro) phenylmethylene (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) 1.31g (2.02mmol) and anhydrous diethyl ether 30ml fully having carried out the nitrogen metathetical; After the stirring of magnetic agitation, be cooled to-78 ℃.Behind the hexane solution 2.60ml of the n-Butyl Lithium that wherein adds 1.60mmol/L (4.20mmol), slowly heat up then, at room temperature stirred 22 hours.This slurry is cooled to after-78 ℃ once more, adds zirconium tetrachloride 0.45g (1.90mmol), at room temperature stirred 19 hours.After the volatile component of this slurry is removed in underpressure distillation, clean residue, filter insolubles with anhydrous hexane 40ml.Carry out recrystallization to filtering gained solution, obtain title product (0.12g, yield 7%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.8(s，6H)，0.9(s，6H)，1.4(s，6H)，1.5(s，6H)，1.6-1.7(m，8H)，5.6(dd，2H)，6.2(s，2H)，6.3(dd，2H)，7.2-7.5(m，5H)，7.9(d，2H)，8.0(d，2H)，8.1(s，2H).
MS(FD)：M/z?811(M +).
[synthetic routine 2-7]
Two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride Synthetic
(i) 6,6-two-2-naphthyl fulvene synthetic
Two mouthfuls of flasks of 200ml that will possess magnetic agitation son and three pistons have fully carried out after nitrogen replaces; Adding is according to Heterocycles, vol.40, No.1; Two-2-naphthyl ketone 1.55g (5.48mmol) that 79～83 (1995) described methods are made adds THF 40ml.With the ice-water bath cooling, and after slowly adding cyclopentadiene sodium/tetrahydrofuran solution 5.50ml (11.0mmol) of 2.0mol/l, under nitrogen environment, at room temperature stirred 65 hours.Then slowly add 3N hydrochloric acid 100ml and diethyl ether 100ml, the Dualayer solution of gained is moved to 300ml separating funnel and vibration several after, remove water layer.Extract this water layer once with diethyl ether 30ml, merge with the organic layer that obtains before.Water 100ml cleans the organic layer three times of gained then, with saturated aqueous common salt 100ml cleaning once, and with anhydrous magnesium sulfate drying two hours.Solids filtered, distillation removes and desolvates, and obtains solid.Use the silica gel chromatography separation and purification, obtain title product (receipts amount 1.21g, yield 67%).The evaluation of title product is adopted 1The H-NMR spectrum is carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?6.3-6.5(m，Cp，2H)，6.6-6.7(m，Cp，2H)，7.3-7.5(m，Ar，2H)，7.5-7.6(m，Ar，4H)，7.7-7.9(m，Ar，8H).
(ii) two-2-naphthyl (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) methane is synthetic
After the 200ml twoport flask that will possess magnetic agitation, three pistons and 100ml tap funnel carries out sufficient nitrogen displacement, add prestox octahydro dibenzo fluorenes 1.35g (3.48mmol), add THF 40ml.With the ice-water bath cooling, slowly add n-Butyl Lithium/hexane solution 2.30ml (3.60mmol) of 1.58mol/l simultaneously, under nitrogen environment, at room temperature stirred 20 hours then.With methyl alcohol/the dry ice bath cooling, be dissolved in 6 among the THF 30ml in advance, 6-two-2-naphthyl fulvene 1.18g (3.57mmol) with slow adding in 30 minutes simultaneously.Slowly be warmed up to room temperature then, under nitrogen environment, at room temperature stirred 20 hours.Slowly add 1N hydrochloric acid 100ml, add diethyl ether 100ml then.After the Dualayer solution of gained moved to 300ml separating funnel and vibration for several times, remove water layer.Water 100ml cleans twice to the gained organic layer then, with saturated aqueous common salt 100ml cleaning once, and with anhydrous magnesium sulfate drying 3 hours.Solids filtered, distillation removes and desolvates, and uses the silica gel chromatography separation and purification, obtains title product (receipts amount 1.28g, yield 51%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?1.1-1.3(m，Me(OMOHDBFlu)，24H)，1.4-1.7(br，CH 2(OMOHDBFlu)，8H)，2.8-3.2(br，CH 2(Cp)，1H)，5.56(s，CH(9-OMOHDBFlu)，1H)，6.1-6.5(br，Cp，4H)，7.1-8.0(br，Ar(OMOHDBFlu)&Ar(Nap)，18H)
MS(FD)：M/z?716(M +)
(iii) two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride is synthetic
After the 100ml Ji Yedashi Kjeldahl flask (Kjeldahlflask ギ Le ダ one Le Off ラ ス コ) that will possess magnetic agitation son has carried out sufficient nitrogen displacement; Add two (2-naphthyl) (cyclopentadienyl moietys) (prestox octahydro dibenzo fluorenyl) methane 0.50g (0.70mmol), add diethyl ether 40ml.With the ice-water bath cooling, behind n-Butyl Lithium/hexane solution 0.92ml (1.5mmol) of slow simultaneously dropping 1.58mol/l, under nitrogen environment, at room temperature stirred 24 hours.With methyl alcohol/the dry ice bath cooling, add zirconium tetrachloride-THF coordination compound (1: 2) 0.25g (0.67mmol) simultaneously, slowly be warmed up to room temperature then, under nitrogen environment, at room temperature stirred 24 hours.With decompression down distillation remove the solid that obtains that desolvates and under nitrogen environment, extract with pentane ,-18 ℃ of held one day.The white solid that filtration is separated out is again in-18 ℃ of held one day.Refilter the white solid of separating out, the solvent of gained filtrating is removed in decompression distillation down, obtains pink solid-like title product (receipts amount 0.35g, yield 58%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.6-1.8(m，Me(OMOHDBFlu)&CH 2(OMOHDBFlu)，32H)，5.5-6.4(m，Cp，4H)，7.3-8.6(m，Ar，18H).
MS(FD)：M/z?876(M +).
[synthetic routine 2-8]
Two (4-xenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) dichloride Synthesizing of zirconium
(i) 6, two (4-xenyl) fulvene of 6-synthetic
In fully having carried out nitrogen metathetical reaction vessel; Add THF (60ml) and cyclopentadiene 2.47ml (29.9mmol); With this solution of dry ice/methanol bath cooling; Add n-Butyl Lithium/hexane solution 19.6ml (30.8mmol) of 1.57mol/l simultaneously, slowly be warmed up to room temperature, and stir an evening.Reaction soln is being cooled in 0 ℃, with 4,4 '-solution that phenylbenzene UVNUL MS-40 10g (29.9mmol) is dissolved in THF (50ml) uses tap funnel slowly to drip, at room temperature stirred then 3 days.Extract this reaction solution with diethyl ether, clean organic layer with saturated aqueous ammonium chloride, water and saturated aqueous common salt, use dried over mgso, underpressure distillation removes and desolvates.Use the silica gel chromatography separation and purification, obtain title product (receipts amount 0.80g, yield 7%).The evaluation of title product is adopted 1H-NMR carries out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?6.3-6.4(m，2H，Cp)，6.6-6.7(m，2H，Cp)，7.3-7.5(m，10H，Ar)，7.6-7.7(m，8H，Ar).
(ii) two (4-xenyl) cyclopentadienyl moiety (prestox octahydro dibenzo fluorenyl) methane is synthetic
In reaction vessel; Under nitrogen environment; Add t-butyl methyl ether (60ml) and prestox octahydro dibenzo fluorenes 2.09g (5.41mmol), this solution is cooled to 0 ℃, the n-Butyl Lithium/hexane solution 3.90ml (6.14mmol) that slowly drips 1.58mol/l simultaneously also stirs.This solution is cooled to-78 ℃, adds solid 6 simultaneously, two (4-xenyl) the fulvene 1.38g (3.61mmol) of 6-directly slowly are returned to room temperature, and stirred one day.Extract this reaction solution with diethyl ether, clean organic layer, use dried over mgso with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt; Underpressure distillation removes and desolvates, and uses the silica gel chromatography separation and purification, re-uses normal hexane and carries out recrystallization; Obtain title product (receipts amount 1.15g, yield 41%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.93(b，6H)，1.12(b，6H)，1.24(s，6H)，1.26(s，6H)，1.61(b，8H)，2.93-3.05(b，2H)，5.44(s，1H)，6.34(b，3H)，7.30-7.64(m，22H).
MS(FD)：M/z?768(M +).
(iii) two (4-xenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichlorides is synthetic
Under nitrogen environment; (20ml) adds two (4-xenyl) cyclopentadienyl moiety (prestox octahydro dibenzo fluorenyl) methane 0.50g (0.65mmol) in diethylether solvent; This solution is cooled to 0 ℃; Slowly drip n-Butyl Lithium/hexane solution 0.91ml (1.43mmol) of 1.58mol/l simultaneously, stir an evening.Then, be cooled to-78 ℃, add zirconium tetrachloride-THF coordination compound (1: 2) 0.23g (0.62mmol) simultaneously, stir an evening.The solid that removing desolvates obtains is distilled in decompression down under nitrogen environment, dissolve,, clean, be not dissolved in the part of hexane with dichloromethane rinse with hexane through having filled diatomaceous glass filter with hexane.Methylene dichloride is dissolved partially concd, clean and drying, obtain title product (receipts amount 0.14g, yield 24%) with diethyl ether and hexane.The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.84(s，6H)，0.97(s，6H)，1.43(s，6H)，1.50(s，6H)，1.60-1.71(m，8H)，5.62-5.64(m，2H)，6.27(s，2H)，6.31-6.33(m，2H)，7.26-7.47(m，6H)，7.56-7.61(m，6H)，7.71(dd，2H，J＝1.89Hz，7.83Hz)，7.97(dd，2H，J＝2.16Hz，8.1Hz)，8.05-8.09(m，4H).
MS(FD)：M/z?928(M +).
[synthetic routine 2-9]
Two (4-[p-trifluoromethyl phenyl]-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro two The benzo fluorenyl) zirconium dichloride is synthetic
(i) 6, two (4-bromine) fulvene of 6-
Under nitrogen gas stream, 4,4 '-add anhydrous THF 80ml in the dibromo UVNUL MS-40 5.50 (16.2mmol), stir.Under-78 ℃, slowly drip cyclopentadiene sodium/tetrahydrofuran solution 9.70ml (19.4mmol) of 2.0mol/l.Be warmed up to-10 ℃, stirred 3 hours.Confirm reaction terminating, with 1N hydrochloric acid termination reaction.Carry out separatory, extract water layer twice with diethyl ether.Merge with organic layer before, after cleaning with saturated sodium bicarbonate aqueous solution, water and saturated aqueous common salt, use dried over mgso, distillation removes and desolvates, and separates with silica gel chromatography, obtains title product (receipts amount 5.20g, yield 83%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?6.22(d，2H)，6.63(d，2H)，7.14(d，4H)，7.54(d，4H).
MS(FD)：M/z?386(M +).
(ii) 6, two (4-[p-trifluoromethyl phenyl]-phenyl) fulvene of 6-synthetic
Under nitrogen gas stream,, add methyl alcohol 100ml, stirring among two (4-bromine) the fulvene 1.28g (3.30mmol) of 6-to 6.Add 4-(trifluoromethyl) phenyl-boron dihydroxide 1.68g (8.80mmol), tetrakis triphenylphosphine palladium 0.21g (0.165mmol), yellow soda ash 2.09g (1.98mmol), under 55 ℃, stirred 2 hours.Water, methylene dichloride carry out separatory, with twice of dichloromethane extraction water layer.After the saturated aqueous common salt cleaning, use dried over mgso.Distillation removes and desolvates, and separates with silica gel chromatography, obtains title product (receipts amount 1.38g, yield 81%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?6.34(d，2H)，6.65(d，2H)，7.46(d，4H)，7.66.(d，4H)，7.75(t，8H).
