CN105017455B - A kind of ethylene-alpha-olefin copolymer, its manufacture method and its application - Google Patents
A kind of ethylene-alpha-olefin copolymer, its manufacture method and its application Download PDFInfo
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- CN105017455B CN105017455B CN201410149399.XA CN201410149399A CN105017455B CN 105017455 B CN105017455 B CN 105017455B CN 201410149399 A CN201410149399 A CN 201410149399A CN 105017455 B CN105017455 B CN 105017455B
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Abstract
The present invention relates to a kind of ethylene-alpha-olefin copolymer, its manufacture method and its application in moulded products manufacture.The ethylene-alpha-olefin copolymer shows the processing characteristics and mechanical property of balancing good compared with prior art.
Description
Technical field
The present invention relates to a kind of ethylene copolymer.Specifically, the present invention relates to a kind of ethene-alpha-olefin copolymer, its
Manufacture method and its application in moulded products manufacture.
Background technology
Polyolefin is the synthetic resin of yield maximum in the world, with boundless application market.Polyolefin is mainly wrapped
Include polyethylene(PE), polypropylene(PP)And the copolymer of the alpha-olefin such as ethene and propylene, 1- butylene, 1- hexenes and 1- octenes.
In general, the intensity of polyolefin such as polyethylene depends on its molecular weight, and molecular weight is higher, the intensity of material,
Elasticity and environmental stress cracking resistance are higher, but the processing characteristics of the higher polyethylene of molecular weight can be deteriorated.Known to this
It is to improve the molecular weight distribution of polymer to realize the balance of polymer rigid, toughness and processing characteristics three, i.e., in molecule
The relatively low component of the molecular weight for increasing to improve processing characteristics in higher polyvinyl resin is measured, so that the molecular weight of polyethylene
Bimodal distribution is presented.Double peak weight distributing polyethylene refer to molecular weight distribution in bimodal pattern linear polyethylene and ethene-α-
The blend of olefin copolymer, including low molecule amount, lightly branched part and HMW, highly -branched degree two parts.Bimodal poly- second
High molecular weight moieties can assign its good intensity, toughness and environmental stress cracking resistance in alkene(ESCR), and low molecule amount
Part can ensure the rigidity of polymer, while there is provided lubrication to improve the processing characteristics of resin.Due to bimodal polyethylene
The processing characteristics and performance of material has been reached good balance, have become the weight of polyolefin synthetic resin high performance
Want direction.Double-peak high-density polytene, makes the more difficult film of original production and processing and tubing have the development advanced by leaps and bounds, film
Become easy processing, tensile strength is improved;Tubing also has breakthrough in processing characteristics and environmental stress cracking resistance.
Chinese patent 200810213620.8 discloses a kind of ethene-alpha-olefin copolymer.Because molecular weight distribution is narrow,
The ethene-alpha-olefin copolymer is only used for manufacturing polyethylene crosslinking product, and is not suitable for manufacture rotomoulded articles and high-performance pipe
Material.Moreover, in the manufacture method of the ethene-alpha-olefin copolymer disclosed in the Chinese patent, the catalysis of polymerization catalyst is lived
Property can not be fully played, and copolymerization effect also has the leeway further improved.
Chinese patent 200810213619.5 discloses a kind of ultra-high molecular weight polyethylene.Because molecular weight is higher, this surpasses
The processing characteristics of High molecular weight polyethylene is poor, can be only applied to the high abrasion goods such as extruding pipe material under sintering process molding and low speed,
Application is smaller.
Therefore, current present situation is to be still required for a kind of ethene-alpha-olefin copolymer, and it has appropriate molecular weight point
The characteristic such as cloth and oligomer, and take into account processing characteristics and mechanical property.Prior art is also required to a kind of ethene-alpha-olefin and is total to
The manufacture method of polymers, it enables to the catalytic activity of polymerization catalyst more to be fully played, and copolymerization effect
It is more notable.
The content of the invention
The present inventor has found by diligent research on the basis of existing technology, by using a kind of specific manufacturer
Method manufactures the ethene-alpha-olefin copolymer, it is possible to solves foregoing problems, and this completes the present invention.
Specifically, the present invention relates to the content of following aspect.
