CN104231125A - Loaded non-metallocene catalyst and preparation method and application thereof - Google Patents
Loaded non-metallocene catalyst and preparation method and application thereof Download PDFInfo
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- CN104231125A CN104231125A CN201310227393.5A CN201310227393A CN104231125A CN 104231125 A CN104231125 A CN 104231125A CN 201310227393 A CN201310227393 A CN 201310227393A CN 104231125 A CN104231125 A CN 104231125A
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Abstract
The invention relates to a loaded non-metallocene catalyst and a preparation method thereof. The loaded non-metallocene catalyst has the characteristics of high catalytic activity, remarkable copolymerization effect and the like. The invention also relates to an application of the loaded non-metallocene catalyst in olefin homopolymerization/ copolymerization; and a prepared olefin homopolymer/copolymer has the characteristics of good particle morphology, narrow molecular weight distribution, reduced contents of oligomers and fine powder and the like.
Description
The application is based on " national 11th Five-Year supporting plan problem " item understudied.This project obtains the great attention of the Ministry of Science and Technology and supports energetically, its target forms the polyolefin catalyst technology of new generation with independent intellectual property right, and improve domestic related products unification, improve China's polyolefine kind class, promote that it is to the future development of variation, seriation, customizations, high performance.
Technical field
The present invention relates to a kind of non-metallocene catalyst.Specifically, the present invention relates to a kind of load type non-metallocene catalyst, its preparation method and the application in alkene homopolymerization/copolymerization thereof.
Background technology
The non-metallocene catalyst that middle and later periods nineteen nineties occurs, after the non cyclopentadienyl catalyst time appears at metallocene catalyst, be therefore otherwise known as " after luxuriant " olefin polymerization catalysis.It has the feature similar to metallocene catalyst, can customize polymkeric substance as required, and cost is lower.The central atom of non-metallocene catalyst includes nearly all transition metal, reaches, even exceed metallocene catalyst at some aspect of performance, becomes the olefin polymerization catalysis of new generation after Ziegler-Natta and metallocene catalyst.According to the difference of the central atom of Primary Catalysts, non-metallocene (IIIB race, IVB race, VB race, group vib, VIIB race) catalyzer and non-luxuriant rear transition metal (VIII) catalyzer can be divided into again further.The excellent property of the polyolefin products manufactured by such catalyzer, and low cost of manufacture.Non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, not containing cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and there is cis alkyl or halogen metal division center, easily carry out alkene to insert and σ-key transfer, the easy alkylation of central metal, is conducive to the generation at cation activity center; The title complex formed has the geometric configuration of restriction, and stereoselectivity, electronegativity and chirality controllability, in addition, the metal-carbon key formed easily polarizes, and is more conducive to polymerization and the copolymerization of alkene.Therefore, even if the olefin polymer of higher molecular weight also can be obtained under higher polymeric reaction temperature.
But homogeneous catalyst has been proved it in olefinic polyreaction has that active duration is short, easily sticky still, high methylaluminoxane consumption, and obtain the too low or too high weak point of polymericular weight, only can be used for solution polymerization process or high-pressure polymerization process, seriously limit its industrial applicability.
Common way be by non-metallocene catalyst by certain supported technology, make loaded catalyst, thus improve the polymerization of alkene and the particle form of resulting polymers.It shows as the initial activity suitably reducing catalyzer to a certain extent, the polymerization activity life-span of extending catalyst, reduce the caking or cruelly poly-phenomenon that even avoid in polymerization process, improve the form of polymkeric substance, improve the apparent density of polymkeric substance, it can be made to meet more polymerisation process, as vapour phase polymerization or slurry polymerization etc.
Chinese patent CN1539856A discloses a kind of supported method of non-metallocene catalyst of composite carrier load, it is characterized in that the method comprises the following steps: (1) using as carrier porosu solid 100-1000 DEG C, under inert atmosphere or reduced pressure, dry or roasting 1 ~ 24h carries out thermal activation; (2) be dissolved in by magnesium compound in tetrahydrofuran (THF)-ol mixed system and form solution, then join in this solution by the porosu solid of thermal activation, under 0 ~ 60 DEG C of agitation condition, fully reaction forms transparent system; Wash after filtration, dry and drain rear obtained complex carrier; Or this transparent solvent is added non-polar organic solvent to make it to precipitate abundant precipitation, then obtained complex carrier is drained in filtration washing, drying; (3) non-metallocene olefin polymerization catalyst is dissolved in solvent, then with complex carrier or modify complex carrier contact 12 ~ 72 hours after washing and filtering, drying drain, become load type non-metallocene catalyst.From embodiment, catalyzer is that activity is lower at catalysis in olefine polymerization.
Patent 200910180601.4 discloses a kind of preparation method of load type non-metallocene catalyst, it makes magnesium compound and Nonmetallocene title complex be dissolved in solvent, add after the porous support of thermal activation treatment dry, obtain load type non-metallocene catalyst.Patent 200910180606.7 discloses a kind of preparation method of load type non-metallocene catalyst, it makes magnesium compound and Nonmetallocene title complex be dissolved in solvent, add after the porous support of thermal activation treatment, after adding precipitation agent again, filtration washing is dry, obtains load type non-metallocene catalyst.The porous support that these two kinds of methods all use thermal activation treatment to cross, although porous support is through thermal activation treatment, dehydration and dehydroxylation, still also have the free hydroxyl of more amount on the surface, follow-up load non-metallocene metal complexes is had a negative impact, limits its activation plays.
Load type non-metallocene catalyst preparation method disclosed in Chinese patent 200910180100.6,200910180607.1,200910210988.3,200910210984.5,200910210987.9,200910210991.5 and above-mentioned patent similar, the porous support all using thermal activation treatment to cross reacts with the magnesium compound solution containing Nonmetallocene part or Nonmetallocene title complex, finally react with the chemical processing agent containing IVB race metallic compound again, obtain load type non-metallocene catalyst.
Chinese patent 200910180602.9 discloses a kind of preparation method of load type non-metallocene catalyst, and it makes magnesium compound and Nonmetallocene title complex be dissolved in solvent, obtains load type non-metallocene catalyst after drying.Patent 200910180605.2 discloses a kind of preparation method of load type non-metallocene catalyst, and it makes magnesium compound and Nonmetallocene title complex be dissolved in solvent, adds precipitation agent precipitation, obtains load type non-metallocene catalyst after filtration washing drying.What these two kinds of methods adopted is magnesium compound carrier, and the particle form of catalyzer is difficult to control, and limits the morphology being polymerized thus and obtaining.
Patent 200910180603.3,200910180604.8,200910210989.8,200910210986.4, load type non-metallocene catalyst preparation method disclosed in 200910210985.X, 200910210990.0 and above-mentioned patent similar, all use magnesium compound as carrier, the particle form that still there is catalyzer is difficult to control, and limits the morphology being polymerized thus and obtaining.
Therefore, current present situation is, still needs a kind of load type non-metallocene catalyst, and its preparation method is simple, is applicable to suitability for industrialized production, and can overcomes those problems existed in prior art load type non-metallocene catalyst.
Summary of the invention
The present inventor finds through diligent research on the basis of existing technology, by using a kind of specific preparation method to manufacture described load type non-metallocene catalyst, just can solve foregoing problems, and this completes the present invention.
In the preparation method of load type non-metallocene catalyst of the present invention, do not add any proton (such as this area routine use those).In addition, in the preparation method of load type non-metallocene catalyst of the present invention, be not added to electron compounds such as (such as this area when manufacturing Ziegler or Ziegler-Natta catalyst) conventional monoesters class, di-esters, two ethers, diones and the diol-lipids used.Moreover, in the preparation method of load type non-metallocene catalyst of the present invention, also need not harsh reaction requirement and reaction conditions.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.
Specifically, the present invention relates to the content of following aspect:
1.a preparation method for load type non-metallocene catalyst, comprises the following steps:
Magnesium compound and Nonmetallocene part are dissolved in solvent in the presence of an alcohol, obtain the step of magnesium compound solution;
In described magnesium compound solution, add precipitation agent or dry described magnesium compound solution, obtain the step of magnesium compound carrier;
Described magnesium compound carrier is contacted with the chemical processing agent being selected from IV B race metallic compound with the silicon compound of following formula (X), obtains the step of described load type non-metallocene catalyst,
Si (OR)
mx
4-mformula (X)
Wherein, each R is identical or different, is selected from C independently of one another
1-8straight or branched alkyl, is preferably selected from C independently of one another
1-4straight or branched alkyl, is preferably ethyl; M is the integer of 0,1,2,3 or 4; Each X is identical or different, is selected from halogen independently of one another, preferred chlorine,
Described preparation method is optionally also included in and makes before described magnesium compound carrier and described silicon compound contact with described chemical processing agent, by the step helping magnesium compound carrier described in chemical processing agent pre-treatment being selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.
According to the preparation method described in any preceding aspect, it is characterized in that, described magnesium compound be selected from magnesium halide, Alkoxymagnesium halides, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium one or more, be preferably selected from magnesium halide one or more, more preferably magnesium chloride.
According to the preparation method described in any preceding aspect, it is characterized in that, described solvent is selected from C
6-12aromatic hydrocarbon, halo C
6-12one or more in aromatic hydrocarbon, ester and ether, preferred C
6-12one or more in aromatic hydrocarbon and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF), described alcohol be selected from fatty alcohol, aromatic alcohol and alicyclic ring alcohol one or more, wherein said alcohol is optionally selected from halogen atom or C
1-6the substituting group of alkoxyl group replaces, described alcohol be preferably selected from fatty alcohol one or more, be more preferably selected from ethanol and butanols one or more.
According to the preparation method described in any preceding aspect, it is characterized in that, described Nonmetallocene part be selected from the compound with following chemical structural formula one or more:
，
Be preferably selected from the compound (A) and compound (B) with following chemical structural formula one or more:
with
,
（A） （B）
More preferably the compound (A-1) with following chemical structural formula is selected to compound (A-4) and compound (B-1) to one or more in compound (B-4):
、
、
（A-1） （A-2）
、
、
（A-3） （A-4）
、
、
（B-1） （B-2）
with
,
（B-3） （B-4）
In chemical structural formulas all above,
Q is 0 or 1;
D is 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
,-NR
23r
24,-N (O) R
25r
26,
,-PR
28r
29,-P (O) R
30oR
31, sulfuryl, sulfoxide group or-Se (O) R
39, wherein N, O, S, Se and P are coordination atom separately;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C
1-C
30alkyl;
D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C
1-C
30alkyl, sulfuryl, sulfoxide group,
,-N (O) R
25r
26,
or-P (O) R
32(OR
33), wherein N, O, S, Se and P are coordination atom separately;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and P are coordination atom separately;
F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;
G is selected from C
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group;
Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and P are coordination atom separately;
represent singly-bound or double bond;
-represent covalent linkage or ionic linkage;
R
1to R
4, R
6to R
36, R
38and R
39be selected from hydrogen, C independently of one another
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, is preferably formed aromatic ring;
Described safing function groups be selected from halogens, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, containing tin group, C
1-C
10ester group and nitro;
R
5be selected from lone-pair electron on nitrogen, hydrogen, C
1-C
30the C of alkyl, replacement
1-C
30alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups; Work as R
5for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups time, R
5in N, O, S, P and Se can carry out coordination as coordination atom and described center IV B race atoms metal;
The C of described replacement
1-C
30alkyl is selected from one or more halogen or C
1-C
30the C of alkyl alternatively base
1-C
30alkyl,
Described Nonmetallocene part be preferably selected from the compound with following chemical structural formula further one or more:
,
,
,
,
with
,
Described Nonmetallocene part be most preferably selected from the compound with following chemical structural formula one or more:
with
.
According to the preparation method described in any preceding aspect, it is characterized in that,
Described halogen is selected from F, Cl, Br or I;
Described nitrogen-containing group is selected from
,-NR
23r
24,-T-NR
23r
24or-N (O) R
25r
26;
Described phosphorus-containing groups is selected from
,-PR
28r
29 -,-P (O) R
30r
31or-P (O) R
32(OR
33);
Described oxy radical is selected from hydroxyl ,-OR
34with-T-OR
34;
Described sulfur-containing group is selected from-SR
35,-T-SR
35,-S (O) R
36or-T-SO
2r
37;
The described seleno group that contains is selected from-SeR
38,-T-SeR
38,-Se (O) R
39or-T-Se (O) R
39;
Described group T is selected from C
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group;
Described R
37be selected from hydrogen, C
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group;
Described C
1-C
30alkyl is selected from C
1-C
30alkyl, C
7-C
50alkaryl, C
7-C
50aralkyl, C
3-C
30cyclic alkyl, C
2-C
30thiazolinyl, C
2-C
30alkynyl, C
6-C
30aryl, C
8-C
30condensed ring radical or C
4-C
30heterocyclic radical, wherein said heterocyclic radical contains the heteroatoms that 1-3 is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;
Described silicon-containing group is selected from-SiR
42r
43r
44or-T-SiR
45;
Described germanic group is selected from-GeR
46r
47r
48or-T-GeR
49;
The described tin group that contains is selected from-SnR
50r
51r
52,-T-SnR
53or-T-Sn (O) R
54;
Described R
42to R
54be selected from hydrogen, aforementioned C independently of one another
1-C
30the C of alkyl, aforementioned replacement
1-C
30alkyl or aforementioned safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and
Described group T ditto defines.
According to the preparation method described in any preceding aspect, it is characterized in that, in the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part for 1:0.0001-1, preferred 1:0.0002-0.4, more preferably 1:0.0008-0.2, preferred 1:0.001-0.1 further, the ratio of described magnesium compound and described solvent is 1mol:75 ~ 400ml, preferred 1mol:150 ~ 300ml, more preferably 1mol:200 ~ 250ml, in the mol ratio of the described magnesium compound of Mg element and described alcohol for 1:0.02 ~ 4.00, preferred 1:0.05 ~ 3.00, more preferably 1:0.10 ~ 2.50, the volume ratio of described precipitation agent and described solvent is 1:0.2 ~ 5, preferred 1:0.5 ~ 2, more preferably 1:0.8 ~ 1.5, in the described magnesium compound carrier of Mg element with in the mol ratio of the described silicon compound of Si element for 1:0.01-1, preferred 1:0.01-0.50, more preferably 1:0.05-0.25, in the described magnesium compound carrier of Mg element with the mol ratio of the described chemical processing agent of IVB race elemental metal for 1:0.01-1, preferred 1:0.01-0.50, more preferably 1:0.10-0.30, and in the described magnesium compound carrier of Mg element and to help the mol ratio of chemical processing agent for 1:0-1.0 described in Al element, preferred 1:0-0.5, more preferably 1:0.1-0.5.
According to the preparation method described in any preceding aspect, it is characterized in that, described precipitation agent is selected from alkane, naphthenic hydrocarbon, one or more in halogenated alkane and halo naphthenic hydrocarbon, be preferably selected from pentane, hexane, heptane, octane, nonane, decane, hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane, methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane, three n-butyl bromide, chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, one or more in bromo cyclononane and bromo cyclodecane, be preferably selected from hexane further, heptane, one or more in decane and hexanaphthene, most preferably hexane.