MS(FD)：M/z?518(M +).
(iii) two (4-[p-trifluoromethyl phenyl]-phenyl) cyclopentadienyl moiety (prestox octahydro dibenzo fluorenyl) methane is synthetic
Under nitrogen environment, add prestox octahydro dibenzo fluorenes 0.81g (2.20mmol) and dehydration t-butyl methyl ether 100ml, stirring.This solution is cooled to 0 ℃, adds the hexane solution 1.59ml (2.42mmol) of the n-Butyl Lithium of 1.52mol/l.Then, at room temperature stir 24 hours.Gained solution is cooled to-78 ℃, adds 6, two (4-[p-trifluoromethyl phenyl]-phenyl) the fulvene 1.04g (2mmol) of 6-.At room temperature stirred 3 hours, and behind the affirmation reaction terminating, in reaction soln, added 1N hydrochloric acid.Carry out separatory, extract water layer twice,, after saturated sodium bicarbonate aqueous solution, water, saturated aqueous common salt cleaning, use dried over mgso with organic layer merging before with diethyl ether.Distillation removes and desolvates, and separates with silica gel chromatography, obtains title product (receipts amount 0.92g, yield 47%).The evaluation of title product is adopted 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm?0.8-1.7(m，24H)，2.1-2.4(br，8H)，2.7-3.1(br，1H)，5.2-5.4(m，1H)，5.8-6.5(br，4H)，6.7-7.5(br，8H)，7.29(s，2H).
MS(FD)：M/z?904(M +).
(iv) two (4-[p-trifluoromethyl phenyl]-phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichlorides is synthetic
Under nitrogen environment, in diethyl ether 30ml, add two (4-[p-trifluoromethyl phenyl]-phenyl) cyclopentadienyl moiety (prestox octahydro dibenzo fluorenyl) methane 456mg (0.50mmol), this solution is cooled to-78 ℃.Slowly be warmed up to room temperature, and slowly drip the hexane solution 0.69ml (1.05mmol) of the n-Butyl Lithium of 1.52mol/l, stirred 19 hours.Then, be cooled to-78 ℃ once more, add zirconium tetrachloride 0.12g (0.50mmol), slowly be warmed up to room temperature, and stirred 19 hours.This reaction soln is concentrated, and under nitrogen gas stream, 30ml dissolves with hexane.With the partially concd that dissolves in hexane, carry out recrystallization with pentane 10ml.Remove impurity, obtain title product (receipts amount 0.08g, yield 15%).The identification and utilization of title product 1H-NMR, FD-MS spectrum are carried out.
1H-NMR(270MHz，CDCl 3，TMS)：δ/ppm0.84(s，6H)，0.97(s，6H)，1.43(s，6H)，1.50(s，6H)，1.60-1.71(m，8H)，5.62-5.64(m，2H)，6.27(s，2H)，6.31-6.33(m，2H)，7.26-7.47(m，6H)，7.56-7.61(m，4H)，7.71(dd，2H)，7.97(dd，2H)，8.05-8.09(m，4H).
MS(FD)：M/z?1062(M +).
[embodiment 2-1]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
Drying under reduced pressure with carried out in the poly-unit of abundant nitrogen metathetical 2000ml; The dry hexane, 1-butylene 120g and the triisobutyl aluminium (1.0mmol) that add 700ml at normal temperatures; Then the poly-unit internal temperature is warming up to 65 ℃, is forced into 6.1kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make synthetic routine 2-1 synthetic two [(trifluoromethyl) phenyl] methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.002mmol and be converted into the MAO that aluminium is 0.6mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets and add in the polymerizer; Keeping internal temperature is 65 ℃, ethylene pressure 6.2kg/cm 2Under the G, polymerization 15 minutes, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 54.0g, and polymerization activity is 108.0kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 55.0mol%, and ethylene content is 6.5mol%, and 1-butylene content is 38.5mol%, and limiting viscosity [η] is 2.79dl/g.
[embodiment 2-2]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
At drying under reduced pressure with fully carried out in the poly-unit of nitrogen metathetical 2000ml; The dry hexane, 1-butylene 120g and the triisobutyl aluminium (1.0mmol) that add 700ml at normal temperatures; Then the poly-unit internal temperature is warming up to 65 ℃, is forced into 6.1kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make synthetic routine 2-2 synthetic two [rubigan] methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.002mmol and be converted into the MAO that aluminium is 0.6mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets and add in the polymerizer; Keeping internal temperature is 65 ℃, ethylene pressure 6.2kg/cm 2Under the G, polymerization 20 minutes, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 72.8g, and polymerization activity is 109.1kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 53.0mol%, and ethylene content is 10.0mol%, and 1-butylene content is 37.0mol%, and limiting viscosity [η] is 2.35dl/g.
[embodiment 2-3]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
At drying under reduced pressure with fully carried out in the poly-unit of nitrogen metathetical 2000ml; The dry hexane, 1-butylene 120g and the triisobutyl aluminium (1.0mmol) that add 700ml at normal temperatures; Then the poly-unit internal temperature is warming up to 65 ℃, is forced into 6.1kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make synthetic routine 2-3 synthetic two (chloro-phenyl-) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.004mmol and be converted into the MAO that aluminium is 1.2mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets and add in the polymerizer; Keeping internal temperature is 65 ℃, ethylene pressure 6.2kg/cm 2Under the G, polyase 13 5 minutes, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 65.4g, and polymerization activity is 28.0kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 51.0mol%, and ethylene content is 17.0mol%, and 1-butylene content is 32.0mol%, and limiting viscosity [η] is 2.48dl/g.
[embodiment 2-4]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
At drying under reduced pressure with fully carried out in the poly-unit of nitrogen metathetical 2000ml; The dry hexane, 1-butylene 120g and the triisobutyl aluminium (1.0mmol) that add 700ml at normal temperatures; Then the poly-unit internal temperature is warming up to 65 ℃, is forced into 6.1kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make synthetic routine 2-4 synthetic two (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3; 6-di-t-butyl-fluorenyl) zirconium dichloride 0.002mmol be converted into the MAO that aluminium is 0.6mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets and add in the polymerizer, be 65 ℃ keeping internal temperature, ethylene pressure 6.2kg/cm 2Under the G, polymerization 60 minutes, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 8.1g, and polymerization activity is 4.1kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 61.0mol%, and ethylene content is 2.0mol%, and 1-butylene content is 37.0mol%, and limiting viscosity [η] is 2.42dl/g.
[embodiment 2-5]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
At drying under reduced pressure with fully carried out in the poly-unit of nitrogen metathetical 2000ml; The dry hexane, 1-butylene 120g and the triisobutyl aluminium (1.0mmol) that add 700ml at normal temperatures; Then the poly-unit internal temperature is warming up to 65 ℃, is forced into 6.1kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make synthetic routine 2-5 synthetic two (rubigan) methylene radical (cyclopentadienyl moiety) (2; 7-dimethyl--3; 6-di-t-butyl-fluorenyl) zirconium dichloride 0.002mmol be converted into the MAO that aluminium is 0.6mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets and add in the polymerizer, be 65 ℃ keeping internal temperature, ethylene pressure 6.2kg/cm 2Under the G, polymerization 60 minutes, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 22.6g, and polymerization activity is 11.3kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 51.0mol%, and ethylene content is 8.0mol%, and 1-butylene content is 41.0mol%, and limiting viscosity [η] is 2.10dl/g.
[embodiment 2-6]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
At drying under reduced pressure with fully carried out in the poly-unit of nitrogen metathetical 2000ml; The dry hexane, 1-butylene 120g and the triisobutyl aluminium (1.0mmol) that add 700ml at normal temperatures; Then the poly-unit internal temperature is warming up to 65 ℃, is forced into 6.1kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make synthetic routine 2-6 synthetic (chloro-phenyl-) (phenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.002mmol and be converted into the MAO that aluminium is 0.6mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets and add in the polymerizer; Keeping internal temperature is 65 ℃, ethylene pressure 6.2kg/cm 2Under the G, polymerization 15 minutes, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 30.4g, and polymerization activity is 26.1kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 58.0mol%, and ethylene content is 5.0mol%, and 1-butylene content is 37.0mol%, and limiting viscosity [η] is 2.29dl/g.
[embodiment 2-7]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
At drying under reduced pressure with fully carried out in the poly-unit of nitrogen metathetical 2000ml; The dry hexane, 1-butylene 120g and the triisobutyl aluminium (1.0mmol) that add 700ml at normal temperatures; Then the poly-unit internal temperature is warming up to 65 ℃, is forced into 6.1kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make synthetic routine 2-7 synthetic two (2-naphthyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.002mmol and be converted into the MAO that aluminium is 0.6mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets and add in the polymerizer; Keeping internal temperature is 65 ℃, ethylene pressure 6.2kg/cm 2Under the G, polymerization 12 minutes, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 25.8g, and polymerization activity is 64.6kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 56.5mol%, and ethylene content is 7.0mol%, and 1-butylene content is 36.5mol%, and limiting viscosity [η] is 2.73dl/g.
[embodiment 2-8]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
At drying under reduced pressure with fully carried out in the poly-unit of nitrogen metathetical 2000ml; The dry hexane, 1-butylene 120g and the triisobutyl aluminium (1.0mmol) that add 700ml at normal temperatures; Then the poly-unit internal temperature is warming up to 65 ℃, is forced into 6.1kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make two (between the 4-xenyl) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) the zirconium dichloride 0.002mmol of synthetic routine 2-8 synthetic and be converted into the MAO that aluminium is 0.6mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets and add in the polymerizer; Keeping internal temperature is 65 ℃, ethylene pressure 6.2kg/cm 2Under the G, polyase 13 0 minute, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 40.1g, and polymerization activity is 40.1kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 54.5mol%, and ethylene content is 13.0mol%, and 1-butylene content is 32.5mol%, and limiting viscosity [η] is 2.44dl/g.
[embodiment 2-9]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
At drying under reduced pressure with fully carried out in the poly-unit of nitrogen metathetical 1500ml; The dry hexane, 1-butylene 90g and the triisobutyl aluminium (0.75mmol) that add 525ml at normal temperatures; Then the poly-unit internal temperature is warming up to 65 ℃, is forced into 6.1kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make synthetic routine 2-9 synthetic two (4-[p-trifluoromethyl phenyl]-phenyl] methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.0015mmol be converted into the MAO that aluminium is 0.45mmol (production of Tosoh FineChem company) and contact the toluene solution that gets and add in the poly-unit; Keeping internal temperature is 65 ℃, ethylene pressure 6.2kg/cm 2Under the G, polyase 13 0 minute, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 16.9g, and polymerization activity is 22.5kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 56.5mol%, and ethylene content is 9.0mol%, and 1-butylene content is 34.5mol%, and limiting viscosity [η] is 2.48dl/g.
[comparative example 2-1]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
At drying under reduced pressure with fully carried out in the poly-unit of nitrogen metathetical 2000ml; The dry hexane, 1-butylene 480g and the triisobutyl aluminium (1.0mmol) that add 100ml at normal temperatures; Then the poly-unit internal temperature is warming up to 35 ℃, is forced into 6.0kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make phenylbenzene methylene radical (cyclopentadienyl moiety) (fluorenyl) zirconium dichloride 0.005mmol and be converted into the MAO that aluminium is 1.5mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets and add in the polymerizer; Keeping internal temperature is 35 ℃, ethylene pressure 6.2kg/cm 2Under the G, polymerization 5 minutes, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 36.1g, and polymerization activity is 86.7kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 58.2mol%, and ethylene content is 4.1mol%, and 1-butylene content is 37.7mol%, and limiting viscosity [η] is 2.69dl/g.