1. a kind of ethene-alpha-olefin copolymer, it is characterised in that the monomeric unit with derived from ethylene is with being derived from
Selected from C3-C12 alpha-olefins(It is preferred that C4-C8 alpha-olefins)At least one alpha-olefin monomeric unit, its heap density be 0.33 ~
0.50g/cm3(It is preferred that 0.35 ~ 0.50g/cm3, more preferably 0.38 ~ 0.45g/cm3), oligomer is less than 2g/L, micro- less than 75
It is 0.02 ~ 20g/10min that the fine powder content of rice, which is less than the melt index determined under the conditions of 3 weight %, 190 DEG C and 2.16 kilograms, is divided
Son amount distribution Mw/Mn is 5 ~ 40, and density is 0.935-0.960g/cm3, average grain diameter is 200-1000 microns, and relative to
The weight % of gross weight 100 of the ethene-alpha-olefin copolymer, the content of the monomeric unit of the derived from ethylene for 88 ~
99.8 weight %, the content of the monomeric unit derived from the alpha-olefin is 0.2 ~ 12 weight %.
2. a kind of manufacture method of ethene-alpha-olefin copolymer, it is characterised in that comprise the following steps A and B or step
Rapid A' and B':
Step A:Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta,
At least one of alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt(It is preferred that in aikyiaiurnirsoxan beta and alkyl aluminum
At least one)As co-catalyst, make the co-catalyst in terms of aluminium or boron and the master in terms of central metal atom
The mol ratio of catalyst reaches 1~1000:1, preferably 5~500:1, more preferably 10~100:1, polymerisation stagnation pressure 0.2 ~
2.0MPa(It is preferred that 0.3 ~ 1.5MPa, most preferably 0.4-0.8MPa), hydrogen and ethylene partial pressure compare 0.01-1:1(It is preferred that 0.02-
0.8:1, most preferably 0.03-0.5:1)With 20 ~ 120 DEG C of polymeric reaction temperature(It is preferred that 60 ~ 100 DEG C, more preferably 75 ~ 95 DEG C)Bar
Under part, make ethylene homo, obtain A stage polymers, and
Step B:Using slurry polymerization process, in the presence of the A stage polymers, polymerisation stagnation pressure 0.1 ~
2.0MPa(It is preferred that 0.2 ~ 1.0MPa, most preferably 0.3-0.6MPa), hydrogen and ethylene partial pressure compare 0.01-0.5:1(It is preferred that 0.02-
0.4:1, most preferably 0.03-0.3:1), 20 ~ 120 DEG C of polymeric reaction temperature(It is preferred that 60 ~ 100 DEG C, more preferably 75 ~ 95 DEG C)With altogether
Polycondensation monomer addition is 0.01 ~ 0.3 gram/milligram major catalyst(It is preferred that 0.015 ~ 0.25 gram/milligram major catalyst, more preferably
0.02 ~ 0.2 gram/milligram major catalyst)Under conditions of, make ethene with being selected from C3-C12 alpha-olefins(It is preferred that C4-C8 alpha-olefins)
At least one alpha-olefin copolymer, obtain the ethene-alpha-olefin copolymer;
Or
Step A':Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from alumina
At least one of alkane, alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt(It is preferred that aikyiaiurnirsoxan beta and alkyl aluminum
At least one of)As co-catalyst, make the co-catalyst in terms of aluminium or boron with described in terms of central metal atom
The mol ratio of major catalyst reaches 1~1000:1, preferably 5~500:1, more preferably 10~100:1, polymerisation stagnation pressure 0.1 ~
2.0MPa(It is preferred that 0.2 ~ 1.0MPa, most preferably 0.3-0.6MPa), hydrogen and ethylene partial pressure compare 0.01-0.5:1(It is preferred that 0.02-
0.4:1, most preferably 0.03-0.3:1), 20 ~ 120 DEG C of polymeric reaction temperature(It is preferred that 60 ~ 100 DEG C, more preferably 75 ~ 95 DEG C)With altogether
Polycondensation monomer addition is 0.01 ~ 0.3 gram/milligram major catalyst(It is preferred that 0.015 ~ 0.25 gram/milligram major catalyst, more preferably
0.02 ~ 0.2 gram/milligram major catalyst)Under conditions of, make ethene with being selected from C3-C12 alpha-olefins(It is preferred that C4-C8 alpha-olefins)
At least one alpha-olefin copolymer, obtain A' stage polymers, and
Step B':Using slurry polymerization process, in the presence of the A' stage polymers, polymerisation stagnation pressure 0.2 ~
2.0MPa(It is preferred that 0.3 ~ 1.5MPa, most preferably 0.4-0.8MPa), hydrogen and ethylene partial pressure compare 0.01-1:1(It is preferred that 0.02-
0.8:1, most preferably 0.03-0.5:1)With 20 ~ 120 DEG C of polymeric reaction temperature(It is preferred that 60 ~ 100 DEG C, more preferably 75 ~ 95 DEG C)Bar
Make ethylene homo under part, obtain the ethene-alpha-olefin copolymer.
3. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the A stage polymers account for institute
State the 0.1-90wt% of ethene-alpha-olefin copolymer gross mass, more preferably preferably 15-85wt%, 30-70wt%, or the A' ranks
Section polymer accounts for the 10-99.9wt%, more preferably preferably 15-85wt%, 30- of the ethene-alpha-olefin copolymer gross mass
70wt%。
4. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the load type non-metallocene is urged
Agent is manufactured by the preparation method comprised the following steps:
Magnesium compound is set to be dissolved in the presence of an alcohol in the first solvent, the step of obtaining magnesium compound solution;
Porous carrier is set to be mixed with the magnesium compound solution, the step of obtaining the first mixed serum;
Precipitating reagent is added into first mixed serum or first mixed serum is dried, complex carrier is obtained
Step;
Make the complex carrier and following formula(X)Silicon compound and chemical treatments selected from IV B races metallic compound connect
Touch, the step of obtaining modification complex carrier,
Si(OR)mX4-mFormula(X)
Wherein, each R is identical or different, is each independently selected from C1-8Straight or branched alkyl, is preferably selected independently of one another
From C1-4Straight or branched alkyl, is preferably all ethyl;M is 0,1,2,3 or 4 integer;Each X is identical or different, each independent
Ground is selected from halogen, preferably chlorine;
Nonmetallocene complex is contacted with the modification complex carrier in the presence of the second solvent, obtain the load
The step of type non-metallocene catalyst,
The preparation method, which is optionally additionally included in, makes the complex carrier and the silicon compound and the chemical treatments
Before contact, with selected from aikyiaiurnirsoxan beta, alkyl aluminum or its step for helping chemical treatments to pre-process the complex carrier being combined
Suddenly.
5. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the porous carrier is selected from alkene
Homopolymer or copolymer, polyvinyl alcohol or its copolymer, cyclodextrin, polyester or copolyesters, polyamide or copolyamide, vinyl chloride
Homopolymer or copolymer, Voncoat R 3310 or copolymer, methacrylate homopolymer or copolymer, styrene homopolymers
Or copolymer, the partial cross-linked form of these homopolymers or copolymer, the A of the periodic table of elements II, III A, IV A or IV B races metal
Refractory oxides or one kind or many in infusibility composite oxides, clay, molecular sieve, mica, montmorillonite, bentonite and diatomite
Kind, it is preferably selected from partial cross-linked styrene polymer, silica, aluminum oxide, magnesia, oxidation sial, oxidation magnalium, two
One or more in titanium oxide, molecular sieve and montmorillonite, are more preferably selected from silica, wherein the porous carrier is optionally passed through
Cross thermal activation treatment and/or handled by the chemical activation of the IV B races metallic compound, the magnesium compound is selected from halogenation
One or more in magnesium, Alkoxymagnesium halides, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium, are preferably selected
From the one or more in magnesium halide, more preferably magnesium chloride.
6. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein first solvent is selected from C6-12
Aromatic hydrocarbon, halo C6-12One or more in aromatic hydrocarbon, ester and ether, preferably C6-12One kind in aromatic hydrocarbon and tetrahydrofuran or
A variety of, most preferably tetrahydrofuran, second solvent is selected from C6-12Aromatic hydrocarbon, halo C6-12Aromatic hydrocarbon, halo C1-10Alkane and ether
In one or more, preferably C6-12One or more in aromatic hydrocarbon, dichloromethane and tetrahydrofuran, most preferably dichloromethane
Alkane, and one or more of the alcohol in fatty alcohol, aromatic alcohol and alicyclic ring alcohol, wherein the alcohol is optionally selected from halogen atom
Or C1-6The substituent substitution of alkoxy, the alcohol is preferably selected from the one or more in fatty alcohol, is more preferably selected from ethanol and fourth
One or more in alcohol.
7. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the Nonmetallocene complex is selected
One or more from the compound with following chemical structural formula:
,
It is preferably selected from the compound with following chemical structural formula(A)And compound(B)In one or more:
With,
(A) (B)
It is more preferably selected from the compound with following chemical structural formula(A-1)To compound(A-4)And compound(B-1)Extremely
Compound(B-4)In one or more:
、、
(A-1)(A-2)
、、
(A-3)(A-4)
、、
(B-1)(B-2)
With,
(B-3)(B-4)
In above all of chemical structural formula,
Q is 0 or 1;
D is 0 or 1;
M is 1,2 or 3;
M is the central metal atom selected from periodic table of elements III-th family to XI races metallic atom, preferably the IVth B races gold
Belong to atom, more preferably Ti (IV) and Zr (IV);
N is 1,2,3 or 4, depending on the valence state of the central metal atom M;
X is selected from halogen, hydrogen atom, C1- C30Alkyl, the C of substitution1- C30Alkyl, oxy radical, nitrogen-containing group, containing sulfenyl
Group, boron-containing group, group containing aluminium base, phosphorus-containing groups, silicon-containing group, germanic group or containing tin group, multiple X can also may be used with identical
, can also bonding or cyclization each other with difference;
A be selected from oxygen atom, sulphur atom, selenium atom,、-NR23R24、-N(O)R25R26、、-PR28R29、-P(O)
R30OR31, sulfuryl, sulfoxide group or-Se (O) R39, wherein N, O, S, Se and P be respectively coordination atom;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C1- C30Alkyl;
D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C1- C30Alkyl,
Sulfuryl or sulfoxide group, wherein N, O, S, Se and P are respectively coordination atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group, wherein N, O, S, Se
Coordination atom is respectively with P;
F be 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 respectively coordination atom;
G is selected from C1- C30Alkyl, the C of substitution1- C30Alkyl or safing function group;
Y be selected from oxygen atom, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S,
Se and P are respectively coordination atom;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group, wherein N, O, S, Se
Coordination atom is respectively with P;
Represent singly-bound or double bond;
- represent covalent bond or ionic bond;
Represent coordinate bond, covalent bond or ionic bond;
R1To R4、R6To R21It is each independently selected from hydrogen, C1- C30Alkyl, the C of substitution1- C30Alkyl or safing function
Group, R22To R36、R38And R39It is each independently selected from hydrogen, C1- C30Alkyl or substituted C1- C30Alkyl, above-mentioned group is each other
Between can be the same or different, wherein adjacent group can combine togather bonding or cyclization, be preferably formed as aromatic series
Ring;
The safing function group be selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, containing sulfenyl
Roll into a ball, containing tin group, C1- C10Ester group or nitro,
R5Lone pair electrons, hydrogen, C on nitrogen1- C30Alkyl, the C of substitution1- C30Alkyl, oxy radical, sulfur-containing group,
Nitrogen-containing group, containing seleno group or phosphorus-containing groups;Work as R5For oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorous-containigroups groups
During group, R5In N, O, S, P and Se can be used as coordination atom;
The substituted C1- C30Alkyl, which is selected from, carries one or more halogens or C1- C30Alkyl is used as substituent
C1- C30Alkyl;
The Nonmetallocene complex further preferably one kind in the compound with following chemical structural formula or
It is a variety of:
、 、 、
、 With,
It is most preferably selected from the one or more in the compound with following chemical structural formula:
With。
8. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein
The halogen is selected from F, Cl, Br or I;
The nitrogen-containing group is selected from、-NR23R24、-T-NR23R24Or-N (O) R25R26;
The phosphorus-containing groups are selected from、-PR28R29、-P(O)R30R31Or-P (O) R32(OR33);
The oxy radical is selected from hydroxyl ,-OR34With-T-OR34;
The sulfur-containing group is selected from-SR35、-T-SR35、-S(O)R36Or-T-SO2R37;
The group containing seleno is selected from-SeR38、-T-SeR38、-Se(O)R39Or-T-Se (O) R39;
The group T is selected from C1- C30Alkyl or substituted C1- C30Alkyl;
The R37Selected from hydrogen, C1- C30Alkyl or substituted C1- C30Alkyl;
The C1- C30Alkyl is selected from C1- C30Alkyl, C7- C30Alkaryl, C7- C30Aralkyl, C3- C30Ring-type alkane
Base, C2- C30Alkenyl, C2- C30Alkynyl, C6- C30Aryl, C8- C30Condensed ring radical or C4- C30Heterocyclic radical, wherein the heterocycle
Base contains the 1-3 hetero atoms for being selected from nitrogen-atoms, oxygen atom or sulphur atom;
The boron-containing group is selected from BF4 -、(C6F5)4B-Or (R40BAr3)-;
The group containing aluminium base is selected from alkyl aluminum, AlPh4 -、AlF4 -、AlCl4 -、AlBr4 -、AlI4 -Or R41AlAr3 -;
The silicon-containing group is selected from-SiR42R43R44Or-T-SiR45;
The germanic group is selected from-GeR46R47R48Or-T-GeR49;
It is described to be selected from-SnR containing tin group50R51R52、-T-SnR53Or-T-Sn (O) R54;
The Ar represents C6- C30Aryl;
R40To R54It is each independently selected from hydrogen, foregoing C1- C30Alkyl or foregoing substituted C1- C30Alkyl, wherein these
Group can be the same or different to each other, and wherein adjacent group can combine togather bonding or cyclization, and
The group T is as previously defined.
9. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the magnesium compound and described the
The ratio of one solvent is 1mol:75~400ml, preferably 1mol:150~300ml, more preferably 1mol:200~250ml, with Mg members
The magnesium compound of element meter is 1 with the mol ratio of the alcohol:0.02~4.00, preferably 1:0.05~3.00, more preferably 1:
0.10~2.50, the magnesium compound and the mass ratio of the porous carrier counted using magnesium compound solid is 1:0.1-20, it is excellent
Select 1:The volume ratio of 0.5-10, the precipitating reagent and first solvent is 1:0.2~5, preferably 1:0.5~2, more preferably 1:
0.8~1.5, the mol ratio of the complex carrier counted using Mg elements and the silicon compound counted using Si elements is 1:0.01-
1, preferably 1:0.01-0.50, more preferably 1:0.05-0.25, the complex carrier in terms of Mg elements with Group IVB metallic element
The mol ratio of the chemical treatments of meter is 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.10-0.30, with Mg members
The complex carrier of element meter is 1 with the mol ratio of the Nonmetallocene complex:0.01-1, preferably 1:0.04-0.4, it is more excellent
Select 1:0.08-0.2, and mole of the complex carrier with helping chemical treatments described in terms of Al elements in terms of Mg elements
Than for 1:0-1.0, preferably 1:0-0.5, more preferably 1:0.1-0.5.
10. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the precipitating reagent be selected from alkane,
One or more in cycloalkane, halogenated alkane and halo cycloalkane, are preferably selected from pentane, hexane, heptane, octane, nonane, the last of the ten Heavenly stems
Alkane, hexamethylene, pentamethylene, cycloheptane, cyclodecane, cyclononane, dichloromethane, dichloro hexane, two chloroheptanes, chloroform, three
Chloroethanes, three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane, three NBBs, chloro ring
Pentane, chlorocyclohexane, chloro cycloheptane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromo ring
One or more in hexane, bromo cycloheptane, bromo cyclooctane, bromo cyclononane and bromo cyclodecane, further preferably choosing
One or more from hexane, heptane, decane and hexamethylene, most preferably hexane.
11. the manufacture method of the ethene-alpha-olefin copolymer of any preceding aspect, wherein the IV B races metallic compound
Selected from IV B races metal halide, IV B races metal alkyl compound, IV B races metal alkoxide, IV B races metal alkyl halogen
One or more in compound and IV B races metal alkoxide halide, are preferably selected from one kind or many in IV B races metal halide
Kind, it is more preferably selected from TiCl4、TiBr4、ZrCl4、ZrBr4、HfCl4And HfBr4In one or more, be most preferably selected from TiCl4
And ZrCl4In one or more, the aikyiaiurnirsoxan beta be selected from MAO, ethylaluminoxane, isobutyl aluminium alkoxide and positive fourth
One or more in base aikyiaiurnirsoxan beta, are more preferably selected from the one or more in MAO and isobutyl aluminium alkoxide, and institute
State alkyl aluminum and be selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminums, triisopentyl aluminium, three just
One or more in amyl group aluminium, three hexyl aluminium, three isohesyl aluminium, diethylmethyl aluminium and dimethyl ethyl aluminium, are preferably selected from
One or more in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, are most preferably selected from triethyl aluminum and three different
One or more in butyl aluminium.