According to the preparation method described in any preceding aspect, it is characterized in that, described IV B race metallic compound be selected from IV B race metal halide, IV B race metal alkyl compound, IV B race metal alkoxide, IV B race metal alkyl halides and IV B race metal alkoxide halogenide one or more, be preferably selected from IV B race metal halide one or more, be more preferably selected from TiCl
4, TiBr
4, ZrCl
4, ZrBr
4, HfCl
4and HfBr
4in one or more, be most preferably selected from TiCl
4and ZrCl
4in one or more, described aikyiaiurnirsoxan beta is selected from methylaluminoxane, ethylaluminoxane, one or more in isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, more preferably be selected from methylaluminoxane and isobutyl aluminium alkoxide one or more, and described aluminum alkyls is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, triisopentyl aluminium, three n-pentyl aluminium, three hexyl aluminium, three isohexyl aluminium, one or more in diethylmethyl aluminium and dimethyl ethyl aluminium, be preferably selected from trimethyl aluminium, triethyl aluminum, one or more in tri-propyl aluminum and triisobutyl aluminium, most preferably be selected from triethyl aluminum and triisobutyl aluminium one or more.
A kind of load type non-metallocene catalyst, it manufactures by according to the preparation method described in any preceding aspect.
A kind of alkene homopolymerization/copolymerization method, it is characterized in that, with according to the load type non-metallocene catalyst described in aspect 9 for Primary Catalysts, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt for promotor, make alkene homopolymerization or copolymerization.
11. 1 kinds of alkene homopolymerization/copolymerization methods, is characterized in that, comprise the following steps:
Load type non-metallocene catalyst is manufactured according to the preparation method described in any preceding aspect, and
With described load type non-metallocene catalyst for Primary Catalysts, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt for promotor, make alkene homopolymerization or copolymerization.
technique effect
Preparation method's technique simple possible of load type non-metallocene catalyst of the present invention, adjustable leeway is large, can effectively control active component content in catalyzer, and then obtain the load type non-metallocene catalyst of different performance.
When the load type non-metallocene catalyst adopting the present invention to obtain and promotor form catalyst system, only need fewer promotor (such as methylaluminoxane or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity, significant comonomer effect is shown during copolymerization, namely, under relatively equal condition, Copolymerization activity is active higher than homopolymerization.
According to the present invention, the particle form of the polyolefine (especially ethene polymers) obtained by alkene homopolymerization/copolymerization method is excellent, bulk density is high, narrow molecular weight distribution, and the ultrahigh molecular weight polyethylene(UHMWPE) molecular weight that under no hydrogen exists prepared by homopolymerization is higher and adjustable.
Embodiment
Below the specific embodiment of the present invention is described in detail, but it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.
In the context of the present invention, unless otherwise defined explicitly, or this implication is beyond the understanding scope of those skilled in the art, hydrocarbon more than 3 carbon atoms or hydrocarbon derivative group (such as propyl group, propoxy-, butyl, butane, butylene, butenyl, hexane etc.) not titled with all have time prefix " just " with titled with implication identical time prefix " just ".Such as, propyl group is generally understood as n-propyl, and butyl is generally understood as normal-butyl.
In this manual, in order to avoid stating complexity, not for each substituting group of compound or group its valence link situation clear and definite be monovalence, divalence, trivalent or tetravalence etc., those skilled in the art specifically can judge according to these substituting groups or group (record in such as this specification sheets or the group G of definition, D, B, A and F etc.) position residing on the structural formula of respective compound or the replacement situation showed, and for the definition selecting in the definition given by these substituting groups or group to be applicable in the valence link situation of this position or the situation of replacement from this specification sheets.
The present invention relates to a kind of preparation method of load type non-metallocene catalyst, comprise the following steps: magnesium compound and Nonmetallocene part are dissolved in solvent in the presence of an alcohol, obtain the step of magnesium compound solution; In described magnesium compound solution, add precipitation agent or dry described magnesium compound solution, obtain the step of magnesium compound carrier; With described magnesium compound carrier is contacted with the chemical processing agent being selected from IV B race metallic compound with the silicon compound of formula (X), obtain the step of described load type non-metallocene catalyst.
Below the step obtaining described magnesium compound solution is specifically described.
According to this step, magnesium compound and Nonmetallocene part are dissolved in suitable solvent (also referred to as dissolved magnesium compound solvent) in the presence of an alcohol, thus obtain described magnesium compound solution.
As described solvent, such as C can be enumerated
6-12aromatic hydrocarbon, halo C
6-12aromatic hydrocarbon, ester and ether equal solvent.Specifically such as can enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene, bromo ethylbenzene, ethyl acetate and tetrahydrofuran (THF) etc.Wherein, preferred C
6-12aromatic hydrocarbon and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF).
These solvents can be used alone one, also can be multiple used in combination with arbitrary ratio.
According to the present invention, term " alcohol " refers to hydrocarbon chain (such as C
1-30hydrocarbon) at least one hydrogen atom be optionally substituted by a hydroxyl group and the compound obtained.
As described alcohol, such as C can be enumerated
1-30fatty alcohol (preferred C
1-30aliphatic monobasic alcohol), C
6-30aromatic alcohol (preferred C
6-30aromatic monoalcohols) and C
4-30alicyclic ring alcohol (preferred C
4-30alicyclic monohydroxy-alcohol), wherein preferred C
1-30aliphatic monobasic alcohol or C
2-8aliphatic monobasic alcohol, more preferably ethanol and butanols.In addition, described alcohol can optionally be selected from halogen atom or C
1-6the substituting group of alkoxyl group replaces.
As described C
1-30fatty alcohol, such as can enumerate methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, amylalcohol, 2-methyl amyl alcohol, 2-ethylpentanol, 2-hexyl butanols, hexanol and 2-Ethylhexyl Alcohol etc., wherein preferred alcohol, butanols and 2-Ethylhexyl Alcohol.
As described C
6-30aromatic alcohol, such as can enumerate phenylcarbinol, phenylethyl alcohol and methylbenzyl alcohol etc., wherein preferred phenylethyl alcohol.
As described C
4-30alicyclic ring alcohol, such as can enumerate hexalin, cyclopentanol, Lotka-Volterra circle system, methylcyclopentanol, ethyl cyclopentanol, propyl group cyclopentanol, methyl-cyclohexanol, ethyl cyclohexanol, cyclohexyl alcohol, methyl Lotka-Volterra circle system, ethyl Lotka-Volterra circle system and propyl group Lotka-Volterra circle system etc., wherein preferred hexalin and methyl-cyclohexanol.
As the described alcohol replaced by halogen atom, such as can enumerate trichlorine methyl alcohol, ethapon and three Mecorals etc., wherein preferred trichlorine methyl alcohol.
As the described alcohol that alkoxy replaces, such as can enumerate glycol-ether, ethylene glycol-n-butyl ether and 1-butoxy-2-propyl alcohol etc., wherein preferred glycol-ether.
These alcohol can be used alone one, also can be multiple used in combination.When using with the form of multiple mixing, the ratio between any two kinds of alcohol in described alcohol mixture can be determined arbitrarily, is not particularly limited.
In order to prepare described magnesium compound solution, described magnesium compound and described Nonmetallocene part can be added in the mixed solvent formed by described solvent and described alcohol and dissolve, or described magnesium compound and described Nonmetallocene part are added in described solvent, and add alcohol simultaneously or subsequently and dissolve, but be not limited to this.
To the preparation time (i.e. the dissolution time of described magnesium compound and described Nonmetallocene part) of described magnesium compound solution, there is no particular limitation, but be generally 0.5 ~ 24h, preferably 4 ~ 24h.In this preparation process, the dissolving of stirring and promoting described magnesium compound and described Nonmetallocene part can be utilized.This stirring can adopt any form, such as stirring rake (rotating speed is generally 10 ~ 1000 revs/min) etc.As required, sometimes can promote to dissolve by suitable heating.
Below described magnesium compound is specifically described.
According to the present invention, term " magnesium compound " uses the common concept in this area, refers to the organic or inorganic solid water-free magnesium-containing compound of the carrier routine use as supported olefin polymerization catalyst.
According to the present invention, as described magnesium compound, magnesium halide, Alkoxymagnesium halides, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium such as can be enumerated.
Specifically, as described magnesium halide, such as magnesium chloride (MgCl can be enumerated
2), magnesium bromide (MgBr
2), magnesium iodide (MgI
2) and magnesium fluoride (MgF
2) etc., wherein preferred magnesium chloride.
As described Alkoxymagnesium halides, methoxyl group magnesium chloride (Mg (OCH such as can be enumerated
3) Cl), oxyethyl group magnesium chloride (Mg (OC
2h
5) Cl), propoxy-magnesium chloride (Mg (OC
3h
7) Cl), n-butoxy magnesium chloride (Mg (OC
4h
9) Cl), isobutoxy magnesium chloride (Mg (i-OC
4h
9) Cl), methoxyl group magnesium bromide (Mg (OCH
3) Br), oxyethyl group magnesium bromide (Mg (OC
2h
5) Br), propoxy-magnesium bromide (Mg (OC
3h
7) Br), n-butoxy magnesium bromide (Mg (OC
4h
9) Br), isobutoxy magnesium bromide (Mg (i-OC
4h
9) Br), methoxyl group magnesium iodide (Mg (OCH
3) I), oxyethyl group magnesium iodide (Mg (OC
2h
5) I), propoxy-magnesium iodide (Mg (OC
3h
7) I), n-butoxy magnesium iodide (Mg (OC
4h
9) I) and isobutoxy magnesium iodide (Mg (i-OC
4h
9) I) etc., wherein preferred methoxyl group magnesium chloride, oxyethyl group magnesium chloride and isobutoxy magnesium chloride.
As described alkoxyl magnesium, magnesium methylate (Mg (OCH such as can be enumerated
3)
2), magnesium ethylate (Mg (OC
2h
5)
2), propoxy-magnesium (Mg (OC
3h
7)
2), butoxy magnesium (Mg (OC
4h
9)
2), isobutoxy magnesium (Mg (i-OC
4h
9)
2) and 2-ethyl hexyl oxy magnesium (Mg (OCH
2cH (C
2h
5) C
4h
-)
2) etc., wherein preferred magnesium ethylate and isobutoxy magnesium.
As described alkyl magnesium, methyl magnesium (Mg (CH such as can be enumerated
3)
2), magnesium ethide (Mg (C
2h
5)
2), propyl group magnesium (Mg (C
3h
7)
2), normal-butyl magnesium (Mg (C
4h
9)
2) and isobutyl-magnesium (Mg (i-C
4h
9)
2) etc., wherein preferred magnesium ethide and normal-butyl magnesium.
As described alkyl halide magnesium, methylmagnesium-chloride (Mg (CH such as can be enumerated
3) Cl), ethylmagnesium chloride (Mg (C
2h
5) Cl), propyl group magnesium chloride (Mg (C
3h
7) Cl), n-butylmagnesium chloride magnesium (Mg (C
4h
9) Cl), isobutyl-magnesium chloride (Mg (i-C
4h
9) Cl), methyl-magnesium-bromide (Mg (CH
3) Br), ethylmagnesium bromide (Mg (C
2h
5) Br), propyl group magnesium bromide (Mg (C
3h
7) Br), normal-butyl magnesium bromide (Mg (C
4h
9) Br), selenium alkynide (Mg (i-C
4h
9) Br), methylpyridinium iodide magnesium (Mg (CH
3) I), ethyl phosphonium iodide magnesium (Mg (C
2h
5) I), propyl group magnesium iodide (Mg (C
3h
7) I), normal-butyl magnesium iodide (Mg (C
4h
9) I) and isobutyl-magnesium iodide (Mg (i-C
4h
9) I) etc., wherein preferable methyl magnesium chloride, ethylmagnesium chloride and isobutyl-magnesium chloride.
As described alkyl alkoxy magnesium, methyl methoxy base magnesium (Mg (OCH such as can be enumerated
3) (CH
3)), methyl ethoxy magnesium (Mg (OC
2h
5) (CH
3)), methyl propoxy-magnesium (Mg (OC
3h
7) (CH
3)), methyl n-butoxy magnesium (Mg (OC
4h
9) (CH
3)), methyl tert-butyl oxygen base magnesium (Mg (i-OC
4h
9) (CH
3)), ethyl magnesium methylate (Mg (OCH
3) (C
2h
5)), ethyl magnesium ethylate (Mg (OC
2h
5) (C
2h
5)), ethylpropoxy magnesium (Mg (OC
3h
7) (C
2h
5)), ethyl n-butoxy magnesium (Mg (OC
4h
9) (C
2h
5)), ethyl isobutyl oxygen base magnesium (Mg (i-OC
4h
9) (C
2h
5)), propylmethoxy magnesium (Mg (OCH
3) (C
3h
7)), propyl group magnesium ethylate (Mg (OC
2h
5) (C
3h
7)), propyl group propoxy-magnesium (Mg (OC
3h
7) (C
3h
7)), propyl group n-butoxy magnesium (Mg (OC
4h
9) (C
3h
7)), propyl group isobutoxy magnesium (Mg (i-OC
4h
9) (C
3h
7)), normal-butyl magnesium methylate (Mg (OCH
3) (C
4h
9)), normal-butyl magnesium ethylate (Mg (OC
2h
5) (C
4h
9)), normal-butyl propoxy-magnesium (Mg (OC
3h
7) (C
4h
9)), normal-butyl n-butoxy magnesium (Mg (OC
4h
9) (C
4h
9)), normal-butyl isobutoxy magnesium (Mg (i-OC
4h
9) (C
4h
9)), isobutyl-magnesium methylate (Mg (OCH
3) (i-C
4h
9)), isobutyl-magnesium ethylate (Mg (OC
2h
5) (i-C
4h
9)), isobutyl-propoxy-magnesium (Mg (OC
3h
7) (i-C
4h
9)), isobutyl-n-butoxy magnesium (Mg (OC
4h
9) (i-C
4h
9)) and isobutyl-isobutoxy magnesium (Mg (i-OC
4h
9) (i-C
4h
9)) etc., wherein preferred butyl magnesium ethylate.
These magnesium compounds can be used alone one, also can be multiple used in combination, not special restriction.
When using with the form of multiple mixing, the mol ratio between two kinds of magnesium compounds in described magnesium compound mixture is such as 0.25 ~ 4:1, preferably 0.5 ~ 3:1, more preferably 1 ~ 2:1.
According to the present invention, term " Nonmetallocene title complex " is a kind of single centre olefin polymerization catalysis for metallocene catalyst, not containing the cyclopentadienyl or derivatives thereof such as luxuriant ring, fluorenes ring or indenes ring in structure, and the organometallics (therefore described Nonmetallocene title complex is also sometimes referred to as non-metallocene olefin polymerization title complex) of olefinic polymerization catalysis activity can be demonstrated when combining with promotor (than as mentioned below those).This compound comprises the polydentate ligand (preferred tridentate ligand or more tooth part) that central metal atom is combined with coordinate bond with at least one and described central metal atom, and term " Nonmetallocene part " is aforesaid polydentate ligand.