[comparative example 2-2]
(synthesizing of syndiotactic propene-1-butene-vinyl copolymer)
At drying under reduced pressure with fully carried out in the poly-unit of nitrogen metathetical 2000ml; The dry hexane, 1-butylene 240g and the triisobutyl aluminium (1.0mmol) that add 100ml at normal temperatures; Then the poly-unit internal temperature is warming up to 65 ℃, is forced into 6.0kg/cm with propylene 2G then is forced into 6.2kg/cm with ethene 2G.Then; To make phenylbenzene methylene radical (cyclopentadienyl moiety) (fluorenyl) zirconium dichloride 0.004mmol and be scaled the MAO that aluminium is 1.2mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets and add in the polymerizer; Keeping internal temperature is 65 ℃, ethylene pressure 6.2kg/cm 2Under the G, polymerization 15 minutes, the methyl alcohol of interpolation 20ml stops polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 82.6g, and polymerization activity is 82.6kg-polymer/mmol-cathr.In addition, the consisting of of polymkeric substance, propylene content is 51.0mol%, and ethylene content is 14.0mol%, and 1-butylene content is 34.0mol%, and limiting viscosity [η] is 1.60dl/g.
[EXAMPLE III]
Below, further specifying the present invention (3) according to embodiment, the present invention is not limited to these embodiment.Wherein, each rerum natura is described below and measures among the embodiment.
Limiting viscosity [η]
Limiting viscosity is to use the measured value of naphthane solvent under 135 ℃.That is, polymeric powder, pellet or the resin mass with about 20mg is dissolved in the 15ml naphthane, mensuration specific viscosity η in 135 ℃ oil bath SpAfter in this naphthane solution, adding 5ml naphthane solvent cut, measure specific viscosity η equally SpRepeating twice should operate in dilution, tries to achieve concentration (C) and is extrapolated to 0 o'clock η Sp/ C value is as limiting viscosity (with reference to following formula).
[η]＝lim(η sp/C) (C→0)
Dissolve in the amount of n-decane part
In the sample 5g of syndiotactic propene polymer, add n-decane 200ml, under 145 ℃,, make it dissolving this polymkeric substance heating 30 minutes.Through about 3 hours, gained solution is cooled to 20 ℃, placed 30 minutes.Then, filter precipitate (being insoluble to the part of n-decane).Be about in the acetone of its 3 times of amounts filtrating adding, the one-tenth that is dissolved in the n-decane is analyzed.Filter out precipitate by acetone, dry then.Wherein, even filtrate is not found residue through concentrated, dry, curing yet.The amount that dissolves in the n-decane part is tried to achieve according to following formula.
Dissolve in amount (wt%)=[precipitate weight/example weight] * 100 of n-decane part
MWD (Mw/Mn)
The gel permeation chromatography Alliance GPC-2000 type that MWD (Mw/Mn) uses Waters company to produce is described below and measures.Separator column uses two TSKgelGNH6-HT and two TSKgel GNH6-HTL, and the post specification is diameter 7.5mm, long 300mm; Column temperature is 140 ℃, and mobile phase is used orthodichlorobenzene (the pure pharmaceutical worker's industry of Japan and light), and inhibitor uses BHT (Japanese military field medicine) 0.025 weight %; Moved with 1.0ml/ minute; Sample solution concentration is 15mg/10mL, and the sample IR is 500 microlitres, and detector uses the differential diffractometer.Polystyrene standard is Mw＜1000 and Mw＞4 * 10 about molecular weight 6The product product that uses eastern Cao company to produce, about 1000≤Mw≤4 * 10 6The product product that uses Pressure Chemical company to produce.
Ethene in the polymkeric substance, propylene, terminal olefin content
The JNM GX-500 type NMR determinator that the quantification of ethene, propylene, terminal olefin content uses Jeol Ltd. to produce is described below and measures.Sample 0.35g heating is dissolved among the hexachlorobutadiene 2.0ml.After this solution filtered with glass filter (G2), add deuterate benzene 0.5ml, in the NMR pipe of the internal diameter 10mm that packs into, carry out at 120 ℃ 13C-NMR measures.Cumulative frequency is more than 10,000 times.According to gained 13C-NMR spectrum is carried out quantitatively the composition of ethene, propylene, terminal olefin.
Fusing point (Tm), melting heat (Δ H)
The DSCPyris1 or the DSC7 that use PerkinElmer company to produce under nitrogen environment (20ml/min), are warmed up to 200 ℃ with about 5mg sample, keep being cooled to 30 ℃ with 10 ℃/minute speed after 10 minutes.After 30 ℃ kept 5 minutes, the peak maximum of the crystallization melting peak when being warmed up to 200 ℃ with 10 ℃/minute speed calculated fusing point, calculated melting heat by the integrated value at peak.
Wherein, in the acrylic polymer described in the embodiment of the invention, under the situation that observes two peaks, the low temperature side peak is designated as Tm 1, the high temperature side peak is designated as Tm 2Situation under, with Tm 2The defined Tm of condition [2] for first aspect present invention.
Half isothermal crystal time (t 1/2 )
With being filled in about sample 5mg in the special-purpose aluminium dish; The DSCPyris1 or the DSC7 that use PerkinElmer company to produce; According to being warmed up to 200 ℃ by 30 ℃, after 5 minutes, cool to 110 ℃ of isothermal crystal temperature by 200 ℃ with 320 ℃/min 200 ℃ of maintenances with 320 ℃/min; The DSC curve that keeps each isothermal crystal temperature and obtain obtains hypocrystalline time (t 1/2).Wherein, hypocrystalline time (t 1/2) try to achieve through the isothermal crystal process time opening (by 200 ℃ of moment that reach the isothermal crystal temperature) is made as t=0.Compsn of the present invention can be tried to achieve t as stated 1/2, for example, under certain isothermal crystal temperature, for example under 110 ℃ of non crystallized situation, through under the isothermal crystal temperature below 110 ℃, get a plurality of points and measure easily, ask for hypocrystalline time (t by its extrapolated value 1/2).
MFR
According to JIS K-6721, under 230 ℃, the load of 2.16kgf, measure.
Various mensuration are with the making method of compacting sheet material
Use is set in 200 ℃ refreshing rattan metal industry corporate system hydraulic type thermocompressor, under the pressure of 10MPa, forms sheet material.In the thick sheet material of the 0.5～3mm (shape of spacer; Obtain 80 * 80 * 0.5～3mm, 4 on the thick plate of 240 * 240 * 2mm) situation under; Waste heat through about 5～7 minutes; Pressurization was used another the refreshing rattan metal industry corporate system hydraulic type thermocompressor that is set in 20 ℃, in the 10MPa lower compression after 1～2 minute under 10MPa; Cooled off about 5 minutes, and processed to measure and use sample.As hot plate, use the thick sheet brass of 5mm.Use manufactured samples according to the method described above, be used for various evaluation of physical property samples.
Modulus in tension
By the thick compacting sheet material of 1mm, according to JIS K6301, use the test piece of JIS3 dumbbell with O dumbbell punching press, be used to estimate sample.Sample is measured down at 23 ℃ under distance between bench marks: 30mm, draw speed 30mm/min.
The Izod shock strength
According to ASTM D-256, strike out the test piece of 12.7mm (wide) * 3.2mm (thick) * 64mm (length) by the thick compacting sheet material of 3mm, introduce the breach of mechanical workout, 0 ℃ of mensuration.
TMA measures the softening temperature that obtains
According to JIS K7196, the test piece of used thickness 1mm with the heat-up rate of 5 ℃/min, applies 2Kgf/cm on the pressure head of the plane of Φ 1.8mm 2Pressure, by the TMA curve try to achieve softening temperature (℃).
Inner turbidity is with the making method of working sample
Under the situation of 1mmt compacting sheet material, make test according to above-mentioned various mensuration with the making method of compacting sheet material and use sample.In addition, under the situation of 2mmt injection sheet, the injection machine IS-55 that uses Toshiba Corporation to produce is at 200 ℃ of resin temperatures, injection pressure 1000kgf/cm 2, 40 ℃ of die temperatures condition under be shaped.Make the test film of the square plate of thick 2mm * vertical 120mm * horizontal 130mm.
Inner turbidity (%)
The compacting sheet material of used thickness 1mm is as test film, measures with the digital turbidometer " NDH-20D " that Japanese electric look Industrial Co., Ltd produces.
Injecting formability is estimated
Use 55 tons of injection machines of Toshiba's system, under 200 ℃ of resin temperatures, 40 ℃ of die temperatures, two kinds of conditions of 20 seconds cooling times (condition 1) and 1 second (condition 1), implement.The evaluation of plasticity is through implementing injection forming 5 times; To exist because of thrusting pin and peel off, but the situation of continuous operation is designated as zero, will peel off the situation that once can not realize by mould and be designated as △ from mould; Will less than by the peeling off of mould, can not continuous operation situation be designated as *, estimate.
[the synthetic example of catalyzer]
Dibenzyl methylene radical (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride is according to TOHKEMY 2004-189668 number synthetic routine 3 described method manufacturings.
Dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride according to [1-1] the same method manufacturing of synthetic example.
[polymerization example 3-1]
(synthesizing of syndiotactic propene polymer (A-1))
Fully carrying out nitrogen metathetical internal volume 3m 3Reactive tank in, add normal heptane 1000L, drip toluene solution (Al=1.53mol/l) 610mL (0.93mol) of MAO at normal temperatures.On the other hand; In the flask of the band branch road that has fully carried out nitrogen metathetical internal volume 5L; Add magnetic agitation,, add dibenzyl methylene radical (cyclopentadienyl moiety) (3 then again to the toluene solution that wherein adds MAO (Al=1.53mol/l) 610mL (0.93mol); 6-di-t-butyl fluorenyl) toluene solution of zirconium dichloride 1.30g (1.86mmol) stirred 20 minutes.This solution is added in the reactive tank, use 10 minutes then, with 19Nm 3The flow of/h is supplied with hydrogen 3200NL.Supply with propylene with 65kg/h then, hydrogen supply, making the phase concentrations in the reactive tank is 53mol%, the beginning polymerization.When keeping the phase concentrations of hydrogen in reactive tank to be 53mol%, supply with propylene continuously with the amount of 65kg/h, after 25 degree are implemented polymerization in 4 hours, add a spot of Diethylene Glycol monoisopropyl ether, stop polymerization.Resulting polymers is used heptane 1.8m 3Clean, 80 ℃ of following drying under reduced pressure 15 hours, the result obtained polymkeric substance 100kg.Polymerization activity is 13.4kg-PP/mmol-Zrhr.[η] of resulting polymers is 1.90dl/g, Tm 1=152 ℃, Tm 2=158 ℃, rrrr divides rate=94%.
[polymerization example 3-2]
(synthesizing of syndiotactic propene polymer (A-2))
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 250ml, make the propylene circulation with 150 liters/hour amounts, kept 20 minutes down at 25 ℃.On the other hand; In the flask of the band branch road that has fully carried out nitrogen metathetical internal volume 30ml, add magnetic agitation, again to the toluene solution that wherein adds MAO (Al=1.53mol/l) 5.00mmol, then; Add dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) the toluene solution 5.0 μ mol of zirconium dichloride stirred 20 minutes.This solution is added in the toluene that makes the glass autoclave that flow of propylene passes through in advance the beginning polymerization.Supply with propylene gas continuously with 150 liters/hour amounts, under normal pressure, after carrying out 10 minutes polymerization under 25 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 6.95g.Polymerization activity is 7.58kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.90dl/g, Tm 1=157 ℃, Tm 2=162 ℃, rrrr divides rate=95%.