12. a kind of polymer composition, the ethene-alpha-olefin copolymer comprising any preceding aspect or by foregoing
The ethene-alpha-olefin copolymer of the manufacture method manufacture of the ethene-alpha-olefin copolymer of either side, and antioxidant, optionally
Also include the one or more in halogen-absorber and pigment.
13. a kind of moulded products, are manufactured by the polymer composition and shaping of melt-processed any preceding aspect.
Technique effect
According to the ethene-alpha-olefin copolymer of the present invention, compared with prior art, uniform particle sizes, molecular weight distribution is appropriate,
Oligomer is low, and comonomer distribution is rationally and flexibly adjustable, thus shows the processing characteristics and mechanical property of balancing good
Can, it is very suitable for the moulded products such as manufacture high performance pipe, rotomoulded articles, injection-molded item and film.
According to the manufacture method of the ethene-alpha-olefin copolymer of the present invention, compared with prior art, polymerization catalyst is urged
Change activity more to be fully played, copolymerization effect is more notable, and technological parameter is flexibly adjustable, is conducive to producing knot
Structure parameter(Type, molecular weight and the molecular weight distribution of such as monomer and comonomer, the content of comonomer and its distribution etc.)
Comply with specific requirement or needs and the ethene-alpha-olefin copolymer of flexible customization of moulded products.
By using the ethene-alpha-olefin copolymer of the present invention, it is possible to produce have excellent mechanical property concurrently and excellent
Processing characteristics polymer composition, and the moulded products manufactured using the polymer composition show be used for a long time property
Can excellent and anti-cracking performance it is excellent the features such as.
According to the present invention, pass through two sections of polymerizations(Homopolymerization section+copolymerization section)Mode obtain the ethene-alpha-olefin copolymerization
Thing, wherein homopolymerization section are conducive to improving processing characteristics, and copolymerization Duan Ze is conducive to improving mechanical property.Therefore, it is equal by regulation
The relative scale of poly- section and copolymerization section, can neatly adjust the processing characteristics and mechanical property of product copolymer.Such as, if
Need higher processing characteristics, then can properly increase the ratio of homopolymerization section, and if necessary to higher mechanical property, then can be with
Properly increase the ratio of copolymerization section.
Embodiment
The embodiment to the present invention is described in detail below, it should be noted however that the protection of the present invention
Scope is not limited to these specific embodiments, but determined by claims of annex.
Or the implication is beyond those skilled in the art's in the context of the present invention, unless otherwise defined explicitly,
Understand hydrocarbon or hydrocarbon derivative group more than scope, 3 carbon atoms(Such as propyl group, propoxyl group, butyl, butane, butylene, butylene
Base, hexane etc.)Identical implication during with titled with prefix " just " is respectively provided with when not titled with prefix " just ".Such as, propyl group is typically managed
Solve as n-propyl, and butyl is generally understood as normal-butyl, unless otherwise clear and definite.
In this manual, in order to avoid statement is complicated, not for its clear and definite valency of each substituent or group of compound
Key-like condition be monovalence, divalence, trivalent or tetravalence etc., those skilled in the art can be according to these substituents or group(Than
As described in this specification or definition group G, D, B, A and F etc.)Location or institute on the structural formula of respective compound
The substitution situation of performance specifically judges, and for being selected in these substituents or group given a definition that from this specification
In the position or the definition for replacing the valence link situation of situation to be adapted to.
All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference.
Unless otherwise defined, all technologies and scientific terminology used in this specification all have containing for those skilled in the art's routine understanding
Justice.In case of conflict, the definition by this specification is defined.
When this specification with prefix " as well known to those skilled in the art ", " prior art " or its similar term exports material
When material, material, method, step, device or part etc., object derived from the prefix is covered this area when the application is proposed and routinely made
Those, but also include also being of little use at present, it will but become those art-recognized for suitable for similar purpose.