According to the present invention, described Nonmetallocene part is selected from the compound with following chemical structural formula:
。
According to the present invention, group A, D and E(coordination group in this compound) form coordinate bond by the IV B race atoms metal generation coordination reaction contained by the IV B race metallic compound that uses as chemical processing agent in coordination atom contained by it heteroatomss such as () such as N, O, S, Se and P and the present invention, form the title complex (i.e. Nonmetallocene title complex of the present invention) of atoms metal centered by this IV B race atoms metal thus.
In one more specifically embodiment, described Nonmetallocene part is selected from the compound (A) and compound (B) with following chemical structural formula:
with
.
（A） （B）
In one more specifically embodiment, described Nonmetallocene part is selected from the compound (A-1) with following chemical structural formula to compound (A-4) and compound (B-1) to compound (B-4):
、
、
（A-1） （A-2）
、
、
（A-3） （A-4）
、
、
（B-1） （B-2）
with
.
（B-3） （B-4）
In above all chemical structural formulas,
Q is 0 or 1;
D is 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
,-NR
23r
24,-N (O) R
25r
26,
,-PR
28r
29,-P (O) R
30oR
31, sulfuryl, sulfoxide group or-Se (O) R
39, wherein N, O, S, Se and P are coordination atom separately;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C
1-C
30alkyl;
D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C
1-C
30alkyl, sulfuryl, sulfoxide group,
,-N (O) R
25r
26,
or-P (O) R
32(OR
33), wherein N, O, S, Se and P are coordination atom separately;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group (-CN), wherein N, O, S, Se and P are coordination atom separately;
F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;
G is selected from C
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group;
Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group (-CN), such as can enumerates-NR
23r
24,-N (O) R
25r
26,-PR
28r
29 -,-P (O) R
30r
31,-OR
34,-SR
35,-S (O) R
36,-SeR
38or-Se (O) R
39, wherein N, O, S, Se and P are coordination atom separately;
represent singly-bound or double bond;
-represent covalent linkage or ionic linkage.
R
1to R
4, R
6to R
36, R
38and R
39be selected from hydrogen, C independently of one another
1-C
30the C of alkyl, replacement
1-C
30alkyl (wherein preferred halo alkyl, such as-CH
2cl and-CH
2cH
2or safing function group Cl).Above-mentioned group can be the same or different to each other, wherein adjacent group such as R
1with R
2, R
6with R
7, R
7with R
8, R
8with R
9, R
13with R
14, R
14with R
15, R
15with R
16, R
18with R
19, R
19with R
20, R
20with R
21, R
23with R
24, or R
25with R
26etc. key or Cheng Huan can be combined togather into, be preferably formed aromatic ring, such as unsubstituted phenyl ring or by 1-4 C
1-C
30the C of alkyl, replacement
1-C
30alkyl (wherein preferred halo alkyl, such as-CH
2cl and-CH
2cH
2cl) or safing function group replace phenyl ring.
R
5be selected from lone-pair electron on nitrogen, hydrogen, C
1-C
30the C of alkyl, replacement
1-C
30alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups.Work as R
5for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups time, R
5in N, O, S, P and Se can carry out coordination as coordination atom and described center IV B race atoms metal.
In the context of the present invention, described safing function group such as can enumerate be selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, containing tin group, C
1-C
10ester group or nitro (-NO
2) at least one etc., but usually do not comprise C
1-C
30the C of alkyl and replacement
1-C
30alkyl.
In the context of the present invention, the chemical structure by polydentate ligand of the present invention limit, and described safing function group has following characteristics:
(1) complexation process of described group A, D, E, F, Y or Z and described central metal atom M is not disturbed, and
(2) with the coordination ability of described central metal atom M lower than described A, D, E, F, Y and Z group, and do not replace the existing coordination of these groups and described central metal atom M.
According to the present invention, in aforementioned all chemical structural formulas, as the case may be, any adjacent two or more groups, such as R
21with group Z, or R
13with group Y, ring can be combined togather into, be preferably formed the heteroatomic C comprising and come from described group Z or Y
6-C
30heteroaromatic, such as pyridine ring etc., wherein said heteroaromatic is optionally selected from C by one or more
1-C
30the C of alkyl, replacement
1-C
30the substituting group of alkyl and safing function group replaces.
In the context of the present invention,
Described halogen is selected from F, Cl, Br or I.Described nitrogen-containing group is selected from
,-NR
23r
24,-T-NR
23r
24or-N (O) R
25r
26.Described phosphorus-containing groups is selected from
,-PR
28r
29 -,-P (O) R
30r
31or-P (O) R
32(OR
33).Described oxy radical is selected from hydroxyl ,-OR
34with-T-OR
34.Described sulfur-containing group is selected from-SR
35,-T-SR
35,-S (O) R
36or-T-SO
2r
37.The described seleno group that contains is selected from-SeR
38,-T-SeR
38,-Se (O) R
39or-T-Se (O) R
39.Described group T is selected from C
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group.Described R
37be selected from hydrogen, C
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group.
In the context of the present invention, described C
1-C
30alkyl is selected from C
1-C
30alkyl (preferred C
1-C
6alkyl, such as isobutyl-), C
7-C
50alkaryl (such as tolyl, xylyl, diisobutyl phenyl etc.), C
7-C
50aralkyl (such as benzyl), C
3-C
30cyclic alkyl, C
2-C
30thiazolinyl, C
2-C
30alkynyl, C
6-C
30aryl (such as phenyl, naphthyl, anthryl etc.), C
8-C
30condensed ring radical or C
4-C
30heterocyclic radical, wherein said heterocyclic radical contains the heteroatoms that 1-3 is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom, such as pyridyl, pyrryl, furyl or thienyl etc.
According to the present invention, in the context of the present invention, according to the particular case to its relevant group combined, described C
1-C
30alkyl refers to C sometimes
1-C
30hydrocarbon two base (divalent group, or be called C
1-C
30alkylene) or C
1-C
30hydrocarbon three base (trivalent radical), this is obvious to those skilled in the art.
In the context of the present invention, the C of described replacement
1-C
30alkyl refers to the C with one or more inert substituent
1-C
30alkyl.So-called inert substituent, refers to these substituting groups and aforementioned coordinative group (is referred to aforementioned group A, D, E, F, Y and Z, or also optionally comprises R
5) there is no substantial interference with the complexation process of central metal atom (aforementioned IV B race atoms metal); In other words, the chemical structure by part of the present invention limit, and these substituting groups do not have ability or have no chance (being such as subject to the impact of steric hindrance etc.) and the atoms metal generation coordination reaction of described IV B race and form coordinate bond.Generally speaking, described inert substituent is selected from halogen or C
1-C
30alkyl (preferred C
1-C
6alkyl, such as isobutyl-).
In the context of the present invention, described silicon-containing group is selected from-SiR
42r
43r
44or-T-SiR
45; Described germanic group is selected from-GeR
46r
47r
48or-T-GeR
49; The described tin group that contains is selected from-SnR
50r
51r
52,-T-SnR
53or-T-Sn (O) R
54; And described R
42to R
54be selected from hydrogen, aforesaid C independently of one another
1-C
30the C of alkyl, aforesaid replacement
1-C
30alkyl or aforesaid safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan.Wherein the definition of group T is the same.
As described Nonmetallocene part, such as following compound can be enumerated:
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
、
with
.
Described Nonmetallocene part is preferably selected from following compound:
、
、
、
、
、
、
、
、
,
with
。
Described Nonmetallocene part is preferably selected from following compound further:
,
,
,
,
with
.
Described Nonmetallocene part is more preferably selected from following compound:
with
.
These Nonmetallocene parts can be used alone one, or use multiple with arbitrary ratio combination.
According to the present invention, described Nonmetallocene part is not as the normally used diether compounds of electronic donor compound capable in this area.
Described Nonmetallocene part can manufacture according to any method well known by persons skilled in the art.About the particular content of its manufacture method, such as can see WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 etc., this specification sheets introduces the full text of these documents as a reference at this point.
According to the present invention, by described magnesium compound solution convection drying, a kind of solid product of good fluidity can be obtained, i.e. magnesium compound carrier of the present invention.
Now, described convection drying can adopt ordinary method to carry out, heat drying etc. under dry or vacuum atmosphere under dry under such as inert gas atmosphere, vacuum atmosphere, wherein preferred heat drying under vacuum atmosphere.Drying temperature is generally 30 ~ 160 DEG C, and preferably 60 ~ 130 DEG C, time of drying is generally 2 ~ 24h, but is sometimes not limited to this.
Or, according to the present invention, by being metered into precipitation agent in described magnesium compound solution, solid matter being precipitated out from this magnesium compound solution, obtaining magnesium compound carrier thus.
Below described precipitation agent is specifically described.
According to the present invention, term " precipitation agent " uses the common concept in this area, refers to and can reduce the solubleness of solid substance solute (such as described magnesium compound, porous support, Nonmetallocene part or Nonmetallocene title complex etc.) in its solution and and then the unreactiveness liquid making it separate out in solid form from described solution.
According to the present invention, as described precipitation agent, such as can enumerate for solid substance solute (such as described magnesium compound, porous support, Nonmetallocene part or Nonmetallocene title complex etc.) to be precipitated is poor solvent, and for the described solvent for dissolving described solid substance solute (such as magnesium compound), be the solvent of good solvent, such as can enumerate C
5-12alkane, C
5-12naphthenic hydrocarbon, halo C
1-10alkane and halo C
5-12naphthenic hydrocarbon.
As described C
5-12alkane, such as can enumerate pentane, hexane, heptane, octane, nonane and decane etc., wherein preferred hexane, heptane and decane, most preferably hexane.
As described C
5-12naphthenic hydrocarbon, such as can enumerate hexanaphthene, pentamethylene, suberane, cyclodecane and cyclononane etc., most preferably hexanaphthene.
As described halo C
1-10alkane, such as can enumerate methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane and three n-butyl bromide etc.
As described halo C
5-12naphthenic hydrocarbon, such as can enumerate chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, bromo cyclononane and bromo cyclodecane etc.
These precipitation agents can be used alone one, also can be multiple used in combination with arbitrary ratio.
The feed postition of precipitation agent can add for disposable or drip, and preferably disposablely adds.In this precipitation process, the dispersion of stirring and promoting precipitation agent can be utilized, and be conducive to the final precipitation of solid product.This stirring can adopt any form (such as stirring rake), and rotating speed is generally 10 ~ 1000 revs/min etc.
To the consumption of described precipitation agent, there is no particular limitation, but general by volume, described precipitation agent be 1:0.2 ~ 5 for dissolving the ratio of the described solvent of described magnesium compound, preferred 1:0.5 ~ 2, more preferably 1:0.8 ~ 1.5.
To the temperature of described precipitation agent, also there is no particular limitation, but general preferred normal temperature is to the temperature (preferred 20-80 DEG C, more preferably 40-60 DEG C) of the boiling point lower than used any solvent and precipitation agent, but be sometimes not limited to this.And, this precipitation process general also preferred at normal temperature to temperature (the preferred 20-80 DEG C of the boiling point lower than used any solvent and precipitation agent, more preferably 40-60 DEG C) under carry out 0.3-12 hour, but be sometimes not limited to this, and with solid product substantially completely precipitation be as the criterion.
Completely after precipitation, obtained solid product filtered, wash and drying.Method for described filtration, washing and drying is not particularly limited, this area routine can be used as required to use those.
As required, described washing generally carries out 1 ~ 6 time, preferably 3 ~ 4 times.Wherein, washer solvent preferably uses the solvent identical with precipitation agent, but also can be different.
Described drying can adopt ordinary method to carry out, such as rare gas element desiccating method, boulton process or heating under vacuum desiccating method, preferred rare gas element desiccating method or heating under vacuum desiccating method, most preferably heating under vacuum desiccating method.
The temperature range of described drying is generally normal temperature to 140 DEG C.Time of drying is generally 2-20 hour, but also can be different for the solvent case dissolving described magnesium compound according to what specifically use.Such as, when adopting tetrahydrofuran (THF) as solvent for dissolving described magnesium compound, drying temperature is generally about 80 DEG C, dry 2 ~ 12 hours under vacuo, and when adopting toluene as solvent for dissolving described magnesium compound, drying temperature is generally about 100 DEG C, dry 4 ~ 24 hours under vacuo.
According to the present invention, by making the magnesium compound carrier of aforementioned acquisition contact with the chemical processing agent being selected from IV B race metallic compound with the silicon compound of formula (X), obtain load type non-metallocene catalyst of the present invention thus.
According to the present invention, react by making described chemical processing agent and described magnesium compound carrier, cause aforementioned Nonmetallocene part generation coordination reaction contained on described chemical processing agent and this magnesium compound carrier, thus on this magnesium compound carrier the Nonmetallocene title complex (the supported reaction of original position) of in-situ preparation atoms metal centered by described IVB race atoms metal, this is of the present invention one large feature.
Below the silicon compound of described formula (X) is specifically described.
Si (OR)
mx
4-mformula (X)
Wherein, each R is identical or different, is selected from C independently of one another
1-8straight or branched alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, different heptyl, n-octyl, iso-octyl etc.;
M is the integer of 0,1,2,3 or 4;
Each X is identical or different, is selected from halogen independently of one another.
According to the present invention, as described halogen, such as can enumerate fluorine, chlorine, bromine and iodine, wherein preferred chlorine.
According to the present invention, each R is preferably identical or different, is selected from C independently of one another
1-4straight or branched alkyl, is preferably ethyl.
As the silicon compound of described formula (X), can enumerate but be not limited to following particular compound:
Tetramethoxy-silicane, tetraethoxy-silicane, four positive propoxy silicon, tetraisopropoxide silicon, four n-butoxy silicon, tetraisobutoxy-silicane, four n-pentyloxy silicon, tetraisoamoxy-silicane, four n-octyloxy silicon, four different octyloxy silicon, one methoxyl group triethoxysilicane, dimethoxy diethoxy silicon, trimethoxy one oxyethyl group silicon, one methoxyl group three n-propyl oxygen base silicon, dimethoxy two positive propoxy silicon, trimethoxy one positive propoxy silicon, one methoxyl group triisopropyl oxygen base silicon, dimethoxy diisopropoxy silicon, trimethoxy one isopropoxy silicon, one methoxyl group three normal-butyl oxygen base silicon, dimethoxy two n-butoxy silicon, trimethoxy one n-butoxy silicon, one methoxyl group triisobutyl oxygen base silicon, dimethoxy two isobutoxy silicon, trimethoxy one isobutoxy silicon, one oxyethyl group three n-propyl oxygen base silicon, diethoxy two positive propoxy silicon, triethoxy one positive propoxy silicon, one oxyethyl group triisopropyl oxygen base silicon, diethoxy diisopropoxy silicon, triethoxy one isopropoxy silicon, one oxyethyl group three normal-butyl oxygen base silicon, diethoxy two n-butoxy silicon, triethoxy one n-butoxy silicon, one oxyethyl group triisobutyl oxygen base silicon, diethoxy two isobutoxy silicon, four C such as triethoxy one isobutoxy silicon
1-8straight or branched alkoxyl silicone, wherein preferred tetramethoxy-silicane, tetraethoxy-silicane, tetraisobutoxy-silicane, more preferably tetraethoxy-silicane,
Trimethoxy chloro silicon, dimethoxy chloro silicon, a methoxychlor for silicon, triethoxy chloro silicon, diethoxy chloro silicon, an oxyethyl group chloro silicon, three isobutoxy chloro silicon, two isobutoxy chloro silicon, an isobutoxy chloro silicon, the C such as trimethoxy bromo silicon, dimethoxy bromo silicon, a methoxyl group bromo silicon, triethoxy bromo silicon, diethoxy bromo silicon, an oxyethyl group bromo silicon, three isobutoxy bromo silicon, two isobutoxy bromo silicon, an isobutoxy bromo silicon
1-8straight or branched halogenated alkoxy silicon, wherein preferred trimethoxy chloro silicon, dimethoxy chloro silicon, triethoxy chloro silicon, diethoxy chloro silicon, more preferably triethoxy chloro silicon;
Silicon tetrafluoride, silicon tetrachloride, Silicon bromide, silicon tetraiodide, the silicon tetrahalogens such as tribromo silicon chlorides, trichlorine silicon bromide, wherein preferred silicon tetrachloride.