[polymerization example 3-3]
(synthesizing of syndiotactic propene polymer (A-3))
The carrying out of thorough drying in the SUS system autoclave of nitrogen metathetical internal volume 2.0L, add heptane 1.0L, under agitation introduce propylene gas then and purge, reach 0.3MPaG until pressure.Implement repeatedly and should operate 3 times.On the other hand; In the flask of the band branch road that has fully carried out nitrogen metathetical internal volume 50ml, add magnetic agitation; Add toluene solution (Al=1.53mol/l) 1.80mmol of MAO then, then add dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3; 6-di-t-butyl fluorenyl) the toluene solution 1.8 μ mol of zirconium dichloride stirred 15 minutes.Add this solution to SUS that flow of propylene is passed through and make in the heptane of autoclave, the beginning polymerization.The continuous propylene gas of supplying with presses in making to be 0.2MPaG, after 25 ℃ of enforcement polymerization in 60 minutes, adds a spot of methyl alcohol, stops polymerization.Utilize filter operation, from the heptane slurry, reclaim polymkeric substance, 80 ℃ of following drying under reduced pressure 6 hours, the result obtained polymkeric substance 75.4g.Polymerization activity is 42.0kg-PP/mmol-Zrhr.[η] of resulting polymers is 2.4dl/g, and Tm=161 ℃, rrrr divides rate=97%.
[embodiment 3-1]
Syndiotactic polypropylenes polymkeric substance 100 weight parts with respect to polymerization example 3-1 gained add three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part as secondary antioxidant, as the phenylpropionic acid of heat-resisting stabilizing agent; 3, two (1, the 1-the dimethyl ethyl)-4-hydroxyls of 5--; 2,2-is two, and [[[3,5-two (1 for 3-; The 1-dimethyl ethyl)-the 4-hydroxy phenyl]-the 1-oxopropoxy] methyl]-1,3-glyceryl ester 0.1 weight part is as calcium stearate 0.1 weight part of neutralizing agent.Use the smart machine corporate system ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) of Japan then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), behind the 50rpm, 5 minutes melting mixings, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 3-2.Cooperate above-mentioned additive with respect to this polymkeric substance with amount again; Twin screw extruder BT-30 (Φ 30mm, L/D=46, the equidirectional rotation of using Pravo company to produce; Needing-zone everywhere); Under 230 ℃ of design temperatures, granulation under the condition of resin extruded amount 50g/min, 200rpm is used for the injection forming evaluation test.The result is shown among the table 3-3.Compare with comparative example, plasticity and good heat resistance, and the harmony of the transparency, mechanical characteristics and intensity is also excellent.
[embodiment 3-2]
Syndiotactic polypropylenes polymkeric substance 100 weight parts with respect to polymerization example 3-2 gained cooperate embodiment 1 employed additive with amount.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 3-2.Compare with comparative example, plasticity and good heat resistance, and the harmony of the transparency, mechanical characteristics and intensity is also excellent.
[embodiment 3-3]
Syndiotactic polypropylenes polymkeric substance (A-3) 100 weight parts with respect to polymerization example 3-3 gained cooperate the employed additive of embodiment 3-1 with amount.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 3-2.Compare with comparative example, plasticity and good heat resistance, and the harmony of the transparency, mechanical characteristics and intensity is also excellent.
[comparative example 3-1]
Vestolen PP 7052 1471 pellets that use TOTAL company to produce are processed the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 3-2.This pellet is used for the injection forming evaluation test.The result is shown among the table 3-3.Compare with embodiment, plasticity and poor heat resistance, the harmony of mechanical characteristics and intensity is also poor.
[comparative example 3-2]
The Vestolen PP 7052 F327 pellet that uses the Prime Polymer of Co., Ltd. to produce is processed the compacting sheet material, measures rerum natura.Various rerum natura results are shown in table 3-2.This pellet is used for the injection forming evaluation test.The result is shown among the table 3-3.Compare with embodiment, poor heat resistance, the harmony of the transparency, mechanical characteristics and intensity is also poor.
Figure GSA00000105371102221
Figure GSA00000105371102231
Table 3-3
Figure GSA00000105371102241
[EXAMPLE IV]
Below, further specifying the present invention (4) according to embodiment, the present invention is not limited to these embodiment.Wherein, each rerum natura is described below and measures among the embodiment.
The physical property measurement method
[limiting viscosity [η]]
According to measuring with the same method of EXAMPLE III.
[dissolving in the amount of n-decane part]
According to measuring with the same method of EXAMPLE III.
[MWD (Mw/Mn)]
According to measuring with the same method of EXAMPLE III.
[ethene in the polymkeric substance, propylene, terminal olefin content]
The JNM GX-400 type NMR determinator that the quantitative use NEC (strain) of ethene, propylene, terminal olefin content produces is described below and measures.Sample 0.35g heating is dissolved among the hexachlorobutadiene 2.0ml.After this solution filtered with glass filter (G2), add deuterate benzene 0.5ml, in the NMR test tube of the internal diameter 10mm that packs into, carry out at 120 ℃ 13C-NMR measures.Cumulative frequency is more than 8,000 times.According to gained 13The C-NMR spectrum is to the composition quantification of ethene, propylene, terminal olefin.
[(AA) fusing point of composition (Tm), melting heat (Δ H)]
According to measuring with the same method of EXAMPLE III.
[half isothermal crystal time t 1/2]
According to measuring with the same method of EXAMPLE III.
[(B2) second-order transition temperature of composition (Tg), fusing point (Tm)]
The DSC that uses Seiko-Instruments company to produce; In measuring, pile up the sample of about 5mg, according to being warmed up to 200 ℃, after keeping 5 minutes under 200 ℃ with 100 ℃/min with the aluminium dish; Cool to-150 ℃ with 10 ℃/min, then be warmed up to 200 ℃ endothermic curve and try to achieve with 10 ℃/min.
[MFR]
The MFR of syndiotactic propene polymer (AA) and propylene-alpha-olefin copolymers (B3) is according to JIS K-6721, under 230 ℃, the load of 2.16kg, measures.
Ethylene-butene copolymer (C0) is according to JIS K-6721, under 190 ℃, the load of 2.16kg, measures.
[various mensuration are with the making method of compacting sheet material]
According to measuring with the same method of EXAMPLE III.
[modulus in tension]
According to measuring with the same method of EXAMPLE III.
[Izod shock strength]
According to measuring with the same method of EXAMPLE III.
[TMA measures the softening temperature that obtains]
According to measuring with the same method of EXAMPLE III.
[inner turbidity (%)]
The test film of used thickness 1mm is measured with the digital turbidometer " NDH-20D " that Japanese electric look Industrial Co., Ltd produces.
[learning the glossiness velocity of variation (%) after vibration is decreased]
Use the smart mechanism of Japan to learn vibration and decrease trier; The test piece of used thickness 2mm; The tip of the wearing and tearing pressure head 470g of 45R, SUS system is covered with cotton duck #10, with its 23 ℃, come and go number of times 100 times, 33 times/min of shuttle speed; The sample that rubs under the condition of stroke 100mm is described below and tries to achieve the glossiness velocity of variation Δ Gloss before and after it.
Gloss * 100 before Δ Gloss=(Gloss after the Gloss-friction before the friction)/friction
[residual strain (%) after 200% stretching]
To have long 50mm (L 0), the dumbbell plate of the thickness 1mmt of the shape of the length 15mm between graticule, wide 5mm is installed on the anchor clamps of distance between bench marks 30mm; Under draw speed 30mm/min; Apply the strain of 200% (distance between bench marks is to 90mm), measure then under the draw speed, eliminate strain; Remove in the process of load the length during the stress vanishing (L).Residual strain (%)=L/L 0* 100
[evaluation of film shaped property]
With the granulation pellet of compsn as sample, with the single screw extrusion machine of Φ 20mmL/D=28, at the die head of Φ 25mm; The wide 250mm of flange is under the condition of processing temperature=210 ℃, 40 ℃ of roll temperatures; Under the winding speed 0.63m/min, the film of extrusion molding thickness=250 μ m.Being evaluated as of plasticity, but will there be 1 hour situation of collaring continuous operation to be designated as zero, collaring will more or less be arranged, but the situation that can turn round is designated as △, will there be collaring, situation that can not continuous operation is designated as *, estimate.The result is shown in table 4-2.
The synthetic example of catalyzer
[synthetic routine 4-1]
Dibenzyl methylene radical (cyclopentadienyl moiety) (3,6-di-t-butyl fluorenyl) zirconium dichloride is according to TOHKEMY 2004-189666 number synthetic routine 3 described method manufacturings.
[synthetic routine 4-2]
Dibenzyl methylene radical (cyclopentadienyl moiety) (2,7-phenylbenzene-3,6-di-t-butyl fluorenyl) zirconium dichloride according to [synthetic routine 1-1] same method manufacturing.
[synthetic routine 4-3]
Two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride according to [synthetic routine 2-2] same method manufacturing.
[synthetic routine 4-4]
Synthesizing of phenylbenzene methylene radical (the 3-tertiary butyl-5-ethyl cyclopentadienyl moiety) (2,7-di-t-butyl fluorenyl) zirconium dichloride
(i) 1-ethyl-3-tertiary butyl cyclopentadiene is synthetic
Under nitrogen environment, in the there-necked flask of the 300ml that possesses magnetic agitation and three pistons, add the diethyl ether solution 52ml (154mmol) of anhydrous diethyl ether 200ml, 3.0M ethylmagnesium bromide.Under ice-water bath, with 1 hour dropping 3-tertiary butyl ketopentamethylene 17.8g (129mmol).After at room temperature stirring 20 hours, reaction soln is injected 2N hydrochloric acid 100ml.Separate organic layer, extract water layer twice with ether 50ml.The gained organic layer is merged, clean twice with saturated sodium bicarbonate aqueous solution, water cleans twice, cleans twice with saturated aqueous common salt.Use dried over mgso, distillation removes and desolvates.Refining with column chromatography then, obtain light yellow transparent liquid 20.2g (GC purity 75%).Yield is 78%.Identify and adopt 1The H-NMR spectrum is carried out.Represent it below and measure the result.
1H-NMR composes (270MHz, CDCl 3, the TMS standard): δ/ppm 6.19+6.05+5.81+5.77 (m+m+m+m, 2H), 2.91+2.85 (m+m, 2H), 2.48-2.27 (m, 2H), 1.15-1.08 (s+s+m, 12H)
The (ii) 3-tertiary butyl-1-ethyl-6,6-phenylbenzene fulvene synthetic
Under nitrogen environment, in the there-necked flask of the 300ml that possesses magnetic agitation and three pistons, add 1-ethyl-3-tertiary butyl cyclopentadiene 5.11g (23.9mmol) (GC purity 75%) and THF150ml.Under dry ice/methanol bath, slowly drip the hexane solution 16ml (25.2mmol) of 1.56M n-Butyl Lithium, at room temperature stirred then 20 hours.In the gained reaction solution, add 1,3-dimethyl--2-imidazolone 3.1ml (28.8mmol) then adds UVNUL MS-40 5.3g (28.8mmol), under refluxing, stirs 48 hours.Reaction soln is injected 2N hydrochloric acid 100ml.Separate organic layer, extract water layer twice with hexane 50ml.Merge with organic layer before, clean with saturated sodium bicarbonate aqueous solution, water, saturated sodium-chloride water solution.After dried over mgso, distillation removes and desolvates.Refining with column chromatography then, obtain orange solids 4.2g.Yield is 56%.Identify and adopt 1The H-NMR spectrum is carried out.Represent it below and measure the result.