In the context of the present specification, in addition to the content clearly stated, any matters or item do not mentioned are equal
Directly be applicable it is known in the art those without carry out it is any change.Moreover, any embodiment described herein can be with
Freely combined with one or more other embodiments described herein, thus formed by technical scheme or technological thought regard
For original disclosure of the invention or a part for original description, and be not considered as not disclosing or be expected herein it is new in
Hold, unless those skilled in the art think that the combination is substantially irrational.
In the case where not clearly indicating, all percentages, number, ratio being previously mentioned in this specification etc. be all with
On the basis of weight, unless do not met the conventional understanding of those skilled in the art when on the basis of weight.
According to the present invention, it is related to a kind of ethene-alpha-olefin copolymer.The ethene-alpha-olefin copolymer is that have to derive
From the copolymer of the monomeric unit and the monomeric unit derived from least one alpha-olefin selected from C3-C12 alpha-olefins of ethene,
It is preferred that the monomeric unit with derived from ethylene and the monomer list derived from least one alpha-olefin selected from C4-C8 alpha-olefins
The copolymer of member.
According to the present invention, as the alpha-olefin, such as can enumerate propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- heptene,
1- octenes, 4-methyl-1-pentene, 1- laurylenes, 4- methyl isophthalic acids-hexene etc., preferably 1- butylene, 1- hexenes, 4- methyl-1-pentenes
Alkene, 1- octenes, more preferably 1- hexenes, 4-methyl-1-pentene, 1- octenes.These alpha-olefins can be used alone, or can be by it
In two or more be applied in combination with any required ratio.
It is total relative to the ethene-alpha-olefin copolymer in the ethene-alpha-olefin copolymer according to the present invention
The weight % of weight 100, the content of the monomeric unit derived from the alpha-olefin is generally 0.2 ~ 12 weight %, preferably 1.0 ~
10 weight %, more preferably 1.2 ~ 6 weight %.
According to the present invention, the heap density of the ethene-alpha-olefin copolymer is 0.33 ~ 0.50g/cm3, preferably 0.35 ~
0.50g/cm3, more preferably 0.38 ~ 0.45g/cm3.The measure reference standard GB 1636-79 of the heap density are carried out(Unit is g/
cm3).
According to the present invention, the oligomer of the ethene-alpha-olefin copolymer is less than 2g/L.Its method of testing is in mistake
Filter or the filtrate center line that centrifuges out takes out 1 liter of solvent, under the conditions of higher than solvent boiling point or closed vacuumize abundant drying
Remaining material gross mass after solvent.Its content height mainly determined by catalyst performance and polymeric reaction condition, while
It is relevant with polymer solvent and filtering or centrifugation temperature.
According to the present invention, the fine powder of the ethene-alpha-olefin copolymer(Less than 75 microns)Content is less than 3 weight %.It is described
Fine powder content uses sieve method, and the powder of the copolymer is passed through into 200 mesh(75 microns of aperture)Sieved through sieve, by fine powder after sieving
Quality divided by the gross mass of copolymer are measured.
According to the present invention, the melt index of the ethene-alpha-olefin copolymer(190 DEG C, 2.16 kilograms)For 0.02 ~ 20g/
10min.The measure reference standard GB T 3682-2000 of the melt index are carried out(Unit is g/10min).
According to the present invention, the molecular weight distribution mw/mn of the ethene-alpha-olefin copolymer is 5 ~ 40.The molecular weight point
Cloth Mw/Mn is measured using the GPC V2000 type gel chromatography analyzers of WATERS companies of the U.S., from 4 Agilent
PLgel Olexis type chromatographic columns, with 1,2,4- trichloro-benzenes for mobile phase, temperature during measure is 150 DEG C.
According to the present invention, the density of the ethene-alpha-olefin copolymer is 0.935-0.960g/cm3.The survey of the density
Determine reference standard GB/T 1033-86 progress(Unit is g/cm3).
According to the present invention, the average grain diameter of the ethene-alpha-olefin copolymer is 200-1000 microns.The average grain diameter
Analysis is carried out on Beckman Coulter LS230 type laser particle size analyzers, and its particle size determination scope is 0.04 ~ 2000 micro-
Rice.
According to the present invention, the ethene-alpha-olefin copolymer can be entered by comprising the following steps A and B manufacture method A
Row manufacture.