These silicon compounds can be used alone one, or use multiple with arbitrary ratio combination.
Below described chemical processing agent is specifically described.
According to the present invention, using IVB race metallic compound as described chemical processing agent.
As described IVB race metallic compound, such as can enumerate and be selected from IVB race metal halide, IVB race metal alkyl compound, IVB race metal alkoxide, IVB race metal alkyl halides and the halid at least one of IVB race metal alkoxide.
As described IVB race metal halide, described IVB race metal alkyl compound, described IVB race metal alkoxide, described IVB race metal alkyl halides and described IVB race metal alkoxide halogenide, the compound of following formula such as can be enumerated:
M(OR
1)
mX
nR
2 4-m－n
Wherein:
M is 0,1,2,3 or 4;
N is 0,1,2,3 or 4;
M is IVB race metal, such as titanium, zirconium and hafnium etc. in the periodic table of elements;
X is halogen, such as F, Cl, Br and I etc.; And
R
1and R
2be selected from C independently of one another
1-
10alkyl, such as methyl, ethyl, propyl group, normal-butyl, isobutyl-etc., R
1and R
2can be identical, also can be different.
Specifically, as described IVB race metal halide, such as titanium tetrafluoride (TiF can be enumerated
4), titanium tetrachloride (TiCl
4), titanium tetrabromide (TiBr
4), titanium tetra iodide (TiI
4);
Zirconium tetrafluoride (ZrF
4), zirconium tetrachloride (ZrCl
4), tetrabormated zirconium (ZrBr
4), zirconium tetraiodide (ZrI
4);
Tetrafluoride hafnium (HfF
4), hafnium tetrachloride (HfCl
4), hafnium (HfBr
4), tetraiodide hafnium (HfI
4).
As described IVB race metal alkyl compound, tetramethyl-titanium (Ti (CH such as can be enumerated
3)
4), tetraethyl-titanium (Ti (CH
3cH
2)
4), four isobutyl-titanium (Ti (i-C
4h
9)
4), tetra-n-butyl titanium (Ti (C
4h
9)
4), triethyl methyl titanium (Ti (CH
3) (CH
3cH
2)
3), diethyl-dimethyl titanium (Ti (CH
3)
2(CH
3cH
2)
2), trimethylethyl titanium (Ti (CH
3)
3(CH
3cH
2)), triisobutyl methyltitanium (Ti (CH
3) (i-C
4h
9)
3), diisobutyl dimethyl titanium (Ti (CH
3)
2(i-C
4h
9)
2), trimethylammonium isobutyl-titanium (Ti (CH
3)
3(i-C
4h
9)), triisobutyl ethyl titanium (Ti (CH
3cH
2) (i-C
4h
9)
3), diisobutyl diethyl titanium (Ti (CH
3cH
2)
2(i-C
4h
9)
2), triethyl isobutyl-titanium (Ti (CH
3cH
2)
3(i-C
4h
9)), three normal-butyl methyltitanium (Ti (CH
3) (C
4h
9)
3), di-n-butyl dimethyl titanium (Ti (CH
3)
2(C
4h
9)
2), trimethylammonium normal-butyl titanium (Ti (CH
3)
3(C
4h
9)), three normal-butyl methyltitanium (Ti (CH
3cH
2) (C
4h
9)
3), di-n-butyl diethyl titanium (Ti (CH
3cH
2)
2(C
4h
9)
2), triethyl normal-butyl titanium (Ti (CH
3cH
2)
3(C
4h
9)) etc.;
Tetramethyl-zirconium (Zr (CH
3)
4), tetraethyl-zirconium (Zr (CH
3cH
2)
4), four isobutyl-zirconium (Zr (i-C
4h
9)
4), tetra-n-butyl zirconium (Zr (C
4h
9)
4), triethyl methyl zirconium (Zr (CH
3) (CH
3cH
2)
3), diethyl-dimethyl zirconium (Zr (CH
3)
2(CH
3cH
2)
2), trimethylethyl zirconium (Zr (CH
3)
3(CH
3cH
2)), triisobutyl methylcyclopentadienyl zirconium (Zr (CH
3) (i-C
4h
9)
3), diisobutyl zirconium dimethyl (Zr (CH
3)
2(i-C
4h
9)
2), trimethylammonium isobutyl-zirconium (Zr (CH
3)
3(i-C
4h
9)), triisobutyl ethyl zirconium (Zr (CH
3cH
2) (i-C
4h
9)
3), diisobutyl diethyl zirconium (Zr (CH
3cH
2)
2(i-C
4h
9)
2), triethyl isobutyl-zirconium (Zr (CH
3cH
2)
3(i-C
4h
9)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH
3) (C
4h
9)
3), di-n-butyl zirconium dimethyl (Zr (CH
3)
2(C
4h
9)
2), trimethylammonium normal-butyl zirconium (Zr (CH
3)
3(C
4h
9)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH
3cH
2) (C
4h
9)
3), di-n-butyl diethyl zirconium (Zr (CH
3cH
2)
2(C
4h
9)
2), triethyl normal-butyl zirconium (Zr (CH
3cH
2)
3(C
4h
9)) etc.;
Tetramethyl-hafnium (Hf (CH
3)
4), tetraethyl-hafnium (Hf (CH
3cH
2)
4), four isobutyl-hafnium (Hf (i-C
4h
9)
4), tetra-n-butyl hafnium (Hf (C
4h
9)
4), triethyl methyl hafnium (Hf (CH
3) (CH
3cH
2)
3), diethyl-dimethyl hafnium (Hf (CH
3)
2(CH
3cH
2)
2), trimethylethyl hafnium (Hf (CH
3)
3(CH
3cH
2)), triisobutyl methylcyclopentadienyl hafnium (Hf (CH
3) (i-C
4h
9)
3), diisobutyl dimethyl hafnium (Hf (CH
3)
2(i-C
4h
9)
2), trimethylammonium isobutyl-hafnium (Hf (CH
3)
3(i-C
4h
9)), triisobutyl ethyl hafnium (Hf (CH
3cH
2) (i-C
4h
9)
3), diisobutyl diethyl hafnium (Hf (CH
3cH
2)
2(i-C
4h
9)
2), triethyl isobutyl-hafnium (Hf (CH
3cH
2)
3(i-C
4h
9)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH
3) (C
4h
9)
3), di-n-butyl dimethyl hafnium (Hf (CH
3)
2(C
4h
9)
2), trimethylammonium normal-butyl hafnium (Hf (CH
3)
3(C
4h
9)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH
3cH
2) (C
4h
9)
3), di-n-butyl diethyl hafnium (Hf (CH
3cH
2)
2(C
4h
9)
2), triethyl normal-butyl hafnium (Hf (CH
3cH
2)
3(C
4h
9)) etc.
As described IVB race metal alkoxide, tetramethoxy titanium (Ti (OCH such as can be enumerated
3)
4), purity titanium tetraethoxide (Ti (OCH
3cH
2)
4), four isobutoxy titanium (Ti (i-OC
4h
9)
4), four titanium n-butoxide (Ti (OC
4h
9)
4), triethoxy methoxyl group titanium (Ti (OCH
3) (OCH
3cH
2)
3), diethoxy dimethoxy titanium (Ti (OCH
3)
2(OCH
3cH
2)
2), trimethoxy ethanolato-titanium (Ti (OCH
3)
3(OCH
3cH
2)), three isobutoxy methoxyl group titanium (Ti (OCH
3) (i-OC
4h
9)
3), two isobutoxy dimethoxy titanium (Ti (OCH
3)
2(i-OC
4h
9)
2), trimethoxy isobutoxy titanium (Ti (OCH
3)
3(i-OC
4h
9)), three isobutoxy ethanolato-titanium (Ti (OCH
3cH
2) (i-OC
4h
9)
3), two isobutoxy diethoxy titanium (Ti (OCH
3cH
2)
2(i-OC
4h
9)
2), triethoxy isobutoxy titanium (Ti (OCH
3cH
2)
3(i-OC
4h
9)), three n-butoxy methoxyl group titanium (Ti (OCH
3) (OC
4h
9)
3), two n-butoxy dimethoxy titanium (Ti (OCH
3)
2(OC
4h
9)
2), trimethoxy titanium n-butoxide (Ti (OCH
3)
3(OC
4h
9)), three n-butoxy methoxyl group titanium (Ti (OCH
3cH
2) (OC
4h
9)
3), two n-butoxy diethoxy titanium (Ti (OCH
3cH
2)
2(OC
4h
9)
2), triethoxy titanium n-butoxide (Ti (OCH
3cH
2)
3(OC
4h
9)) etc.;
Tetramethoxy zirconium (Zr (OCH
3)
4), tetraethoxy zirconium (Zr (OCH
3cH
2)
4), four isobutoxy zirconium (Zr (i-OC
4h
9)
4), four n-butoxy zirconium (Zr (OC
4h
9)
4), triethoxy methoxyl group zirconium (Zr (OCH
3) (OCH
3cH
2)
3), diethoxy dimethoxy zirconium (Zr (OCH
3)
2(OCH
3cH
2)
2), trimethoxy oxyethyl group zirconium (Zr (OCH
3)
3(OCH
3cH
2)), three isobutoxy methoxyl group zirconium (Zr (OCH
3) (i-OC
4h
9)
3), two isobutoxy dimethoxy zirconium (Zr (OCH
3)
2(i-OC
4h
9)
2), trimethoxy isobutoxy zirconium (Zr (OCH
3)
3(i-C
4h
9)), three isobutoxy oxyethyl group zirconium (Zr (OCH
3cH
2) (i-OC
4h
9)
3), two isobutoxy diethoxy zirconium (Zr (OCH
3cH
2)
2(i-OC
4h
9)
2), triethoxy isobutoxy zirconium (Zr (OCH
3cH
2)
3(i-OC
4h
9)), three n-butoxy methoxyl group zirconium (Zr (OCH
3) (OC
4h
9)
3), two n-butoxy dimethoxy zirconium (Zr (OCH
3)
2(OC
4h
9)
2), trimethoxy n-butoxy zirconium (Zr (OCH
3)
3(OC
4h
9)), three n-butoxy methoxyl group zirconium (Zr (OCH
3cH
2) (OC
4h
9)
3), two n-butoxy diethoxy zirconium (Zr (OCH
3cH
2)
2(OC
4h
9)
2), triethoxy n-butoxy zirconium (Zr (OCH
3cH
2)
3(OC
4h
9)) etc.;
Tetramethoxy hafnium (Hf (OCH
3)
4), tetraethoxy hafnium (Hf (OCH
3cH
2)
4), four isobutoxy hafnium (Hf (i-OC
4h
9)
4), four n-butoxy hafnium (Hf (OC
4h
9)
4), triethoxy methoxyl group hafnium (Hf (OCH
3) (OCH
3cH
2)
3), diethoxy dimethoxy hafnium (Hf (OCH
3)
2(OCH
3cH
2)
2), trimethoxy oxyethyl group hafnium (Hf (OCH
3)
3(OCH
3cH
2)), three isobutoxy methoxyl group hafnium (Hf (OCH
3) (i-OC
4h
9)
3), two isobutoxy dimethoxy hafnium (Hf (OCH
3)
2(i-OC
4h
9)
2), trimethoxy isobutoxy hafnium (Hf (OCH
3)
3(i-OC
4h
9)), three isobutoxy oxyethyl group hafnium (Hf (OCH
3cH
2) (i-OC
4h
9)
3), two isobutoxy diethoxy hafnium (Hf (OCH
3cH
2)
2(i-OC
4h
9)
2), triethoxy isobutoxy hafnium (Hf (OCH
3cH
2)
3(i-C
4h
9)), three n-butoxy methoxyl group hafnium (Hf (OCH
3) (OC
4h
9)
3), two n-butoxy dimethoxy hafnium (Hf (OCH
3)
2(OC
4h
9)
2), trimethoxy n-butoxy hafnium (Hf (OCH
3)
3(OC
4h
9)), three n-butoxy methoxyl group hafnium (Hf (OCH
3cH
2) (OC
4h
9)
3), two n-butoxy diethoxy hafnium (Hf (OCH
3cH
2)
2(OC
4h
9)
2), triethoxy n-butoxy hafnium (Hf (OCH
3cH
2)
3(OC
4h
9)) etc.