1H-NMR composes (270MHz, CDCl 3, the TMS standard): δ/ppm 7.2-7.4 (m, 10H), 6.3 (m, 1H), 5.7 (m, 1H), 1.70+1.85 (q, 2H), 1.15 (s, 9H), 0.85 (t, 3H)
(iii) phenylbenzene methylene radical (the 3-tertiary butyl-5-ethyl cyclopentadienyl moiety) (2,7-di-t-butyl fluorenyl) is synthetic
The there-necked flask of the 200ml that possesses magnetic agitation son and three pistons is fully carried out nitrogen replace, under nitrogen environment, with 2 of 3.8g, 7-di-tert-butyl-fluorene (13.7mmol) is dissolved in the anhydrous diethyl ether of 80ml.Under ice-water bath, in this solution, slowly drip n-Butyl Lithium/hexane solution (1.56M:14.3mmol) of 9.2ml, at room temperature stirred 100 hours.In this reaction soln, add the 3-tertiary butyl-1-ethyl-6 of 4.5g, 6-phenylbenzene fulvene (14.3mmol) stirred 30 hours under refluxing.In ice bath, reaction soln injected 2N aqueous hydrochloric acid 100ml after, add diethyl ether, separate organic layer, with twice of diethyl ether 50ml extraction water layer.Merge with organic layer before, clean with saturated sodium bicarbonate aqueous solution, water, saturated sodium-chloride water solution.Use dried over mgso, distillation removes and desolvates.Refining with column chromatography then, obtain white solid 4.2g.Yield is 53%.Identify and adopt FD-mass analysis spectrum (FD-MS) to carry out.Represent it below and measure the result.
FD-MS：m/z＝592(M +)
(iv) phenylbenzene methylene radical (the 3-tertiary butyl-5-ethyl cyclopentadienyl moiety) (2,7-di-t-butyl fluorenyl) zirconium dichloride is synthetic
The schlenk pipe of the 100ml that possesses magnetic agitation son and three pistons is fully carried out nitrogen replaces; Under nitrogen environment; The phenylbenzene methylene radical (the 3-tertiary butyl-5-ethyl cyclopentadienyl moiety) (2,7-di-t-butyl fluorenyl) of 1.0g (1.68mmol) is dissolved in the anhydrous diethyl ether of 40ml.Under ice bath, the hexane solution of the n-Butyl Lithium of the 1.56M of slow dropping 2.2ml (3.4mmol) at room temperature stirred 28 hours in this solution.After with dry ice/methanol bath this reaction soln fully being cooled off, add the zirconium tetrachloride (1.68mmol) of 0.39g.Slowly return to room temperature, and after stirring 48 hours, underpressure distillation removes and desolvates.Process slurry again with hexane, filter with having filled diatomaceous glass filter.With dark brown solid on a spot of dichloromethane extraction strainer and filtration.Respectively its solvent is removed in the hexane solution and the dichloromethane solution decompression that obtain.Clean dark orange solids with a spot of pentane and diethyl ether respectively, carry out drying under reduced pressure, obtain the target compound of orange solids 140mg (0.186mmol) thus.Identify and adopt 1H-NMR spectrum and FD-mass analysis spectrum are carried out.The result is measured in expression below.
1H-NMR composes (270MHz, CDCl 3, the TMS benchmark): δ/ppm 7.90-8.07 (m, 5H), 7.75 (m, 1H), 7.15-7.60 (m, 8H), 6.93 (m, 1H), 6.15-6.25 (m, 2H), 5.6 (d, 1H), 2.05+2.25 (q, 2H), 0.95-1.15 (s+t+s, 30H)
FD-MS：m/z＝752(M +)
The polymerization example
[polymerization example 4A-1]
(synthesizing of syndiotactic propene polymer (4A-1))
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 250ml, make the propylene circulation with 150 liters/hour amounts, kept 20 minutes down at 25 ℃.On the other hand; In the flask of the band branch road that has fully carried out nitrogen metathetical internal volume 30ml; Add magnetic agitation, to the toluene solution that wherein adds MAO (Al=1.53mol/l) 5.00mmol, add dibenzyl methylene radical (cyclopentadienyl moiety) (3 then again; 6-di-t-butyl fluorenyl) the toluene solution 5.0 μ mol of zirconium dichloride stirred 20 minutes.This solution is added in the toluene that makes the glass autoclave that flow of propylene passes through in advance to the beginning polymerization.Supply with propylene gas continuously with 150 liters/hour amounts, under normal pressure, 25 ℃ carry out polymerization in 45 minutes after, add small amount of methanol, stop polymerization.Resulting polymers solution is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out.80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 2.38g.Polymerization activity is 0.63kg-PP/mmol-Zrhr.[η] of resulting polymers is 1.9dl/g, Tm 1=152 ℃, Tm 2=158 ℃, rrrr divides rate=93.5%, Mw/Mn=2.0.Implement repeatedly and should operate, the polymkeric substance that obtains necessary amount supplies embodiment to use.And in the evaluation of film shaped property, use according to above-mentioned method of manufacture, amplify in proportion having of making and above-mentioned polymer phase with the polymkeric substance of TMA softening temperature, rrrr branch rate, [η] and Mw/Mn.
[polymerization example 4A-2]
(synthesizing of syndiotactic propene polymer (4A-2))
In the glass autoclave that has fully carried out nitrogen metathetical internal volume 500ml, add toluene 250ml, make the propylene circulation with 150 liters/hour amounts, kept 20 minutes down at 25 ℃.On the other hand; In the flask of the band branch road that has fully carried out nitrogen metathetical internal volume 30ml, add magnetic agitation, again to the toluene solution that wherein adds MAO (Al=1.53mol/l) 5.00mmol, then; Add dibenzyl methylene radical (cyclopentadienyl moiety) (2; 7-phenylbenzene-3,6-di-t-butyl fluorenyl) the toluene solution 5.0 μ mol of zirconium dichloride stirred 20 minutes.This solution is added in the toluene that makes the glass autoclave that flow of propylene passes through in advance the beginning polymerization.Supply with propylene gas continuously with 150 liters/hour amounts, under normal pressure, after carrying out 10 minutes polymerization under 25 ℃, add small amount of methanol, stop polymerization.Polymers soln is added in a large amount of excessive methyl alcohol, polymkeric substance is separated out, 80 ℃ of following drying under reduced pressure 12 hours, the result obtained polymkeric substance 6.95g.Polymerization activity is 7.58kg-PP/mmol-Zrhr, and [η] of resulting polymers is 2.9dl/g, and Tm=162.0 ℃, rrrr divides rate=95.3%.Implement repeatedly and should operate, the polymkeric substance that obtains necessary amount supplies embodiment to use.
(syndiotactic propene polymer (4A-3))
The syndiotactic polypropylenes (trade(brand)name: Finaplas1471, MFR=5.0g/10 minute) that Total company is produced is used for embodiment.Rerum natura is shown among the table 4-1.
[polymerization example 4A-4]
(synthesizing of syndiotactic propene polymer (4A-4))
Except introducing hydrogen (promptly; In polymerization system, also supply with the hydrogen); Method of manufacture according to polymerization example 4A-1; Manufacturing has the TMA softening temperature identical with above-mentioned polymkeric substance (4A-1), rrrr branch rate, Mw/Mn, the syndiotactic propene polymer (4A-4) (alfon) of [η]=1.4dl/g.The rerum natura of polymkeric substance (4A-4) is shown among the table 4-4.
[polymerization example 4A-5]
(synthesizing of syndiotactic propene polymer (4A-5))
Except introducing hydrogen (promptly; In polymerization system, also supply with the hydrogen); Method of manufacture according to polymerization example 4A-1; Manufacturing has the TMA softening temperature identical with above-mentioned polymkeric substance (4A-1), rrrr branch rate, Mw/Mn, the syndiotactic propene polymer (4A-5) (alfon) of [η]=1.2dl/g.The rerum natura of polymkeric substance (4A-5) is shown among the table 4-4.
(syndiotactic propene polymer (4A-6)
The syndiotactic polypropylenes (trade(brand)name: Finaplas1571, MFR=9.1g/10 minute) that Total company is produced is used for embodiment.Rerum natura is shown among the table 4-4.
[polymerization example 4B-1]
(synthesizing of propylene-alpha-olefin copolymers (4B-1))
In the poly-unit that has fully carried out nitrogen metathetical internal volume 4000ml; Add at normal temperatures after the dry hexane and triisobutyl aluminium (1.0mmol) of 1834ml; The poly-unit internal temperature is warmed up to 70 ℃; With propylene the exert pressure in the system is arrived 0.66MPa, with ethene the pressure in the system is adjusted to 1.36MPa then.Then; In poly-unit, add and make two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.001mmol and to be converted into the MAO that aluminium is 0.3mmol (production of Tosoh Fine Chem company) and to contact the toluene solution that gets; When 70 ℃ of internal temperatures, system internal pressure utilize ethene to remain on 1.36MPa; Carry out 15 minutes polymerization, add the methyl alcohol of 20ml, stop polymerization.Behind the decompress(ion), in the methyl alcohol of 4L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 105g, and MFR is 0.7 (g/10min), [η]=2.5 of in 135 ℃ of naphthane, measuring (dL/g).The rerum natura that resulting polymers is measured is shown in table 4-1.And the rr1 value is 78%.
[polymerization example 4B-2]
(propylene-alpha-olefin copolymers (4B-2))
In the poly-unit that has fully carried out nitrogen metathetical internal volume 4000ml; Add at normal temperatures after the dry hexane and triisobutyl aluminium (1.0mmol) of 1834ml; The poly-unit internal temperature is warmed up to 70 ℃; With propylene with the exert pressure in the system after 0.64MPa, with ethene the pressure in the system is adjusted to 1.34MPa.Then; In polymerizer, add and make two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.001mmol and to be converted into the MAO that aluminium is 0.3mmol (production of Tosoh Fine Chem company) and to contact the toluene solution that gets; When 70 ℃ of internal temperatures, system internal pressure utilize ethene to remain on 1.34MPa; Carry out 15 minutes polymerization, add the methyl alcohol of 20ml, stop polymerization.Behind the decompress(ion), in the methyl alcohol of 4L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 109g, and MFR is 0.6 (g/10min), [η]=2.6 of in 135 ℃ of naphthane, measuring (dL/g).The rerum natura that resulting polymers is measured is shown in table 4-1.And the rr1 value is 76%.Implement repeatedly and should operate, the polymkeric substance that obtains necessary amount supplies embodiment to use.And in the evaluation of film shaped property, use and to create conditions, amplify the polymkeric substance of having of making and the same ethylene content of above-mentioned polymer phase, rr branch rate, [η], Mw/Mn in proportion according to above-mentioned.
[polymerization example 4B-3]
Propylene-alpha-olefin copolymers (4B-3)
In the poly-unit that has fully carried out nitrogen metathetical internal volume 4000ml; Add at normal temperatures after the dry hexane and triisobutyl aluminium (1.0mmol) of 1834ml; The poly-unit internal temperature is warmed up to 70 ℃; With propylene with the exert pressure in the system after 0.67MPa, with ethene the pressure in the system is adjusted to 1.37MPa.Then; In polymerizer, add and make two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.001mmol and to be converted into the MAO that aluminium is 0.3mmol (production of Tosoh Fine Chem company) and to contact the toluene solution that gets; When 70 ℃ of internal temperatures, system internal pressure utilize ethene to remain on 1.37MPa; Carry out 10 minutes polymerization, add the methyl alcohol of 20ml, stop polymerization.Behind the decompress(ion), in the methyl alcohol of 4L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 90g, and MFR is 1.0 (g/10min), [η]=2.3 of in 135 ℃ of naphthane, measuring (dL/g).And rr 1Value is 75%.The rerum natura that resulting polymers is measured is shown in table 4-1.