As described IVB race metal alkyl halides, trimethyl ammonia chloride titanium (TiCl (CH such as can be enumerated
3)
3), triethyl titanium chloride (TiCl (CH
3cH
2)
3), triisobutyl titanium chloride (TiCl (i-C
4h
9)
3), three n-butylmagnesium chloride titanium (TiCl (C
4h
9)
3), dimethyl titanium dichloride (TiCl
2(CH
3)
2), diethyl titanium dichloride (TiCl
2(CH
3cH
2)
2), diisobutyl titanium dichloride (TiCl
2(i-C
4h
9)
2), three n-butylmagnesium chloride titanium (TiCl (C
4h
9)
3), methyl titanous chloride (Ti (CH
3) Cl
3), ethyl titanous chloride (Ti (CH
3cH
2) Cl
3), isobutyl-titanous chloride (Ti (i-C
4h
9) Cl
3), normal-butyl titanous chloride (Ti (C
4h
9) Cl
3);
Trimethylammonium titanium bromide (TiBr (CH
3)
3), triethyl titanium bromide (TiBr (CH
3cH
2)
3), triisobutyl titanium bromide (TiBr (i-C
4h
9)
3), three normal-butyl titanium bromide (TiBr (C
4h
9)
3), dimethyl dibrominated titanium (TiBr
2(CH
3)
2), diethyl dibrominated titanium (TiBr
2(CH
3cH
2)
2), diisobutyl dibrominated titanium (TiBr
2(i-C
4h
9)
2), three normal-butyl titanium bromide (TiBr (C
4h
9)
3), methyl titanium tribromide (Ti (CH
3) Br
3), ethyl titanium tribromide (Ti (CH
3cH
2) Br
3), isobutyl-titanium tribromide (Ti (i-C
4h
9) Br
3), normal-butyl titanium tribromide (Ti (C
4h
9) Br
3);
Trimethyl ammonia chloride zirconium (ZrCl (CH
3)
3), triethyl zirconium chloride (ZrCl (CH
3cH
2)
3), triisobutyl zirconium chloride (ZrCl (i-C
4h
9)
3), three n-butylmagnesium chloride zirconium (ZrCl (C
4h
9)
3), dimethyl zirconium dichloride (ZrCl
2(CH
3)
2), diethyl zirconium dichloride (ZrCl
2(CH
3cH
2)
2), diisobutyl zirconium dichloride (ZrCl
2(i-C
4h
9)
2), three n-butylmagnesium chloride zirconium (ZrCl (C
4h
9)
3), methyl tri-chlorination zirconium (Zr (CH
3) Cl
3), ethyl tri-chlorination zirconium (Zr (CH
3cH
2) Cl
3), isobutyl-tri-chlorination zirconium (Zr (i-C
4h
9) Cl
3), normal-butyl tri-chlorination zirconium (Zr (C
4h
9) Cl
3);
Trimethylammonium zirconium bromide (ZrBr (CH
3)
3), triethyl zirconium bromide (ZrBr (CH
3cH
2)
3), triisobutyl zirconium bromide (ZrBr (i-C
4h
9)
3), three normal-butyl zirconium bromide (ZrBr (C
4h
9)
3), dimethyl dibrominated zirconium (ZrBr
2(CH
3)
2), diethyl dibrominated zirconium (ZrBr
2(CH
3cH
2)
2), diisobutyl dibrominated zirconium (ZrBr
2(i-C
4h
9)
2), three normal-butyl zirconium bromide (ZrBr (C
4h
9)
3), methyl tribromide zirconium (Zr (CH
3) Br
3), ethyl tribromide zirconium (Zr (CH
3cH
2) Br
3), isobutyl-tribromide zirconium (Zr (i-C
4h
9) Br
3), normal-butyl tribromide zirconium (Zr (C
4h
9) Br
3);
Trimethyl ammonia chloride hafnium (HfCl (CH
3)
3), triethyl hafnium chloride (HfCl (CH
3cH
2)
3), triisobutyl hafnium chloride (HfCl (i-C
4h
9)
3), three n-butylmagnesium chloride hafnium (HfCl (C
4h
9)
3), dimethyl hafnium dichloride (HfCl
2(CH
3)
2), diethyl hafnium dichloride (HfCl
2(CH
3cH
2)
2), diisobutyl hafnium dichloride (HfCl
2(i-C
4h
9)
2), three n-butylmagnesium chloride hafnium (HfCl (C
4h
9)
3), methyl tri-chlorination hafnium (Hf (CH
3) Cl
3), ethyl tri-chlorination hafnium (Hf (CH
3cH
2) Cl
3), isobutyl-tri-chlorination hafnium (Hf (i-C
4h
9) Cl
3), normal-butyl tri-chlorination hafnium (Hf (C
4h
9) Cl
3);
Trimethylammonium bromination hafnium (HfBr (CH
3)
3), triethyl bromination hafnium (HfBr (CH
3cH
2)
3), triisobutyl bromination hafnium (HfBr (i-C
4h
9)
3), three normal-butyl bromination hafnium (HfBr (C
4h
9)
3), dimethyl dibrominated hafnium (HfBr
2(CH
3)
2), diethyl dibrominated hafnium (HfBr
2(CH
3cH
2)
2), diisobutyl dibrominated hafnium (HfBr
2(i-C
4h
9)
2), three normal-butyl bromination hafnium (HfBr (C
4h
9)
3), methyl tribromide hafnium (Hf (CH
3) Br
3), ethyl tribromide hafnium (Hf (CH
3cH
2) Br
3), isobutyl-tribromide hafnium (Hf (i-C
4h
9) Br
3), normal-butyl tribromide hafnium (Hf (C
4h
9) Br
3).
As described IVB race metal alkoxide halogenide, trimethoxy titanium chloride (TiCl (OCH such as can be enumerated
3)
3), triethoxy titanium chloride (TiCl (OCH
3cH
2)
3), three isobutoxy titanium chloride (TiCl (i-OC
4h
9)
3), three n-Butoxyl titanium-chlorides (TiCl (OC
4h
9)
3), dimethoxy titanium dichloride (TiCl
2(OCH
3)
2), diethoxy titanium dichloride (TiCl
2(OCH
3cH
2)
2), two isobutoxy titanium dichloride (TiCl
2(i-OC
4h
9)
2), three n-Butoxyl titanium-chlorides (TiCl (OC
4h
9)
3), methoxytitanium trichloride (Ti (OCH
3) Cl
3), oxyethyl group titanous chloride (Ti (OCH
3cH
2) Cl
3), isobutoxy titanous chloride (Ti (i-C
4h
9) Cl
3), nbutoxytitanium trichloride (Ti (OC
4h
9) Cl
3);
Trimethoxy titanium bromide (TiBr (OCH
3)
3), triethoxy titanium bromide (TiBr (OCH
3cH
2)
3), three isobutoxy titanium bromide (TiBr (i-OC
4h
9)
3), three n-butoxy titanium bromide (TiBr (OC
4h
9)
3), dimethoxy dibrominated titanium (TiBr
2(OCH
3)
2), diethoxy dibrominated titanium (TiBr
2(OCH
3cH
2)
2), two isobutoxy dibrominated titanium (TiBr
2(i-OC
4h
9)
2), three n-butoxy titanium bromide (TiBr (OC
4h
9)
3), methoxyl group titanium tribromide (Ti (OCH
3) Br
3), oxyethyl group titanium tribromide (Ti (OCH
3cH
2) Br
3), isobutoxy titanium tribromide (Ti (i-C
4h
9) Br
3), n-butoxy titanium tribromide (Ti (OC
4h
9) Br
3);
Trimethoxy zirconium chloride (ZrCl (OCH
3)
3), triethoxy zirconium chloride (ZrCl (OCH
3cH
2)
3), three isobutoxy zirconium chloride (ZrCl (i-OC
4h
9)
3), three n-butoxy zirconium chloride (ZrCl (OC
4h
9)
3), dimethoxy zirconium dichloride (ZrCl
2(OCH
3)
2), diethoxy zirconium dichloride (ZrCl
2(OCH
3cH
2)
2), two isobutoxy zirconium dichloride (ZrCl
2(i-OC
4h
9)
2), three n-butoxy zirconium chloride (ZrCl (OC
4h
9)
3), methoxyl group tri-chlorination zirconium (Zr (OCH
3) Cl
3), oxyethyl group tri-chlorination zirconium (Zr (OCH
3cH
2) Cl
3), isobutoxy tri-chlorination zirconium (Zr (i-C
4h
9) Cl
3), n-butoxy tri-chlorination zirconium (Zr (OC
4h
9) Cl
3);
Trimethoxy zirconium bromide (ZrBr (OCH
3)
3), triethoxy zirconium bromide (ZrBr (OCH
3cH
2)
3), three isobutoxy zirconium bromide (ZrBr (i-OC
4h
9)
3), three n-butoxy zirconium bromide (ZrBr (OC
4h
9)
3), dimethoxy dibrominated zirconium (ZrBr
2(OCH
3)
2), diethoxy dibrominated zirconium (ZrBr
2(OCH
3cH
2)
2), two isobutoxy dibrominated zirconium (ZrBr
2(i-OC
4h
9)
2), three n-butoxy zirconium bromide (ZrBr (OC
4h
9)
3), methoxyl group tribromide zirconium (Zr (OCH
3) Br
3), oxyethyl group tribromide zirconium (Zr (OCH
3cH
2) Br
3), isobutoxy tribromide zirconium (Zr (i-C
4h
9) Br
3), n-butoxy tribromide zirconium (Zr (OC
4h
9) Br
3);
Trimethoxy hafnium chloride (HfCl (OCH
3)
3), triethoxy hafnium chloride (HfCl (OCH
3cH
2)
3), three isobutoxy hafnium chloride (HfCl (i-OC
4h
9)
3), three n-butoxy hafnium chloride (HfCl (OC
4h
9)
3), dimethoxy hafnium dichloride (HfCl
2(OCH
3)
2), diethoxy hafnium dichloride (HfCl
2(OCH
3cH
2)
2), two isobutoxy hafnium dichloride (HfCl
2(i-OC
4h
9)
2), three n-butoxy hafnium chloride (HfCl (OC
4h
9)
3), methoxyl group tri-chlorination hafnium (Hf (OCH
3) Cl
3), oxyethyl group tri-chlorination hafnium (Hf (OCH
3cH
2) Cl
3), isobutoxy tri-chlorination hafnium (Hf (i-C
4h
9) Cl
3), n-butoxy tri-chlorination hafnium (Hf (OC
4h
9) Cl
3);
Trimethoxy bromination hafnium (HfBr (OCH
3)
3), triethoxy bromination hafnium (HfBr (OCH
3cH
2)
3), three isobutoxy bromination hafnium (HfBr (i-OC
4h
9)
3), three n-butoxy bromination hafnium (HfBr (OC
4h
9)
3), dimethoxy dibrominated hafnium (HfBr
2(OCH
3)
2), diethoxy dibrominated hafnium (HfBr
2(OCH
3cH
2)
2), two isobutoxy dibrominated hafnium (HfBr
2(i-OC
4h
9)
2), three n-butoxy bromination hafnium (HfBr (OC
4h
9)
3), methoxyl group tribromide hafnium (Hf (OCH
3) Br
3), oxyethyl group tribromide hafnium (Hf (OCH
3cH
2) Br
3), isobutoxy tribromide hafnium (Hf (i-C
4h
9) Br
3), n-butoxy tribromide hafnium (Hf (OC
4h
9) Br
3).
As described IVB race metallic compound, preferred described IVB race metal halide, more preferably TiCl
4, TiBr
4, ZrCl
4, ZrBr
4, HfCl
4and HfBr
4, most preferably TiCl
4and ZrCl
4.
These IVB race metallic compounds can be used alone one, or use multiple with arbitrary ratio combination.
When described chemical processing agent is liquid at normal temperatures, this chemical processing agent can be directly used to carry out described chemical treatment reaction.When described chemical processing agent is solid-state at normal temperatures, in order to measure with easy to operate for the purpose of, preferably use described chemical processing agent as a solution.Certainly, when described chemical processing agent is liquid at normal temperatures, sometimes also can uses described chemical processing agent as a solution as required, be not particularly limited.
When preparing the solution of described chemical processing agent, to now used solvent, there is no particular limitation, as long as it can dissolve this chemical processing agent and do not destroy the existing carrier structure of (such as dissolving) described magnesium compound carrier.
Specifically, C can be enumerated
5-12alkane, C
5-12naphthenic hydrocarbon, halo C
5-12alkane and halo C
5-12naphthenic hydrocarbon etc., such as can enumerate pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, pentamethylene, hexanaphthene, suberane, cyclooctane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro undecane, chlorinated dodecane and chlorocyclohexane etc., wherein preferred pentane, hexane, decane and hexanaphthene, most preferably hexane.
These solvents can be used alone one, or use multiple with arbitrary ratio combination.
In addition, to the concentration of described chemical processing agent in its solution, there is no particular limitation, can suitably select as required, as long as it can realize reacting to carry out described chemical treatment with the described chemical processing agent of predetermined amount.As previously mentioned, if chemical processing agent is liquid, chemical processing agent directly can be used to carry out described process, but use after also can being modulated into the solution of chemical processing agent.
Generally speaking, the volumetric molar concentration of described chemical processing agent in its solution is generally set as 0.01 ~ 1.0mol/L, but is not limited to this.
According to the present invention, that reacts as described chemical treatment carries out mode, such as can enumerate and make described magnesium compound carrier and described silicon compound and described chemical processing agent under the existence of solvent (also referred to as chemical treatment solvent), carry out the mode contacted.
According to the present invention, to described chemical treatment solvent, there is no particular limitation, as long as it can dissolve described silicon compound and described chemical processing agent, and do not destroy the existing carrier structure of (such as dissolving) described magnesium compound carrier.
Specifically, as described chemical treatment solvent, C can be enumerated
5-12alkane, C
5-12naphthenic hydrocarbon, halo C
5-12alkane and halo C
5-12naphthenic hydrocarbon etc., such as can enumerate pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, pentamethylene, hexanaphthene, suberane, cyclooctane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro undecane, chlorinated dodecane and chlorocyclohexane etc., wherein preferred pentane, hexane, decane and hexanaphthene, most preferably hexane.
These solvents can be used alone one, or use multiple with arbitrary ratio combination.
According to the present invention, as the consumption of described chemical treatment solvent, make described magnesium compound carrier be 1g:1-100ml relative to the ratio of described chemical treatment solvent, preferred 1g:2-40ml, but be sometimes not limited to this.In addition, when using chemical processing agent as previously mentioned as a solution, suitably can reduce the consumption of described chemical treatment solvent according to practical situation, but being not particularly limited.
According to the present invention, as the consumption of described silicon compound, make in the described magnesium compound carrier of Mg element and reach 1:0.01-1 in the mol ratio of the described silicon compound of Si element, preferred 1:0.01-0.50, more preferably 1:0.05-0.25.
According to the present invention, as the consumption of described chemical processing agent, make in the described magnesium compound carrier of Mg element and reach 1:0.01-1 with the mol ratio of the described chemical processing agent of IVB race elemental metal, preferred 1:0.01-0.50, more preferably 1:0.10-0.30.
It is known that when using IVB race metallic compound chemical treatment carrier, meeting immobilized a certain amount of IVB race metallic compound on this carrier.The present inventor is found by research, in the IVB race metallic compound that this is immobilized, have a sizable part to be rendered as non-activity state, that is, this part IVB race metallic compound is for the olefinic polymerization catalysis activity not contribution of the final loaded catalyst manufactured.For this reason, the present inventor is by further studying discovery, if when using IVB race metallic compound chemical treatment carrier also with the aforementioned specific silicon compound of the present invention, the ratio of this non-activity part can be reduced significantly or reduce the supported quantity of described IVB race metallic compound on carrier significantly, thus correspondingly improving the charge capacity of Nonmetallocene title complex or the load percentage relative to IVB race metallic compound.As a result, with not and with compared with the situation of described silicon compound, the present invention and with described silicon compound time, the olefinic polymerization catalysis that can significantly improve the final load type non-metallocene catalyst obtained is active.In addition, the present inventor also finds, by and use described silicon compound, can also the molecular weight distribution that narrows be realized, improve mechanical properties of polymer, and make the comonomer more regular function of sequence distribution in the polymer.These discoveries are all Promethean in the art.
According to the present invention, to the engagement sequence of described magnesium compound carrier and described silicon compound and described chemical processing agent, there is no particular limitation, and such as this three can contact simultaneously, also can according to arbitrary order successively contact.
According to the present invention one preferred embodiment, under the existence of described chemical treatment solvent, described magnesium compound carrier is first contacted with described silicon compound (the first contact procedure), and then add described chemical processing agent and further contact (the second contact procedure), carry out described chemical treatment reaction thus.
Mode is carried out as described first contact procedure, such as can enumerate under agitation, by described magnesium compound carrier and described silicon compound simultaneously or successively add in described chemical treatment solvent, continue to stir under 0-100 DEG C (preferred 20-80 DEG C) and react and form the mode of slurry.To the reaction times now, there is no particular limitation, such as can enumerate 0-6h, preferred 0.5-4h.
After obtaining slurry as previously mentioned, this slurry is further contacted (the second contact procedure) with described chemical processing agent.
Mode is carried out as described second contact procedure, such as can enumerate under agitation, the solution of (preferably dripping) described chemical processing agent or described chemical processing agent is added in described slurry, and after this adds end, continue to stir and the mode of reacting under 0-100 DEG C (preferred 20-80 DEG C).To the reaction times now, there is no particular limitation, such as can enumerate 0.5-8h, preferred 1-4h.
After described chemical treatment reaction terminates, by filtering, washing and drying, can obtain through chemically treated product (load type non-metallocene catalyst of the present invention).
According to the present invention, described filtration, washing and drying can adopt ordinary method to carry out, and wherein washer solvent can adopt the solvent same with described chemical treatment solvent phase.As required, this washing generally carries out 1 ~ 8 time, preferably 2 ~ 6 times, most preferably 2 ~ 4 times.
Described drying can adopt ordinary method to carry out, such as rare gas element desiccating method, boulton process or heating under vacuum desiccating method, preferred rare gas element desiccating method or heating under vacuum desiccating method, most preferably heating under vacuum desiccating method.The temperature range of described drying is generally normal temperature to 140 DEG C, and time of drying is generally 2-20 hour, but is not limited to this.
According to the present invention, the preparation method of described load type non-metallocene catalyst as required, optional being also included in makes before described magnesium compound carrier and described silicon compound contact with described chemical processing agent, by the step (pre-treatment step) helping magnesium compound carrier described in chemical processing agent pre-treatment being selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.
In the context of the present specification, unless specifically stated otherwise or obviously unreasonable, without exception will through this pretreated magnesium compound carrier also referred to as magnesium compound carrier.
Below the described chemical processing agent that helps is specifically described.
According to the present invention, help chemical processing agent as described, such as can enumerate aikyiaiurnirsoxan beta and aluminum alkyls.
As described aikyiaiurnirsoxan beta, such as can enumerate the linear alumoxanes shown in following general formula (I): (R) (R) Al-(Al (R)-O)
n-O-Al (R) (R), and the Cyclic aluminoxane shown in following general formula (II) :-(Al (R)-O-)
n+2-.
（I）
（II）
In aforementioned formula, radicals R is same to each other or different to each other (preferably identical), is selected from C independently of one another
1-C
8alkyl, preferable methyl, ethyl and isobutyl-, most preferable; N is the arbitrary integer within the scope of 1-50, the arbitrary integer preferably in 10 ~ 30 scopes.
As described aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, further preferable methyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.
These aikyiaiurnirsoxan beta can be used alone one, or use multiple with arbitrary ratio combination.
As described aluminum alkyls, such as the compound shown in following general formula can be enumerated:
Al(R)
3
Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from C independently of one another
1-C
8alkyl, preferable methyl, ethyl and isobutyl-, most preferable.
Specifically, as described aluminum alkyls, trimethyl aluminium (Al (CH such as can be enumerated
3)
3), triethyl aluminum (Al (CH
3cH
2)
3), tri-n-n-propyl aluminum (Al (C
3h
7)
3), triisopropylaluminiuand (Al (i-C
3h
7)
3), triisobutyl aluminium (Al (i-C
4h
9)
3), three n-butylaluminum (Al (C
4h
9)
3), triisopentyl aluminium (Al (i-C
5h
11)
3), three n-pentyl aluminium (Al (C
5h
11)
3), tri-n-hexyl aluminum (Al (C
6h
13)
3), three isohexyl aluminium (Al (i-C
6h
13)
3), diethylmethyl aluminium (Al (CH
3) (CH
3cH
2)
2) and dimethyl ethyl aluminium (Al (CH
3cH
2) (CH
3)
2) etc., wherein preferred trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.
These aluminum alkylss can be used alone one, or use multiple with arbitrary ratio combination.
According to the present invention, help chemical processing agent as described, can only adopt described aikyiaiurnirsoxan beta, also can only adopt described aluminum alkyls, but also can adopt any mixture of described aikyiaiurnirsoxan beta and described aluminum alkyls.And to the ratio of component each in this mixture, there is no particular limitation, can select arbitrarily as required.
According to the present invention, described in help chemical processing agent generally to use as a solution.When helping the solution of chemical processing agent described in preparing, to now used solvent, there is no particular limitation, as long as it can dissolve this help chemical processing agent and the existing carrier structure not destroying (such as dissolving) described magnesium compound carrier.
Specifically, C can be enumerated
5-12alkane, C
5-12naphthenic hydrocarbon, halo C
5-12alkane and halo C
5-12naphthenic hydrocarbon etc., such as can enumerate pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, pentamethylene, hexanaphthene, suberane, cyclooctane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro undecane, chlorinated dodecane and chlorocyclohexane etc., wherein preferred pentane, hexane, decane and hexanaphthene, most preferably hexane.
These solvents can be used alone one, or use multiple with arbitrary ratio combination.
In addition, help the concentration of chemical processing agent in its solution to described there is no particular limitation, can suitably select as required, as long as it can realize helping chemical processing agent to carry out described pre-treatment step described in predetermined amount.
As the method for carrying out described pre-treatment step, such as can enumerate, first the solution of chemical processing agent is helped described in preparing, then help in the pretreated described magnesium compound carrier of chemical processing agent described in using to plan to be metered into described in (preferably dripping) and help chemical treatment agent solution (wherein helping chemical processing agent containing described in predetermined amount), or add described magnesium compound carrier, forming reactions mixed solution thus to the described chemical treatment agent solution amount of falling into a trap that helps.Now, temperature of reaction is generally-40 ~ 60 DEG C, and preferably-30 ~ 30 DEG C, the reaction times is generally 1 ~ 8h, preferably 2 ~ 6h, and most preferably 3 ~ 4h(is if desired by stirring).Then, by filtering, washing and drying, isolate from this reaction mixture through pretreated magnesium compound carrier.Then, use this through pretreated magnesium compound carrier, according to describe entirely identical mode before, carry out and the contacting of silicon compound and chemical processing agent.
According to the present invention, described filtration, washing and drying can adopt ordinary method to carry out, wherein washer solvent can adopt with dissolve described in help chemical processing agent time identical solvent used.As required, this washing generally carries out 1 ~ 8 time, preferably 2 ~ 6 times, most preferably 2 ~ 4 times.Described drying can adopt ordinary method to carry out, such as rare gas element desiccating method, boulton process or heating under vacuum desiccating method, preferred rare gas element desiccating method or heating under vacuum desiccating method, most preferably heating under vacuum desiccating method.The temperature range of described drying is generally normal temperature to 140 DEG C, and time of drying is generally 2-20 hour, but is not limited to this.
According to the present invention, as the consumption of described Nonmetallocene part, make in the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part for 1:0.0001-1, preferred 1:0.0002-0.4, more preferably 1:0.0008-0.2, further preferred 1:0.001-0.1.
According to the present invention, as the consumption of described solvent, the ratio of described magnesium compound and described solvent is made to be 1mol:75 ~ 400ml, preferred 1mol:150 ~ 300ml, more preferably 1mol:200 ~ 250ml.
According to the present invention, as the consumption of described alcohol, make in the mol ratio of the described magnesium compound of Mg element and described alcohol for 1:0.02 ~ 4.00, preferred 1:0.05 ~ 3.00, more preferably 1:0.10 ~ 2.50.
According to the present invention, as the consumption of described precipitation agent, the volume ratio of described precipitation agent and described solvent is made to be 1:0.2 ~ 5, preferred 1:0.5 ~ 2, more preferably 1:0.8 ~ 1.5.
According to the present invention, as the consumption of described silicon compound, make in the described magnesium compound carrier of Mg element with in the mol ratio of the described silicon compound of Si element for 1:0.01-1, preferred 1:0.01-0.50, more preferably 1:0.05-0.25.
According to the present invention, as the consumption of described chemical processing agent, make in the described magnesium compound carrier of Mg element with the mol ratio of the described chemical processing agent of IVB race elemental metal for 1:0.01-1, preferred 1:0.01-0.50, more preferably 1:0.10-0.30.
According to the present invention, as the described consumption helping chemical processing agent, make in the described magnesium compound carrier of Mg element and to help the mol ratio of chemical processing agent for 1:0-1.0 described in Al element, preferred 1:0-0.5, more preferably 1:0.1-0.5.
Known to those skilled in the art, aforementioned all method stepss are all preferred to carry out under the condition of anhydrous and oxygen-free substantially.Substantially the content that anhydrous and oxygen-free mentioned here refers to water and oxygen in system continues to be less than 100ppm.And load type non-metallocene catalyst of the present invention needs pressure-fired rare gas element (such as nitrogen, argon gas, helium etc.) in confined conditions to save backup under existing after the production usually.
In one embodiment, the invention still further relates to the load type non-metallocene catalyst (sometimes also referred to as carry type non-metallocene calalyst for polymerization of olefine) manufactured by the preparation method of aforesaid load type non-metallocene catalyst.
In a further embodiment, the present invention relates to a kind of alkene homopolymerization/copolymerization method, wherein using load type non-metallocene catalyst of the present invention as catalyst for olefines polymerizing, make alkene homopolymerization or copolymerization.
With regard to this alkene homopolymerization/copolymerization method involved in the present invention, except the following content particularly pointed out, other contents do not explained (such as the addition manner etc. of polymerization reactor, alkene consumption, catalyzer and alkene), directly can be suitable for conventional known those in this area, not special restriction, at this, the description thereof will be omitted.
According to homopolymerization/copolymerization method of the present invention, with load type non-metallocene catalyst of the present invention for Primary Catalysts, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt for promotor, make alkene homopolymerization or copolymerization.
Primary Catalysts and promotor can be first add Primary Catalysts to the feed postition in polymerization reaction system, and then add promotor, or first add promotor, and then add Primary Catalysts, or both first contact mixing after add together, or to add respectively simultaneously.Primary Catalysts and promotor are added respectively and fashionablely both can to add successively in same Feed lines, also can add successively in multichannel Feed lines, and both add respectively simultaneously and fashionablely should select multichannel Feed lines.For continous way polyreaction, preferred multichannel Feed lines adds simultaneously continuously, and for intermittence type polymerization reaction, preferably adds together in same Feed lines after both first mixing, or in same Feed lines, first add promotor, and then add Primary Catalysts.
According to the present invention, to the reactive mode of described alkene homopolymerization/copolymerization method, there is no particular limitation, can adopt well known in the art those, such as can enumerate slurry process, substance law and vapor phase process etc., wherein preferred slurries method and vapor phase process.
According to the present invention, as described alkene, such as C can be enumerated
2~ C
10monoolefine, diolefin, cyclic olefin and other ethylenically unsaturated compounds.
Specifically, as described C
2~ C
12monoolefine, such as can enumerate ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene and vinylbenzene etc.; As described cyclic olefin, such as 1-cyclopentenes and norbornylene etc. can be enumerated; As described diolefin, Isosorbide-5-Nitrae-divinyl, 2,5-pentadienes, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc. such as can be enumerated; And as other ethylenically unsaturated compounds described, vinyl acetate and (methyl) acrylate etc. such as can be enumerated.
According to the present invention, the homopolymerization of further optimal ethylene, or ethene and be selected from the copolymerization of at least one alpha-olefin (being called comonomer) of C3-C12 alpha-olefin.As described C3-C12 alpha-olefin more preferably C3-C8 alpha-olefin.As alpha-olefin used herein, such as can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-laurylene and 4-methyl isophthalic acid-hexene etc., preferred propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene and 1-octene etc., more preferably propylene, 1-hexene, 4-methyl-1-pentene and 1-octene etc.These alpha-olefins can be used alone, and maybe two or more in them can be combinationally used.
According to the present invention, in use, the usage quantity of described comonomer is generally 0.5 ~ 10 gram of/milligram of Primary Catalysts, preferably 1 ~ 5 gram of/milligram of Primary Catalysts.
According to the present invention, described promotor is selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, at least one wherein preferably in aikyiaiurnirsoxan beta and aluminum alkyls.
As described aikyiaiurnirsoxan beta, such as can enumerate the linear alumoxanes shown in following general formula (I-1): (R) (R) Al-(Al (R)-O)
n-O-Al (R) (R), and the Cyclic aluminoxane shown in following general formula (II-1) :-(Al (R)-O-)
n+2-.
（I-1）
（II-1）
In aforementioned formula, radicals R is same to each other or different to each other (preferably identical), is selected from C independently of one another
1-C
8alkyl, preferable methyl, ethyl and isobutyl-, most preferable.N is the arbitrary integer within the scope of 1-50, the arbitrary integer preferably in 10 ~ 30 scopes.
As described aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, further preferable methyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide, and most preferable aikyiaiurnirsoxan beta.
These aikyiaiurnirsoxan beta can be used alone one, or use multiple with arbitrary ratio combination.
As described aluminum alkyls, such as the compound shown in following general formula can be enumerated:
Al(R)
3
Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from C independently of one another
1-C
8alkyl, preferable methyl, ethyl and isobutyl-, most preferable.
Specifically, as described aluminum alkyls, trimethyl aluminium (Al (CH such as can be enumerated
3)
3), triethyl aluminum (Al (CH
3cH
2)
3), tri-n-n-propyl aluminum (Al (C
3h
7)
3), triisobutyl aluminium (Al (i-C
4h
9)
3), three n-butylaluminum (Al (C
4h
9)
3), triisopentyl aluminium (Al (i-C
5h
11)
3), three n-pentyl aluminium (Al (C
5h
11)
3), tri-n-hexyl aluminum (Al (C
6h
13)
3), three isohexyl aluminium (Al (i-C
6h
13)
3), diethylmethyl aluminium (Al (CH
3) (CH
3cH
2)
2) and dimethyl ethyl aluminium (Al (CH
3cH
2) (CH
3)
2) etc., wherein preferably trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum and triisobutyl aluminium, further preferably triethyl aluminum and triisobutyl aluminium, and most preferably triethyl aluminum.
These aluminum alkylss can be used alone one, or use multiple with arbitrary ratio combination.
As described haloalkyl aluminium, such as the compound shown in following general formula can be enumerated:
Al(R)
nX
3-n
Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from C independently of one another
1-C
8alkyl, preferable methyl, ethyl and isobutyl-, most preferable.Radicals X is halogen, preferred chlorine.N is 1 or 2.