[polymerization example 4B-4]
(synthesizing of propylene-alpha-olefin copolymers (4B-4))
In the poly-unit that has fully carried out nitrogen metathetical internal volume 4000ml; Add at normal temperatures after the 1-butylene and triisobutyl aluminium (1.0mmol) of dry hexane, 20g of 1834ml; The poly-unit internal temperature is warmed up to 70 ℃; With propylene with the exert pressure in the system after 0.63MPa, with ethene the pressure in the system is adjusted to 1.33MPa.Then; In polymerizer, add and make two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.001mmol and to be converted into the MAO that aluminium is 0.3mmol (production of Tosoh FineChem company) and to contact the toluene solution that gets; When 70 ℃ of internal temperatures, system internal pressure utilize ethene to remain on 1.33MPa; Carry out 10 minutes polymerization, add the methyl alcohol of 20ml, stop polymerization.Behind the decompress(ion), in the methyl alcohol of 4L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 102g, and MFR is 1.0 (g/10min), [η]=2.3 of in 135 ℃ of naphthane, measuring (dL/g).The rerum natura that resulting polymers is measured is shown in table 4-1.And the rr1 value is 75%.
[polymerization example 4B-5]
(synthesizing of propylene-alpha-olefin copolymers (4B-5))
In the poly-unit that has fully carried out nitrogen metathetical internal volume 4000ml; Add at normal temperatures after the dry hexane and triisobutyl aluminium (1.0mmol) of 1834ml; The poly-unit internal temperature is warmed up to 50 ℃; With propylene with the exert pressure in the system after 0.67MPa, with ethene the pressure in the system is adjusted to 1.37MPa.Then; In polymerizer, add and make two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.001mmol and to be converted into the MAO that aluminium is 0.3mmol (production of Tosoh Fine Chem company) and to contact the toluene solution that gets; When 50 ℃ of internal temperatures, system internal pressure utilize ethene to remain on 1.37MPa; Carry out 10 minutes polymerization, add the methyl alcohol of 20ml, stop polymerization.Behind the decompress(ion), in the methyl alcohol of 4L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 78g, [η]=3.5 of in 135 ℃ of naphthane, measuring (dL/g).Utilize 13The ethylene content that C-NMR measures is 18mol%.The rerum natura that resulting polymers is measured is shown in table 4-4.
In addition, the particular content of ethylene-butene copolymer (4C) and propene polymer (4D-1)～(4D～8) is described below.
(ethylene-butene copolymer (4C))
Shown in the table 4-1, MFR=4.0g/10 minute
(propene polymer (4D-1))
The PP (trade(brand)name F102W, MFR=2.1g/10 minute) that Prime Polymer company produces
(propene polymer (4D-2))
The PP (trade(brand)name J104W, MFR=5.2g/10 minute) that Prime Polymer company produces
(propene polymer (4D-3))
The PP (trade(brand)name B101, MFR=0.7g/10 minute) that Prime Polymer company produces
(propene polymer (4D-4))
The PP (trade(brand)name J106G, MFR=15.0g/10 minute) that Prime Polymer company produces
(propene polymer (4D-5))
The PP (trade(brand)name J107G, MFR=30.0g/10 minute) that Prime Polymer company produces
(propene polymer (4D-6))
The PP (trade(brand)name J108M, MFR=45.0g/10 minute) that Prime Polymer company produces
(propene polymer (4D-7))
(synthesizing of propylene-ethylene-butene multipolymer)
In the poly-unit that has fully carried out nitrogen metathetical 4000ml; Add at normal temperatures after dry hexane, 1-butylene 110g and the triisobutyl aluminium (1.0mmol) of 1834ml; The poly-unit internal temperature is warmed up to 55 ℃; With propylene with the exert pressure in the system after 0.58MPa, with ethene the pressure in the system is adjusted to 0.75MPa.Then; In polymerizer, add and make synthetic routine 4-4 synthetic phenylbenzene methylene radical (the 3-tertiary butyl-5-ethyl cyclopentadienyl moiety) (2; 7-di-t-butyl fluorenyl) zirconium dichloride 0.001mmol be converted into the MAO that aluminium is 0.3mmol (production of Tosoh Fine Chem company) and contact the toluene solution that gets, when 55 ℃ of internal temperatures, system internal pressure utilize ethene to remain on 0.75MPa, carry out 25 minutes polymerization; Add the methyl alcohol of 20ml, stop polymerization.Behind the decompress(ion), in the methyl alcohol of 4L, from polymeric solution, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours.Resulting polymers is 120.2g, and MFR is 0.7 (g/10min).The rerum natura that resulting polymers is measured is shown in table 4-5.
(propene polymer (4D-8))
Except polymerization temperature is 40 ℃, make according to the creating conditions of aforesaid propylene polymkeric substance (4D-7), make the identical ethylene content, the butene content that have with above-mentioned polymkeric substance (4D-7), the polymkeric substance of [η]=4.0, Mw/Mn=2.1 (4D-8).The character of resulting polymers is shown in table 4-5.
The rerum natura of aforesaid propylene polymkeric substance (4D-1)～(4D-8) is shown in table 4-5.
Polymkeric substance (4B-1)～(4B-5), (4A-1), (4A-3), (4A-4), (4A-5) and the MFR (4A-6) that isotactic acrylic polymer (4D-1)～(4D-8) and the present invention (4) are used and the graphic representation of [η] are shown in Fig. 3.Hence one can see that, and isotactic propene polymer (4D-1)～(4D-8) is distinguished by condition (b-2) with the used polymkeric substance of the present invention (4).
[embodiment 4-1]
Propylene-ethylene copolymers (4B-2) 20 weight parts that syndiotactic polypropylenes (4A-1) 80 weight parts that [polymerization example (4A-1)] obtains and [polymerization example (4B-2)] obtain; With respect to 100 weight part said compositions; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-2.Plasticity and excellent heat resistance, and the transparency, shock resistance, anti-impaired property are excellent.
[embodiment 4-2]
Propylene-ethylene copolymers (4B-2) 30 weight parts that syndiotactic polypropylenes (4A-1) 70 weight parts that [polymerization example (4A-1)] obtains and [polymerization example (4B-2)] obtain; With respect to 100 weight part said compositions; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-2.Plasticity and excellent heat resistance, and the transparency, shock resistance, anti-impaired property are excellent.
[embodiment 4-3]
Propylene-ethylene copolymers (4B-2) 40 weight parts that syndiotactic polypropylenes (4A-1) 60 weight parts that [polymerization example (4A-1)] obtains and [polymerization example (4B-2)] obtain; With respect to 100 weight part said compositions; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-2.Plasticity and excellent heat resistance, and the transparency, shock resistance, anti-impaired property are excellent.
[embodiment 4-4]
Propylene-ethylene copolymers (4B-1) 40 weight parts that syndiotactic polypropylenes (4A-1) 60 weight parts that [polymerization example (4A-1)] obtains and [polymerization example (4B-1)] obtain; With respect to 100 weight part said compositions; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-2.Plasticity and excellent heat resistance, and the transparency, shock resistance, anti-impaired property are excellent.
[embodiment 4-5]
Syndiotactic polypropylenes (4A-1) 60 weight parts that [polymerization example (4A-1)] obtains and propylene-ethylene copolymers (4B-4) 40 weight parts that obtain according to [polymerization example (4B-4)]; With respect to 100 weight part said compositions; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-2.Plasticity and excellent heat resistance, and the transparency, shock resistance, anti-impaired property are excellent.
[comparative example 4-1]
Syndiotactic polypropylenes (the 4A-3) (trade(brand)name: Finaplas1471 that TOTAL company produces; MFR=5.0g/10 minute; Rrrr branch rate=69%) 60 weight parts and propylene-ethylene copolymers (4B-2) 40 weight parts that [polymerization example (4A-4)] obtains with respect to 100 weight part said compositions, cooperate as three (2 of secondary antioxidant; The 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part; As the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-2.Compare plasticity and poor heat resistance with embodiment 4-1～4-5.
[embodiment 4-6]
Propylene-ethylene copolymers (4B-3) 80 weight parts that syndiotactic polypropylenes (4A-1) 20 weight parts that [polymerization example (4A-1)] obtains and [polymerization example (4B-3)] obtain; With respect to 100 weight part said compositions; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-3.Plasticity and excellent heat resistance, and the transparency, shock resistance, anti-impaired property are excellent.
[embodiment 4-7]
Propylene-ethylene copolymers (4B-3) 70 weight parts that syndiotactic polypropylenes (4A-1) 30 weight parts that [polymerization example (4A-1)] obtains and [polymerization example (4B-3)] obtain; With respect to 100 weight part said compositions; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-3.Plasticity and excellent heat resistance, and the transparency, shock resistance, anti-impaired property are excellent.
[embodiment 4-8]
Propylene-ethylene copolymers (4B-3) 80 weight parts that syndiotactic polypropylenes (4A-2) 20 weight parts that [polymerization example (4A-2)] obtains and [polymerization example (4B-3)] obtain; With respect to 100 weight part said compositions; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-3.Plasticity and excellent heat resistance, and the transparency, shock resistance, anti-impaired property are excellent.
[comparative example 4-2]
Syndiotactic polypropylenes (the 4A-3) (trade(brand)name: Finaplas1471 that TOTAL company produces; MFR=5.0g/10 minute) propylene-ethylene copolymers (4B-3) 80 weight parts that obtain of 20 weight parts and [polymerization example (4B-3)]; With respect to 100 weight part said compositions; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-3.Compare plasticity and poor heat resistance with embodiment 4-6,4-7.
[comparative example 4-3]
Syndiotactic polypropylenes (the 4A-3) (trade(brand)name: Finaplas1471 that TOTAL company produces; MFR=5.0g/10 minute) 30 weight parts and ethylene-butene copolymer (C) 70 weight parts; With respect to 100 weight part said compositions; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 4-3.Compare with embodiment 4-6,4-7, plasticity and poor heat resistance, and transparent, anti-impaired property is poor.
Figure GSA00000105371102421
Figure GSA00000105371102441
[EXAMPLE V]
Below, further specifying the present invention (5) according to embodiment, the present invention is not limited to these embodiment.Wherein, each rerum natura is described below and measures among the embodiment.
The physical property measurement method
[limiting viscosity [η]]
According to measuring with the same method of EXAMPLE IV.
[dissolving in the amount of n-decane part]
According to measuring with the same method of EXAMPLE IV.
[MWD (Mw/Mn)]
According to measuring with the same method of EXAMPLE IV.
[ethene in the polymkeric substance, propylene, terminal olefin content]
According to measuring with the same method of EXAMPLE IV.
[fusing point (Tm), melting heat (Δ H)]
The DSC7 that uses PerkinElmer company to produce according under nitrogen environment (20ml/min), is warmed up to 200 ℃ with about 5mg sample, keeps being cooled to 30 ℃ with 10 ℃/minute after 10 minutes.After 30 ℃ kept 5 minutes, the peak maximum of the crystallization melting peak when being warmed up to 200 ℃ with 10 ℃/minute calculated fusing point, calculated melting heat by the integrated value at peak.
[half isothermal crystal time (t 1/2)]
According to measuring with the same method of EXAMPLE IV.
[glass transition point (Tg)]
According to measuring with the same method of EXAMPLE IV.
[MFR]
According to measuring with the same method of EXAMPLE IV.
[various mensuration are with the making method of compacting sheet material]
According to making with the same method of EXAMPLE IV.
[modulus in tension]
According to measuring with the same method of EXAMPLE IV.
[Izod shock strength]
According to measuring with the same method of EXAMPLE IV.
[TMA measures the softening temperature that obtains]
According to measuring with the same method of EXAMPLE IV.
[inner turbidity (%)]
According to measuring with the same method of EXAMPLE IV.
Polymkeric substance
Syndiotactic polypropylenes (5A-1)～(5A～6), propylene-alpha-olefin copolymers (5B-1)～(5B～5), ethylene-butene copolymer (C) and specifying of propene polymer (D-1)～(D-8) are described below.
(syndiotactic polypropylenes (5A-1)～(5A～6))
Respectively and (4A-6) and (5A-6) as syndiotactic polypropylenes (5A-1), (5A-2), (5A-3), (5A-4), (5A-5) with the syndiotactic polypropylenes (4A-1) of EXAMPLE IV, (4A-2), (4A-3), (4A-4), (4A-5).