Specifically, as described haloalkyl aluminium, a Chlorodimethyl aluminium (Al (CH such as can be enumerated
3)
2cl), dichloromethyl aluminium (Al (CH
3) Cl
2)), aluminium diethyl monochloride (Al (CH
3cH
2)
2cl), ethyl aluminum dichloride (Al (CH
3cH
2) Cl
2), a chlorine dipropyl aluminium (Al (C
3h
7)
2cl), two chloropropyl aluminium (Al (C
3h
7) Cl
2)), a chlorine di-n-butyl aluminium (Al (C
4h
9)
2cl), dichloro n-butylaluminum (Al (C
4h
9) Cl
2), a chloro-di-isobutyl aluminum (Al (i-C
4h
9)
2cl), dichloro aluminium isobutyl (Al (i-C
4h
9) Cl
2), a chlorine two n-pentyl aluminium (Al (C
5h
11)
2cl), dichloro n-pentyl aluminium (Al (C
5h
11) Cl
2), a chlorine diisoamyl aluminium (Al (i-C
5h
11)
2cl), dichloro isopentyl aluminium (Al (i-C
5h
11) Cl
2), a chlorine di-n-hexyl aluminium (Al (C
6h
13)
2cl), dichloro n-hexyl aluminium (Al (C
6h
13) Cl
2), a chlorine two isohexyl aluminium (Al (i-C
6h
13)
2cl), dichloro isohexyl aluminium (Al (i-C
6h
13) Cl
2),
Chloromethyl aluminium triethyl (Al (CH
3) (CH
3cH
2) Cl), chloromethyl propyl group aluminium (Al (CH
3) (C
3h
7) Cl), chloromethyl n-butylaluminum (Al (CH
3) (C
4h
9) Cl), chloromethyl aluminium isobutyl (Al (CH
3) (i-C
4h
9) Cl), a chloroethyl propyl group aluminium (Al (CH
2cH
3) (C
3h
7) Cl), a chloroethyl n-butylaluminum (AlCH
2cH
3) (C
4h
9) Cl), chloromethyl aluminium isobutyl (AlCH
2cH
3) (i-C
4h
9) Cl) etc., wherein preferred aluminium diethyl monochloride, ethyl aluminum dichloride, a chlorine di-n-butyl aluminium, dichloro n-butylaluminum, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl, a chlorine di-n-hexyl aluminium, dichloro n-hexyl aluminium, further preferably chlorodiethyl aluminium, ethyl aluminum dichloride and a chlorine di-n-hexyl aluminium, and most preferably aluminium diethyl monochloride.
These haloalkyl aluminium can be used alone one, or use multiple with arbitrary ratio combination.
As described boron fluothane, described boron alkyl and described boron alkyl ammonium salt, directly can use those of this area routine use, not special restriction.
In addition, according to the present invention, described promotor can be used alone one, also can use multiple aforesaid promotor with arbitrary ratio combination as required, not special restriction.
According to the present invention, according to the difference (such as slurry polymerization) of the reactive mode of described alkene homopolymerization/copolymerization method, sometimes need to use solvent for polymerization.
As described solvent for polymerization, can use this area when carrying out alkene homopolymerization/copolymerization conventional use those, not special restriction.
As described solvent for polymerization, such as C can be enumerated
4-10alkane (such as butane, pentane, hexane, heptane, octane, nonane or decane etc.), halo C
1-10alkane (such as methylene dichloride), C
6-12naphthenic hydrocarbon (hexanaphthene, suberane, cyclooctane, cyclononane or cyclodecane), C
6-20aromatic hydrocarbon (such as toluene and dimethylbenzene) etc.Wherein, pentane, hexane, heptane and cyclohexane give is preferably used to be described solvent for polymerization, most preferably hexane.
These solvent for polymerization can be used alone one, or use multiple with arbitrary ratio combination.
According to the present invention, the polymerization pressure of described alkene homopolymerization/copolymerization method is generally 0.1 ~ 10MPa, preferably 0.1 ~ 4MPa, more preferably 0.4 ~ 3MPa, but is sometimes not limited to this.According to the present invention, polymeric reaction temperature is generally-40 DEG C ~ 200 DEG C, preferably 10 DEG C ~ 100 DEG C, more preferably 40 DEG C ~ 95 DEG C, but is sometimes not limited to this.
In addition, according to the present invention, described alkene homopolymerization/copolymerization method can be carried out having under hydrogen existent condition, also can not have to carry out under hydrogen existent condition.In case of presence, the dividing potential drop of hydrogen can be 0.01% ~ 99% of described polymerization pressure, preferably 0.01% ~ 50%, but be sometimes not limited to this.
According to the present invention, when carrying out described alkene homopolymerization/copolymerization method, in the described promotor of aluminium or boron be generally 1 ~ 1000:1 in the mol ratio of the described load type non-metallocene catalyst of described central metal atom, preferably 10 ~ 500:1, more preferably 15 ~ 300:1, but be sometimes not limited to this.
Embodiment
Below adopt embodiment in further detail the present invention to be described, but the present invention is not limited to these embodiments.
(unit is g/cm to polymer stacks density
3) mensuration carry out with reference to CNS GB 1636-79.
In load type non-metallocene catalyst, the content of IV B race metal (such as Ti) and Mg element adopts ICP-AES method to measure, and the content of Nonmetallocene part or title complex adopts analyses.
The polymerization activity of catalyzer calculates in accordance with the following methods: after polyreaction terminates, polymerisate in reactor is filtered and drying, then weigh the quality of this polymerisate, represent the polymerization activity (unit is kg polymkeric substance/g catalyzer or kg polymkeric substance/gCat) of this catalyzer with this polymerisate quality divided by the ratio of the quality of load type non-metallocene catalyst used.
Molecular weight Mw, Mn of polymkeric substance and molecular weight distribution (Mw/Mn) adopt the GPC V2000 type gel chromatography analyser of WATERS company of the U.S. to measure, and with 1,2,4-trichlorobenzene for solvent, temperature during mensuration is 150 DEG C.
The viscosity-average molecular weight of polymkeric substance calculates in accordance with the following methods: according to standard A STM D4020-00, (capillary inner diameter is 0.44mm to adopt high temperature dilution type Ubbelohde viscometer method, thermostatic bath medium is No. 300 silicone oil, dilution solvent is perhydronaphthalene, measuring temperature is 135 DEG C) measure the limiting viscosity of described polymkeric substance, then according to the viscosity-average molecular weight Mv of polymkeric substance described in following formulae discovery.
Wherein, η is limiting viscosity.
Embodiment 1
Magnesium compound adopts Magnesium Chloride Anhydrous, solvent employing tetrahydrofuran (THF), and alcohol adopts propyl carbinol, and silicon compound adopts tetraethoxy-silicane, and the chemical processing agent of IVB race metallic compound adopts titanium tetrachloride, and precipitation agent adopts hexane, and Nonmetallocene part employing structure is
compound.
Take 5g Magnesium Chloride Anhydrous, dissolve completely under normal temperature after adding solvent, Nonmetallocene part and alcohol, obtain magnesium compound solution, add precipitation agent to magnesium compound solution to make it to precipitate completely, filter, adopt precipitation agent to wash 3 times, each precipitation agent consumption is 60ml, vacuumizes drying and obtain magnesium compound carrier at being uniformly heated to 60 DEG C.
Obtained magnesium compound carrier is joined in hexane solvent, normal temperature drips silicon compound and is added dropwise to IVB race chemical processing agent in 30 minutes in lower 10 minutes, then 60 DEG C of isothermal reactions are uniformly heated to after 2 hours, filter, hexane solvent washs 3 times, each consumption is identical with the quantity of solvent added before, finally at 60 DEG C, vacuumizes drying, obtains load type non-metallocene catalyst.
Wherein proportioning is, magnesium compound and solvent burden ratio are 1mol:210ml; Magnesium compound and alcohol mol ratio are 1:0.5; The mol ratio of magnesium compound and Nonmetallocene part is 1:0.08; Precipitation agent and solvent volume proportioning are 1:1; In the magnesium compound carrier of Mg element with in the mol ratio of the silicon compound of Si element for 1:0.1; In the magnesium compound carrier of Mg element with the chemical processing agent mol ratio of IVB race elemental metal for 1:0.15.
Load type non-metallocene catalyst is designated as CAT-1.
Embodiment 2
Substantially the same manner as Example 1, but have following change:
Before magnesium compound carrier and described silicon compound contact with described chemical processing agent, first through helping chemical processing agent triethyl aluminum process magnesium compound carrier.
Namely, magnesium compound carrier is joined in hexane solvent, slowly drip again and help chemical processing agent triethyl aluminum (concentration is 0.88mol/L, hexane solution), stir at 60 DEG C after 2 hours and filter, hexanes wash 3 times, each consumption is identical with the quantity of solvent added before, finally at 60 DEG C, vacuumize drying, obtain pretreated magnesium compound carrier.Wherein in the magnesium compound carrier of Mg element with help the mol ratio of chemical processing agent for 1:0.2 in Al element.
Load type non-metallocene catalyst is designated as CAT-2.
Embodiment 3
Substantially the same manner as Example 1, but have following change:
Before magnesium compound carrier and described silicon compound contact with described chemical processing agent, first through helping chemical processing agent methylaluminoxane process magnesium compound carrier.
Namely, magnesium compound carrier is joined in toluene solvant, slowly drip again and help chemical processing agent methylaluminoxane (concentration is 10wt%, toluene solution), stir at 60 DEG C after 2 hours and filter, toluene wash 3 times, each consumption is identical with the quantity of solvent added before, finally at 100 DEG C, vacuumize drying, obtain pretreated magnesium compound carrier.Wherein in the magnesium compound carrier of Mg element with help the mol ratio of chemical processing agent for 1:0.4 in Al element.
Load type non-metallocene catalyst is designated as CAT-3.
Embodiment 4
Substantially the same manner as Example 1, but have following change:
Magnesium compound changes into magnesium ethide (Mg (C
2h
5)
2), alcohol adopts ethanol, and toluene changed into by solvent, and silicon compound changes tetraisobutoxy-silicane into, and the chemical processing agent of IVB race metallic compound changes into zirconium tetrachloride (ZrCl
4), precipitation agent changes hexanaphthene into, and Nonmetallocene part adopts
.
Wherein proportioning is, magnesium compound and solvent burden ratio are 1mol:150ml; Magnesium compound and alcohol mol ratio are 1:1.64; The mol ratio of magnesium compound and Nonmetallocene part is 1:0.04; Precipitation agent and solvent volume proportioning are 1:2; In the magnesium compound carrier of Mg element with in the mol ratio of the silicon compound of Si element for 1:0.05, in the magnesium compound carrier of Mg element with the chemical processing agent mol ratio of IVB race elemental metal for 1:0.20.
Load type non-metallocene catalyst is designated as CAT-4.
Embodiment 5
Substantially the same manner as Example 1, but have following change:
Magnesium compound changes into anhydrous magnesium bromide (MgBr
2), trichlorine methyl alcohol changed into by alcohol, and Nonmetallocene part adopts
, ethylbenzene changed into by solvent, and silicon compound changes triethoxy chloro silicon into, and the chemical processing agent of IVB race metallic compound changes into titanium tetrabromide (TiBr
4).
Precipitation agent is added and filtration washing drying step changes into and directly at 110 DEG C, vacuumizes drying and obtain magnesium compound carrier in magnesium compound solution.
Wherein proportioning is, magnesium compound and solvent burden ratio are 1mol:250ml; Magnesium compound and alcohol mol ratio are 1:1; The mol ratio of magnesium compound and Nonmetallocene part is 1:0.2; In the magnesium compound carrier of Mg element with in the mol ratio of the silicon compound of Si element for 1:0.25, in the magnesium compound carrier of Mg element with the chemical processing agent mol ratio of IVB race elemental metal for 1:0.30.
Load type non-metallocene catalyst is designated as CAT-5.
Embodiment 6
Substantially the same manner as Example 1, but have following change:
Magnesium compound changes into oxyethyl group magnesium chloride (MgCl (OC
2h
5)), 2-Ethylhexyl Alcohol changed into by alcohol, and Nonmetallocene part adopts
, dimethylbenzene changed into by solvent, and silicide changes silicon tetrachloride into, and the chemical processing agent of IVB race metallic compound changes into tetraethyl-titanium (Ti (CH
3cH
2)
4), decane changed into by precipitation agent.
Wherein proportioning is, magnesium compound and solvent burden ratio are 1mol:300ml; Magnesium compound and alcohol mol ratio are 1:0.25; The mol ratio of magnesium compound and Nonmetallocene part is 1:0.05; Precipitation agent and solvent volume proportioning are 1:1.5; In the magnesium compound carrier of Mg element with in the mol ratio of the silicon compound of Si element for 1:0.14, in the magnesium compound carrier of Mg element with the chemical processing agent mol ratio of IVB race elemental metal for 1:0.05.
Load type non-metallocene catalyst is designated as CAT-6.
Embodiment 7
Substantially the same manner as Example 1, but have following change:
Magnesium compound changes into magnesium ethylate (Mg (OC
2h
5)
2), phenylethyl alcohol changed into by alcohol, and Nonmetallocene part adopts
, diethylbenzene changed into by solvent, and silicon compound changes tetramethoxy-silicane into, and the chemical processing agent of IVB race metallic compound changes into tetra-n-butyl titanium (Ti (C
4h
9)
4), pentane changed into by precipitation agent.
Wherein proportioning is, magnesium compound and solvent burden ratio are 1mol:400ml; Magnesium compound and alcohol mol ratio are 1:2.5; The mol ratio of magnesium compound and Nonmetallocene part is 1:0.4; Precipitation agent and solvent volume proportioning are 1:0.5; In the magnesium compound carrier of Mg element with in the mol ratio of the silicon compound of Si element for 1:0.45, in the magnesium compound carrier of Mg element with the chemical processing agent mol ratio of IVB race elemental metal for 1:0.50.
Load type non-metallocene catalyst is designated as CAT-7.
Embodiment 8
Substantially the same manner as Example 1, but have following change:
Magnesium compound changes into methylmagnesium-chloride (Mg (CH
3) Cl), alcohol changes hexalin into, and Nonmetallocene part adopts
, it is the mixture of 1:1 that silicon compound to change into by tetraethoxy-silicane and silicon tetrachloride according to mol ratio, and chlorotoluene changed into by solvent.
Wherein proportioning is, magnesium compound and alcohol mol ratio are 1:3.0; The mol ratio of magnesium compound and Nonmetallocene part is 1:0.01; In the magnesium compound carrier of Mg element with in the mol ratio of the silicon compound of Si element for 1:0.02, in the magnesium compound carrier of Mg element with the chemical processing agent mol ratio of IVB race elemental metal for 1:0.10.
Load type non-metallocene catalyst is designated as CAT-8.
Comparative example A
Substantially the same manner as Example 1, but have following change:
In load type non-metallocene catalyst preparation process, magnesium compound carrier is without silicon compound process, but is directly added dropwise to IVB race chemical processing agent and processes;
Catalyzer is designated as CAT-A.
Comparative example B
Substantially the same manner as Example 1, but have following change:
In the magnesium compound carrier of Mg element with in the mol ratio of the silicon compound of Si element for 1:0.05.
Catalyzer is designated as CAT-B.
Comparative example C
Substantially the same manner as Example 1, but have following change:
In the magnesium compound carrier of Mg element with in the mol ratio of the silicon compound of Si element for 1:0.20.
Catalyzer is designated as CAT-C.
Comparative example D
Substantially the same manner as Example 1, but have following change:
Nonmetallocene part is not added in magnesium compound solution preparation process;
Catalyzer is designated as CAT-D.
Application Example
Load type non-metallocene catalyst CAT-1 ~ 8 obtained in the embodiment of the present invention, CAT-A ~ D are carried out respectively under the following conditions in accordance with the following methods homopolymerization and the copolymerization of ethene:
Homopolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, polymerization temperature 85 DEG C, hydrogen partial pressure 0.2MPa, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 20mg load type non-metallocene catalyst and catalyst mixture, then add hydrogen to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction terminates, by gas reactor emptying, release still interpolymer, after drying, weigh quality.Particular case and the polymerization evaluation result of this polyreaction are as shown in table 1.
Copolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, polymerization temperature 85 DEG C, hydrogen partial pressure 0.2MPa, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 20mg load type non-metallocene catalyst and catalyst mixture, disposablely add hexene-1 comonomer 50g, add hydrogen again to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction terminates, by gas reactor emptying, release still interpolymer, after drying, weigh quality.Particular case and the polymerization evaluation result of this polyreaction are as shown in table 1.
The homopolymerization that no hydrogen participates in preparing ultrahigh molecular weight polyethylene(UHMWPE) is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.5MPa, polymerization temperature 70 DEG C, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 20mg load type non-metallocene catalyst and catalyst mixture, continue to pass into ethene after being warmed up to 60 DEG C and make polymerization stagnation pressure constant in 0.5MPa.After reaction terminates, by gas reactor emptying, release still interpolymer, after drying, weigh quality.Particular case and the polymerization evaluation result of this polyreaction are as shown in table 2.
Table 1. load type non-metallocene catalyst is used for olefinic polyreaction effect table look-up
。
Table 2. load type non-metallocene catalyst is for the preparation of ultrahigh molecular weight polyethylene(UHMWPE) polyreaction effect table look-up
。
From table 1, it is narrower that the load type non-metallocene catalyst prepared by method provided by the invention is polymerized the molecular weight distribution obtained, those skilled in the art know, general employing Ziegler-Natta catalyst is polymerized the molecular weight of polyethylene distribution obtained and is greater than 5.
By sequence number in table 12 and 3,5 and 7,8 and 10, and the test-results data of sequence number 3 and 4 are known in table 2, increase the consumption of promotor, namely improve promotor and catalyst activity metal molar than time, impact that is active on polymerization catalyst and polymer stacks density is not remarkable.It can be said that bright, the load type non-metallocene catalyst adopting method provided by the invention to prepare only needs fewer promotor consumption just can obtain high olefin polymerizating activity; And the polymkeric substance such as obtained polyethylene has excellent polymer morphology and high polymer bulk density thus.
In contrast table 1, the test-results data of sequence number 1 and 2,5 and 6,8 and 9 are known, after copolymerization, catalyst activity has increase by a relatively large margin, thus illustrates that the load type non-metallocene catalyst adopting method provided by the invention to prepare has comparatively significant comonomer effect.
By sequence number 1 in contrast table 1 and comparative example sequence number 16, and sequence number 1 is known with contrast sequence number 6 test-results data in table 2, silicon compound is not added in catalyst preparation process, although active metallic content obtains increase in catalyzer, but polymerization catalyst polymer stacks density that is active and that obtain thus all reduces, molecular weight distribution broadens, and the ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight of preparation obtains and significantly reduces.
By sequence number 1 in contrast table 1 and comparative example sequence number 17 and 18, and the test-results data of sequence number 1 and contrast sequence number 7 and 8 are known in table 2, along with the increase of silicon compound add-on in catalyst preparation process, in catalyzer, active metallic content obtains effective reduction, simultaneously the polymerization activity of catalyzer and the polymer stacks density that obtains thus increase all to some extent, molecular weight distribution narrows, prepared ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight increases, illustrate that the present invention introduces silicon compound and has active metallic content invalid in effective reduction catalyzer thus, improve catalyst activity and polymer stacks density simultaneously, narrow molecular weight distribution, and improve the effect of ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight.
By sequence number 1 in contrast table 1 and comparative example sequence number 19, and the test-results data of sequence number 1 and contrast sequence number 9 are known in table 2, Nonmetallocene part is not introduced in catalyst preparation process, the catalyzer obtained thus belongs to Ziegler-Natta type dynamics model catalyzer, polymerization activity and polymer stacks density lower, molecular weight distribution is wider, and prepared ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight is also lower.
Although be described in detail the specific embodiment of the present invention above in conjunction with the embodiments, it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.Those skilled in the art can carry out suitable change to these embodiments in the scope not departing from technological thought of the present invention and purport, and the embodiment after these changes is obviously also included within protection scope of the present invention.
Claims (10)
1. a preparation method for load type non-metallocene catalyst, comprises the following steps:
Magnesium compound and Nonmetallocene part are dissolved in solvent in the presence of an alcohol, obtain the step of magnesium compound solution;
In described magnesium compound solution, add precipitation agent or dry described magnesium compound solution, obtain the step of magnesium compound carrier;
Described magnesium compound carrier is contacted with the chemical processing agent being selected from IV B race metallic compound with the silicon compound of following formula (X), obtains the step of described load type non-metallocene catalyst,
Si (OR)
mx
4-mformula (X)
Wherein, each R is identical or different, is selected from C independently of one another
1-8straight or branched alkyl, is preferably selected from C independently of one another
1-4straight or branched alkyl, is preferably ethyl; M is the integer of 0,1,2,3 or 4; Each X is identical or different, is selected from halogen independently of one another, preferred chlorine,
Described preparation method is optionally also included in and makes before described magnesium compound carrier and described silicon compound contact with described chemical processing agent, by the step helping magnesium compound carrier described in chemical processing agent pre-treatment being selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.
2. according to preparation method according to claim 1, it is characterized in that, described magnesium compound be selected from magnesium halide, Alkoxymagnesium halides, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium one or more, be preferably selected from magnesium halide one or more, more preferably magnesium chloride.
3. according to preparation method according to claim 1, it is characterized in that, described solvent is selected from C
6-12aromatic hydrocarbon, halo C
6-12one or more in aromatic hydrocarbon, ester and ether, preferred C
6-12one or more in aromatic hydrocarbon and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF), described alcohol be selected from fatty alcohol, aromatic alcohol and alicyclic ring alcohol one or more, wherein said alcohol is optionally selected from halogen atom or C
1-6the substituting group of alkoxyl group replaces, described alcohol be preferably selected from fatty alcohol one or more, be more preferably selected from ethanol and butanols one or more.
4., according to preparation method according to claim 1, it is characterized in that, described Nonmetallocene part be selected from the compound with following chemical structural formula one or more:
，
Be preferably selected from the compound (A) and compound (B) with following chemical structural formula one or more:
with
,
（A） （B）
More preferably the compound (A-1) with following chemical structural formula is selected to compound (A-4) and compound (B-1) to one or more in compound (B-4):
、
、
（A-1） （A-2）
、
、
（A-3） （A-4）
、
、
（B-1） （B-2）
with
,
（B-3） （B-4）
In chemical structural formulas all above,
Q is 0 or 1;
D is 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
,-NR
23r
24,-N (O) R
25r
26,
,-PR
28r
29,-P (O) R
30oR
31, sulfuryl, sulfoxide group or-Se (O) R
39, wherein N, O, S, Se and P are coordination atom separately;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C
1-C
30alkyl;
D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C
1-C
30alkyl, sulfuryl, sulfoxide group,
,-N (O) R
25r
26,
or-P (O) R
32(OR
33), wherein N, O, S, Se and P are coordination atom separately;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and P are coordination atom separately;
F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;
G is selected from C
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group;
Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and P are coordination atom separately;
represent singly-bound or double bond;
-represent covalent linkage or ionic linkage;
R
1to R
4, R
6to R
36, R
38and R
39be selected from hydrogen, C independently of one another
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, is preferably formed aromatic ring;
Described safing function groups be selected from halogens, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, containing tin group, C
1-C
10ester group and nitro;
R
5be selected from lone-pair electron on nitrogen, hydrogen, C
1-C
30the C of alkyl, replacement
1-C
30alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups; Work as R
5for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups time, R
5in N, O, S, P and Se can carry out coordination as coordination atom and described center IV B race atoms metal;
The C of described replacement
1-C
30alkyl is selected from one or more halogen or C
1-C
30the C of alkyl alternatively base
1-C
30alkyl,
Described Nonmetallocene part be preferably selected from the compound with following chemical structural formula further one or more:
,
,
,
,
with
,
Described Nonmetallocene part be most preferably selected from the compound with following chemical structural formula one or more:
with
.
5., according to preparation method according to claim 4, it is characterized in that,
Described halogen is selected from F, Cl, Br or I;
Described nitrogen-containing group is selected from
,-NR
23r
24,-T-NR
23r
24or-N (O) R
25r
26;
Described phosphorus-containing groups is selected from
,-PR
28r
29 -,-P (O) R
30r
31or-P (O) R
32(OR
33);
Described oxy radical is selected from hydroxyl ,-OR
34with-T-OR
34;
Described sulfur-containing group is selected from-SR
35,-T-SR
35,-S (O) R
36or-T-SO
2r
37;
The described seleno group that contains is selected from-SeR
38,-T-SeR
38,-Se (O) R
39or-T-Se (O) R
39;
Described group T is selected from C
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group;
Described R
37be selected from hydrogen, C
1-C
30the C of alkyl, replacement
1-C
30alkyl or safing function group;
Described C
1-C
30alkyl is selected from C
1-C
30alkyl, C
7-C
50alkaryl, C
7-C
50aralkyl, C
3-C
30cyclic alkyl, C
2-C
30thiazolinyl, C
2-C
30alkynyl, C
6-C
30aryl, C
8-C
30condensed ring radical or C
4-C
30heterocyclic radical, wherein said heterocyclic radical contains the heteroatoms that 1-3 is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;
Described silicon-containing group is selected from-SiR
42r
43r
44or-T-SiR
45;
Described germanic group is selected from-GeR
46r
47r
48or-T-GeR
49;
The described tin group that contains is selected from-SnR
50r
51r
52,-T-SnR
53or-T-Sn (O) R
54;
Described R
42to R
54be selected from hydrogen, aforementioned C independently of one another
1-C
30the C of alkyl, aforementioned replacement
1-C
30alkyl or aforementioned safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and
Described group T ditto defines.
6. according to preparation method according to claim 1, it is characterized in that, in the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part for 1:0.0001-1, preferred 1:0.0002-0.4, more preferably 1:0.0008-0.2, preferred 1:0.001-0.1 further, the ratio of described magnesium compound and described solvent is 1mol:75 ~ 400ml, preferred 1mol:150 ~ 300ml, more preferably 1mol:200 ~ 250ml, in the mol ratio of the described magnesium compound of Mg element and described alcohol for 1:0.02 ~ 4.00, preferred 1:0.05 ~ 3.00, more preferably 1:0.10 ~ 2.50, the volume ratio of described precipitation agent and described solvent is 1:0.2 ~ 5, preferred 1:0.5 ~ 2, more preferably 1:0.8 ~ 1.5, in the described magnesium compound carrier of Mg element with in the mol ratio of the described silicon compound of Si element for 1:0.01-1, preferred 1:0.01-0.50, more preferably 1:0.05-0.25, in the described magnesium compound carrier of Mg element with the mol ratio of the described chemical processing agent of IVB race elemental metal for 1:0.01-1, preferred 1:0.01-0.50, more preferably 1:0.10-0.30, and in the described magnesium compound carrier of Mg element and to help the mol ratio of chemical processing agent for 1:0-1.0 described in Al element, preferred 1:0-0.5, more preferably 1:0.1-0.5.
7. according to preparation method according to claim 1, it is characterized in that, described precipitation agent is selected from alkane, naphthenic hydrocarbon, one or more in halogenated alkane and halo naphthenic hydrocarbon, be preferably selected from pentane, hexane, heptane, octane, nonane, decane, hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane, methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane, three n-butyl bromide, chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, one or more in bromo cyclononane and bromo cyclodecane, be preferably selected from hexane further, heptane, one or more in decane and hexanaphthene, most preferably hexane.
8. according to preparation method according to claim 1, it is characterized in that, described IV B race metallic compound be selected from IV B race metal halide, IV B race metal alkyl compound, IV B race metal alkoxide, IV B race metal alkyl halides and IV B race metal alkoxide halogenide one or more, be preferably selected from IV B race metal halide one or more, be more preferably selected from TiCl
4, TiBr
4, ZrCl
4, ZrBr
4, HfCl
4and HfBr
4in one or more, be most preferably selected from TiCl
4and ZrCl
4in one or more, described aikyiaiurnirsoxan beta is selected from methylaluminoxane, ethylaluminoxane, one or more in isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, more preferably be selected from methylaluminoxane and isobutyl aluminium alkoxide one or more, and described aluminum alkyls is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, triisopentyl aluminium, three n-pentyl aluminium, three hexyl aluminium, three isohexyl aluminium, one or more in diethylmethyl aluminium and dimethyl ethyl aluminium, be preferably selected from trimethyl aluminium, triethyl aluminum, one or more in tri-propyl aluminum and triisobutyl aluminium, most preferably be selected from triethyl aluminum and triisobutyl aluminium one or more.
9. a load type non-metallocene catalyst, it manufactures by according to the preparation method described in any one of claim 1-8.
10. an alkene homopolymerization/copolymerization method, it is characterized in that, with according to load type non-metallocene catalyst according to claim 9 for Primary Catalysts, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt for promotor, make alkene homopolymerization or copolymerization.
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| US7718566B2 (en) * | 2004-02-17 | 2010-05-18 | Univation Technologies, Llc | Olefin polymerization catalysts |
| CN102059144A (en) * | 2009-11-13 | 2011-05-18 | 中国石油化工股份有限公司 | Loaded non-metallocene catalyst and preparation method and application thereof |
| CN102059149A (en) * | 2009-11-13 | 2011-05-18 | 中国石油化工股份有限公司 | Loaded non-metallocene catalyst and preparation method and application thereof |
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| CN1057467A (en) * | 1990-06-22 | 1992-01-01 | 蒙特代普公司 | The method for preparing ethene (being total to) polymerization solid catalyst component |
| US7718566B2 (en) * | 2004-02-17 | 2010-05-18 | Univation Technologies, Llc | Olefin polymerization catalysts |
| CN1962702A (en) * | 2005-11-10 | 2007-05-16 | 扬子石油化工股份有限公司 | Carry type non-metallocene calalyst for polymerization of olefine, its preparation method and uses |
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