(propylene-alpha-olefin copolymers (5B-1)～(5B～5))
Respectively and (4B-5) and (5B-5) as propylene-alpha-olefin copolymers (5B-1), (5B-2), (5B-3), (5B-4) with the propylene-alpha-olefin copolymers (4B-1) of EXAMPLE IV, (4B-2), (4B-3), (4B-4).
(ethene-crotonyl polymers (5C-1)～(5C-3))
The rerum natura of ethene-butene-1 random copolymers (5C-1)～(5C-3) is shown in table 5-1.
(propene polymer (5D-1)～(5D-8))
Respectively and (4D-8) and (5D-8) as propene polymer (5D-1), (5D-2), (5D-3), (5D-4), (5D-5), (5D-6), (5D-7) with the propene polymer (4D-1) of EXAMPLE IV, (4D-2), (4D-3), (4D-4), (4D-5), (4D-6), (4D-7).
Aforesaid propylene polymkeric substance (5D-1)～(5D-8), promptly the rerum natura of aforesaid propylene polymkeric substance (4D-1)～(4D-8) is shown in table 4-5.
Used polymkeric substance (5B-1)～(5B-5) (5A-1), (5A-3), (5A-4), the MFR of (5A-5), (5A-6) (being above-mentioned polymkeric substance (4B-1)～(4B-5), (4A-1), (4A-3), (4A-4), (4A-5), (4A-6)) and the graphic representation of [η] of isotactic acrylic polymer (5D-1)～(5D-8) (being above-mentioned polymkeric substance (4D-1)～(4D-8)) and the present invention (5) is shown in Fig. 3.Hence one can see that, and the used polymkeric substance of isotactic propene polymer and the present invention (5) is distinguished by condition (b-2).
Figure GSA00000105371102471
[embodiment 5-1]
Syndiotactic polypropylenes (5A-1) 100 weight parts that [polymerization example (5A-1)] obtains; And ethene-1-butylene random copolymers (5C-1) (MFR (190 ℃)=4.0; 1-butylene content 12mol%) 25 weight parts with respect to said composition, cooperate as three (2 of secondary antioxidant; The 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part; As the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 5-2.Plasticity and excellent heat resistance, and the transparency, low-temperature impact resistance is excellent.
[embodiment 5-2]
Syndiotactic polypropylenes (5A-1) 100 weight parts that [polymerization example (5A-1)] obtains; And ethene-1-butylene random copolymers (5C-1) (MFR (190 ℃)=4.0; 1-butylene content 12mol%) 66.7 weight parts with respect to said composition, cooperate as three (2 of secondary antioxidant; The 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part; As the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 5-2.Plasticity and excellent heat resistance, and the transparency, flexibility, low-temperature impact resistance are excellent.
[embodiment 5-3]
Propylene-ethylene copolymers (5B-1) 25 weight parts that syndiotactic polypropylenes (5A-1) 75 weight parts that [polymerization example (5A-1)] obtains, [polymerization example (5B-1)] obtain; And ethene-1-butylene random copolymers (5C-3) (MFR (190 ℃)=4.0; 1-butylene content 15mol%) 25 weight parts with respect to said composition, cooperate as three (2 of secondary antioxidant; The 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part; As the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 5-2.Plasticity and excellent heat resistance, and the transparency, flexibility, low-temperature impact resistance are excellent.
[embodiment 5-4]
Propylene-ethylene copolymers (5B-3) 33.4 weight parts, ethene-1-butylene random copolymers (5C-2) (MFR (190 ℃)=0.5 that syndiotactic polypropylenes (5A-1) 66.7 weight parts that [polymerization example (5A-1)] obtains, [polymerization example (5B-3)] obtain; 1-butylene content 12mol%) 66.7 weight parts; With respect to said composition; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 5-2.Plasticity and excellent heat resistance, and the transparency, flexibility, shock resistance are excellent.
[embodiment 5-5]
Propylene-ethylene copolymers (5B-4) 50 weight parts that syndiotactic polypropylenes (5A-2) 50 weight parts that [polymerization example (5A-2)] obtains, [polymerization example (5B-4)] obtain; And ethene-1-butylene random copolymers (5C-3) (MFR (190 ℃)=4.0; 1-butylene content 15mol%) 25 weight parts with respect to said composition, cooperate as three (2 of secondary antioxidant; The 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part; As the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 5-2.Plasticity and excellent heat resistance, and the transparency, flexibility, shock resistance are excellent.
[reference example 5-1]
Syndiotactic polypropylenes (5A-1) 100 weight parts, ethene-1-butylene random copolymers (5C-1) (MFR (190 ℃)=4.0 that [polymerization example (5A-1)] obtains; 1-butylene content 12mol%) 150 weight parts; With respect to said composition; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 5-2.
[comparative example 5-2]
Syndiotactic polypropylenes (the 5A-3) (trade(brand)name: Finaplas1471 that TOTAL company produces; MFR=5.0g/10 minute, rrrr divided rate=69%) 100 weight parts, ethene-1-butylene random copolymers (5C-1) (MFR (190 ℃)=4.0,1-butylene content 12mol%) 25 weight parts; With respect to said composition; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 5-2.Compare plasticity and poor heat resistance with embodiment.
[comparative example 5-3]
Syndiotactic polypropylenes (the 5A-3) (trade(brand)name: Finaplas1471 that TOTAL company produces; MFR=5.0g/10 minute, rrrr divided rate=69%) propylene-ethylene copolymers (5B-3) 40 weight parts that obtain of 60 weight parts and [polymerization example (5B-3)]; With respect to said composition; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 5-2.Compare with embodiment, plasticity, thermotolerance and shock resistance are poor.
Figure GSA00000105371102521
Figure GSA00000105371102531
[EXAMPLE IV]
Below, further specifying the present invention (6) according to embodiment, the present invention is not limited to these embodiment.Wherein, each rerum natura is described below and measures among the embodiment.
The physical property measurement method
[limiting viscosity [η]]
According to measuring with the same method of EXAMPLE III.
[dissolving in the amount of n-decane part]
According to measuring with the same method of EXAMPLE III.
[MWD (Mw/Mn)]
According to measuring with the same method of EXAMPLE III.
[ethene in the polymkeric substance, propylene, terminal olefin content]
According to measuring with the same method of EXAMPLE IV.
[(AA) fusing point of composition (Tm), melting heat (Δ H)]
According to measuring with the same method of EXAMPLE III.
[half isothermal crystal time t 1/2]
According to measuring with the same method of EXAMPLE III.
[(B3) glass transition point of composition (Tg), fusing point (Tm)]
According to measuring with the same method of EXAMPLE IV.
[MFR]
The MFR of syndiotactic propene polymer (AA) and propylene-alpha-olefin copolymers (B3) is according to JIS K-6721, under 230 ℃, the load of 2.16kgf, measures.
The MFR of ethylene-butene copolymer (C) is according to JIS K-6721, under 190 ℃, the load of 2.16kgf, measures.
[various mensuration are with the making method of compacting sheet material]
According to making with the same method of EXAMPLE III.
[modulus in tension]
According to measuring with the same method of EXAMPLE III.
[Izod shock strength]
According to measuring with the same method of EXAMPLE III.
[TMA measures the softening temperature that obtains]
According to measuring with the same method of EXAMPLE III.
[inner turbidity (%)]
According to measuring with the same method of EXAMPLE IV.
[learning the glossiness velocity of variation (%) after vibration is decreased]
According to measuring with the same method of EXAMPLE IV.
[resilience spring rate (%)]
According to the described デ ユ of JISK6255 プ ケ formula (デ ユ プ ケ method), the test film of used thickness 15mm (5 of the compacting sheet materials of thick 3mm are overlapping) uses the resilience spring rate device that the island making is produced in Co., Ltd. to measure.
The polymerization example
(syndiotactic propene polymer (6A-1)～(6A～5))
Respectively and (4A-6) and (6A-5) as syndiotactic propene polymer (6A-1), (6A-2), (6A-3), (6A-4) with the syndiotactic propene polymer (4A-1) of EXAMPLE IV, (4A-3), (4A-4), (4A-5).
[polymerization example 6B-1]
(synthesizing of propylene-alpha-olefin copolymers (6B-1))
In the poly-unit that has fully carried out nitrogen metathetical internal volume 2000ml; Add at normal temperatures after dry hexane, 1-butylene 120g and the triisobutyl aluminium (1.0mmol) of 833ml; The poly-unit internal temperature is warmed up to 60 ℃; With propylene with the exert pressure in the system after 0.33MPa, with ethene the pressure in the system is adjusted to 0.62MPa.Then; In polymerizer, add and make two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.002mmol and to be scaled the MAO that aluminium is 0.6mmol (production of Tosoh FineChem company) and to contact the toluene solution that gets; When 60 ℃ of internal temperatures, system internal pressure utilize ethene to remain on 0.62MPa; Carry out 20 minutes polymerization, add the methyl alcohol of 20ml, stop polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours from polymeric solution.Resulting polymers is 73g, [η]=2.1 of in 135 ℃ of naphthane, measuring (dL/g).The rerum natura that resulting polymers is measured is shown in table 6-1.
[polymerization example 6B-2]
(propylene-alpha-olefin copolymers (6B-2))
In the poly-unit that has fully carried out nitrogen metathetical 2000ml; Add at normal temperatures after dry hexane, 1-butylene 120g and the triisobutyl aluminium (1.0mmol) of 833ml; The poly-unit internal temperature is warmed up to 60 ℃; With propylene with the exert pressure in the system after 0.33MPa, with ethene the pressure in the system is adjusted to 0.63MPa.Then; In polymerizer, add and make two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.002mmol and to be scaled the MAO that aluminium is 0.6mmol (production of Tosoh Fine Chem company) and to contact the toluene solution that gets; When 60 ℃ of internal temperatures, system internal pressure utilize ethene to remain on 0.63MPa; Carry out 20 minutes polymerization, add the methyl alcohol of 20ml, stop polymerization.Behind the decompress(ion), in the methyl alcohol of 2L, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours from polymeric solution.Resulting polymers is 97g, [η]=2.3 of in 135 ℃ of naphthane, measuring (dL/g).The rerum natura that resulting polymers is measured is shown in table 6-1.
[polymerization example 6B-3]
(propylene-alpha-olefin copolymers (6B-3))
In the poly-unit that has fully carried out nitrogen metathetical 4000ml; Add at normal temperatures after the dry hexane and triisobutyl aluminium (1.0mmol) of 1834ml; The poly-unit internal temperature is warmed up to 70 ℃; With propylene with the exert pressure in the system after 0.67MPa, with ethene the pressure in the system is adjusted to 1.37MPa.Then; In polymerizer, add and make two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.001mmol and to be scaled the MAO that aluminium is 0.3mmol (production of Tosoh Fine Chem company) and to contact the toluene solution that gets; When 70 ℃ of internal temperatures, system internal pressure utilize ethene to remain on 1.37MPa; Carry out 10 minutes polymerization, add the methyl alcohol of 20ml, stop polymerization.Behind the decompress(ion), in the methyl alcohol of 4L, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours from polymeric solution.Resulting polymers is 90g, in [η]=2.2 (dL/g) that 135 ℃ of naphthane are measured.The rerum natura that resulting polymers is measured is shown in table 6-1.
[polymerization example 6B-4]
(synthesizing of propylene-alpha-olefin copolymers (6B-4))
In the poly-unit that has fully carried out nitrogen metathetical 4000ml; Add at normal temperatures after the dry hexane and triisobutyl aluminium (1.0mmol) of 1834ml; The poly-unit internal temperature is warmed up to 50 ℃; With propylene with the exert pressure in the system after 0.67MPa, with ethene the pressure in the system is adjusted to 1.37MPa.Then; In polymerizer, add and make two (rubigan) methylene radical (cyclopentadienyl moiety) (prestox octahydro dibenzo fluorenyl) zirconium dichloride 0.001mmol and to be scaled the MAO that aluminium is 0.3mmol (production of Tosoh Fine Chem company) and to contact the toluene solution that gets; When 50 ℃ of internal temperatures, system internal pressure utilize ethene to remain on 1.37MPa; Carry out 10 minutes polymerization, add the methyl alcohol of 20ml, stop polymerization.Behind the decompress(ion), in the methyl alcohol of 4L, separate out polymkeric substance, under vacuum, 130 ℃ of dryings 12 hours from polymeric solution.Resulting polymers is 78g, [η]=3.5 of in 135 ℃ of naphthane, measuring (dL/g). 13The ethylene content that C-NMR measures is 18mol%.The rerum natura that resulting polymers is measured is shown in table 6-4.
(propylene-alpha-olefin copolymers (6BB-1)～(6BB～4))
Respectively and (4B-4) and (6BB-4) as propylene-alpha-olefin copolymers (6BB-1), (6BB-2), (6BB-3) with the propylene-alpha-olefin copolymers (4B-1) of EXAMPLE IV, (4B-2), (4B-3).
Specifying of other composition is described below.
The hydrogenated terpene resin P150 that hydrocarbon resin (6C-1) Yasuhara Chemical company produces
Thermoplastic elastomer (6C-2): ミ ラ ス ト マ one 7030B (MFR=25.0g/10min) that Mitsui Chemicals, Inc produces
Ethylene-butene copolymer (6C-3): the ethylene-butene copolymer (6C) that Mitsui Chemicals, Inc produces, (trade(brand)name: タ Off マ one A4070, MFR=4.0g/10 minute)
(propene polymer (6D-1)～(6D-8))
Respectively and (4D-8) and (6D-8) as propene polymer (6D-1), (6D-2), (6D-3), (6D-4), (6D-5), (6D-6), (6D-7) with the propene polymer (4D-1) of EXAMPLE IV, (4D-2), (4D-3), (4D-4), (4D-5), (4D-6), (4D-7).
Aforesaid propylene polymkeric substance (6D-1)～(6D-8), promptly the rerum natura of aforesaid propylene polymkeric substance (4D-1)～(4D-8) is shown in table 4-5.
Isotactic acrylic polymer (6D-1)～(6D-8) (being above-mentioned polymkeric substance (4D-1)～(4D-8)), polymkeric substance (6B-1)～(6B-4), polymkeric substance (6BB-1)～(6BB-4) (being above-mentioned polymkeric substance (4B-1)～(4B-4)) and (6A-1)～(6A-5) MFR of (above-mentioned polymkeric substance (4A-1), (4A-3), (4A-4), (4A-5) and (4A-6)) and the graphic representation of [η] are shown in Fig. 4.Hence one can see that, and the used polymkeric substance of isotactic propene polymer and the present invention is distinguished by condition (b-2).
[embodiment 6-1]
Syndiotactic polypropylenes (6A-1) 20 weight parts that obtain with respect to [polymerization example (6A-1)]; And propylene-ethylene-1-butylene random copolymers (6B-1) (MFR (230 ℃)=1.2, [η]=2.1, ethylene content 5mol%; 1-butylene content 29mol%) total 100 weight parts of 80 weight parts; Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 6-2.Excellent heat resistance, and the transparency, wearability, resilience elasticity are excellent.
[embodiment 6-2]
Syndiotactic polypropylenes (6A-1) 20 weight parts that obtain with respect to [polymerization example (6A-1)]; And propylene-ethylene-1-butylene random copolymers (6B-2) (MFR (230 ℃)=0.9; [η]=2.3, ethylene content 10mol%, 1-butylene content 28mol%) total 100 weight parts of 80 weight parts; The hydrogenated terpene resin P150 that cooperates 20 parts by weight resin (6C-1) ヤ ス Ha ラ ケ ミ カ Le ズ company to produce; As three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 6-2.Excellent heat resistance, and transparent, excellent in wear resistance, especially resilience elasticity are more excellent.
[embodiment 6-3]
Syndiotactic polypropylenes (6A-1) 60 weight parts that obtain with respect to [polymerization example (6A-1)]; And total 100 weight parts of aforesaid propylene-ethene-1-butylene random copolymers (6B-2) 40 weight parts; Cooperate 20 parts by weight resin (6C-1) (the hydrogenated terpene resin P150 that ヤ ス Ha ラ ケ ミ カ Le ズ company produces); As three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce is then processed sheet material equally with embodiment 6-2, is cut to suitable size etc., processes to measure and uses sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 6-2.
[comparative example 6-1]
Use syndiotactic polypropylenes (6A-2) 20 weight parts to replace syndiotactic polypropylenes (6A-1) 20 weight parts among the embodiment 6-1; Replace propylene-ethylene-1-butylene random copolymers (6B-1) 80 weight parts with propylene-ethylene-1-butylene random copolymers (6B-3) 80 weight parts; With respect to (6A-2) and 100 weight parts of total (6B-3); Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce is then processed sheet material equally with embodiment 6-1, is cut to suitable size etc., processes to measure and uses sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 6-2.
[comparative example 6-2]
Use syndiotactic polypropylenes (6A-2) 20 weight parts to replace syndiotactic polypropylenes (6A-1) 20 weight parts among the embodiment 6-1; Replace propylene-ethylene-1-butylene random copolymers (6B-1) 80 weight parts with ethene-1-butylene random copolymers (6C-3) 80 weight parts; With respect to (6A-2) and 100 weight parts of total (6C-3); Cooperation is as three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce is then processed sheet material equally with embodiment 6-1, is cut to suitable size etc., processes to measure and uses sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 6-2.
[embodiment 6-4]
Syndiotactic polypropylenes (6A-1) 20 weight parts that obtain with respect to [polymerization example (6A-1)]; And propylene-ethylene-1-butylene random copolymers (6B-1) (MFR (230 ℃)=1.2; [η]=2.1; Ethylene content 5mol%, 1-butylene content 29mol%) total 100 weight parts of 80 weight parts, the ミ ラ ス ト マ one that cooperates 200 weight parts to produce as the Mitsui Chemicals, Inc of thermoplastic elastomer (6C-2) TM(trade(brand)name) 7030B; As three (2 of secondary antioxidant; The 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part; As the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.The ラ ボ プ ラ ス ト ミ Le (twin screw batch-type melting mixing device) that uses Japan smart machine company to produce then, under 200 ℃ of design temperatures, 40g (installs volume=60cm in batches in the resin feeding quantity 3), under the 50rpm, 5 minutes condition behind the melting mixing, take out, carry out film-making with the cooling compacting that is set in 20 ℃, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 6-2.Excellences such as thermotolerance, shock strength, wearability.
[embodiment 6-5]
The propylene-ethylene that syndiotactic polypropylenes (6A-1) 20 weight parts that obtain with respect to [polymerization example (6A-1)] and [polymerization example (6B-2)] obtain-1-butylene random copolymers (6B-2) (MFR=0.9g/10 minute; [η]=2.3dL/g; 10 moles of % of ethylene content; 28 moles of % of 1-butylene content) total 100 weight parts of 80 weight parts are joined and the ミ ラ ス ト マ one of 100 weight parts as Mitsui Chemicals, Inc's production of thermoplastic elastomer (6C-2) TM(trade(brand)name) 7030B; As three (2, the 4-di-tert-butyl-phenyl) phosphoric acid salt 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.Process sheet material equally with embodiment 6-4 then, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 6-3.Excellences such as thermotolerance, shock strength, wearability.
[comparative example 6-3]
Cooperate the ミ ラ ス ト マ one of 100 weight parts as Mitsui Chemicals, Inc's production of thermoplastic elastomer (6C-2) TM(trade(brand)name) 7030B; As three (2, the 4-di-tert-butyl-phenyl) phosphoric acid salt 0.1 weight part of secondary antioxidant, as the Octadecane base-3-of heat-resisting stabilizing agent (4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester 0.1 weight part, as calcium stearate 0.1 weight part of hydrochloric acid absorbent.Process sheet material equally with embodiment 6-4 then, be cut to suitable size etc., process to measure and use sample.In addition, use this sample to process the compacting sheet material, measure rerum natura.Various rerum natura results are shown in table 6-3.
Figure GSA00000105371102621
Figure GSA00000105371102631
Figure GSA00000105371102641
Figure GSA00000105371102651
Utilizability on the industry
The polymerization activity of the present invention's (1) catalyst for olefines polymerizing (1) is excellent, brings huge interests for the olefin polymer industry.
The method of manufacture of the present invention's (2) propylene series copolymer [B1] can obtain the high propylene series copolymer of molecular weight [B1] because of polymerization at high temperature, is useful in industry therefore.
The present invention's (3) syndiotactic propene polymer (A) and existing polymer phase ratio have improved crystallization velocity and Tc, are the syndiotactic propylene that has excellent formability.And the balance of thermotolerance, the transparency, rigidity and the intensity etc. of the molding that this polymkeric substance of reason obtains is excellent, therefore is expected to be applicable to the out of use various new purposes of isotactic Vestolen PP 7052 up to now.

Claims (5)

1. the method for manufacture of a propylene series copolymer (B1); The propylene content of this propylene series copolymer (B1) is 90～51 moles of %; This method of manufacture is characterised in that; In the presence of catalyst for olefines polymerizing (2), make propylene and the terminal olefin and at least a monomer polymerization in the polyenoid that are selected from except propylene, said catalyst for olefines polymerizing (2) contains:
(a-2) the crosslinked metallocene compound shown in the formula [1-2]; With
(b) be selected from (b-1) Organoaluminoxy compound,
(b-2) with the right compound of said crosslinked metallocene compound (a-2) reacting forming ion and
(b-3) organo-aluminium compound
In the compound more than at least a kind,
Figure FSB00000612948800011
In the formula [1-2], R 1, R 2, R 3And R 4Be Wasserstoffatoms;
R 5, R 8, R 9And R 12For being selected from Wasserstoffatoms, alkyl and containing atom or the base in silica-based, separately can be identical also can be different;
R 6, R 11For being selected from alkyl and the identical base that contains in silica-based;
R 7, R 10For being selected from alkyl and the identical base that contains in silica-based;
R 5～R 12In adjacent base can interosculate each other and form ring;
R 13And R 14Be selected from the chlorine aryl of carbonatoms 6～20, the chlorine alkylaryl of carbonatoms 7～40, the bromine aryl of carbonatoms 6～20, the bromine alkylaryl of carbonatoms 7～40, the iodine aryl of carbonatoms 6～20, the iodine alkylaryl of carbonatoms 7～40 and the fluoroalkyl aryl of carbonatoms 7～40;
M is Ti, Zr or Hf;
Y is a carbon;
Q is selected from neutrality, conjugation or non-conjugated diene below 10 of halogen, alkyl, carbonatoms, anion binding base and can be with the identical or different combination in the lone-pair electron coordinate neutral dentate;
J is 1～4 integer.
2. the method for manufacture of propylene series copolymer as claimed in claim 1 (B1) is characterized in that R 13And R 14For substituting group be positioned between the position and/or the substituted-phenyl of contraposition.
3. according to claim 1 or claim 2 the method for manufacture of propylene series copolymer (B1) is characterized in that, carries out above-mentioned polymerization at 40～200 ℃.
4. according to claim 1 or claim 2 the method for manufacture of propylene series copolymer (B1) is characterized in that the propylene content of said propylene series copolymer (B1) is 90～55 moles of %.
5. the method for manufacture of propylene series copolymer as claimed in claim 3 (B1) is characterized in that, the propylene content of said propylene series copolymer (B1) is 90～55 moles of %.
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