Specifically, the present invention relates to a kind of manufacture method A of ethene-alpha-olefin copolymer, it is characterised in that including with
Lower step:
Step A:Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta,
At least one of alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt are anti-in polymerization as co-catalyst
0.2 ~ 2.0MPa of stagnation pressure is answered, hydrogen and ethylene partial pressure compare 0.01-1:1st, ethene is made under conditions of 20 ~ 120 DEG C of polymeric reaction temperature
Homopolymerization, obtains A stage polymers.
According to the present invention, the step A polymerisation stagnation pressure is generally 0.2 ~ 2.0MPa, preferably 0.3 ~ 1.5MPa, most
It is preferred that 0.4-0.8MPa.
According to the present invention, the step A hydrogen and ethylene partial pressure ratio is generally 0.01-1:1, preferably 0.02-0.8:1,
Most preferably 0.03-0.5:1.
According to the present invention, the step A polymeric reaction temperature is generally 20 ~ 120 DEG C, preferably 60 ~ 100 DEG C, more preferably
75~95℃。
According to the present invention, the step A can be carried out according to conventionally known in the art any mode, not special
Limit.As its embodiment, such as it can enumerate and solvent for polymerization is added to slurry polymerization reactor(Such as gather
Close autoclave)In, then into the reactor add predetermined volume major catalyst and co-catalyst, add hydrogen to make a reservation for
Hydrogen partial pressure, being finally continually fed into ethene makes polymerisation stagnation pressure constant in predetermined value, while keeping predetermined polymerisation
Temperature carries out the homopolymerization of ethene, that is, obtains the A stage polymers.
Step B:Using slurry polymerization process, in the presence of the A stage polymers, polymerisation stagnation pressure 0.1 ~
2.0MPa, hydrogen and ethylene partial pressure compare 0.01-0.5:1st, 20 ~ 120 DEG C of polymeric reaction temperature and comonomer addition be 0.01 ~
Under conditions of 0.3 gram/milligram major catalyst, make ethene and at least one alpha-olefin selected from C3-C12 alpha-olefins(Referred to as copolymerization
Monomer)Copolymerization, obtains the ethene-alpha-olefin copolymer.
According to the present invention, the step B polymerisation stagnation pressure is generally 0.1 ~ 2.0MPa, preferably 0.2 ~ 1.0MPa, most
It is preferred that 0.3-0.6MPa.
According to the present invention, the step B hydrogen and ethylene partial pressure ratio is generally 0.01-0.5:1, preferably 0.02-0.4:
1, most preferably 0.03-0.3:1.
According to the present invention, the step B polymeric reaction temperature is generally 20 ~ 120 DEG C, preferably 60 ~ 100 DEG C, more preferably
75~95℃。
According to the present invention, the step B comonomer addition is generally 0.01 ~ 0.3 gram/milligram major catalyst, excellent
Select 0.015 ~ 0.25 gram/milligram major catalyst, more preferably 0.02 ~ 0.2 gram/milligram major catalyst.
As the non-limiting embodiment of the step B, such as it can enumerate after the step A terminates,
The polymerization reaction mixture that the step that do not discharge A is obtained(Contain the A stage polymers)In the case of i.e. to step A reactor
In it is disposable add the comonomer of predetermined volume in step B, then adjust and add hydrogen and divide to hydrogen predetermined step B
Pressure, finally adjusting and being continually fed into ethene makes the constant predetermined value in step B of polymerisation stagnation pressure, while keeping step B to make a reservation for
Polymeric reaction temperature carry out the copolymerization of ethene and the comonomer, that is, obtain the ethene-alpha-olefin copolymer of the present invention.
Or, reactor of the polymerization reaction mixture that step A is obtained from step A(Now it is referred to as first reactor)In go out
Material, is added to(Second)Slurry polymerization reactor(Such as polymerization autoclave)In, it is then disposable into the second reactor
The comonomer of predetermined volume in step B is added, hydrogen is added to hydrogen partial pressure predetermined step B, finally persistently leads to
Entering ethene makes the constant predetermined value in step B of polymerisation stagnation pressure, while keeping the predetermined polymeric reaction temperatures of step B to carry out
The copolymerization of ethene and the comonomer, that is, obtain the ethene-alpha-olefin copolymer of the present invention.
According to the present invention, according to actual needs, the homopolymerization of the step A is typically carried out 2 ~ 8 hours, and preferably 3 ~ 5 is small
When, the copolyreaction of the step B is typically carried out 0.2 ~ 4 hour, preferably 0.5 ~ 2 hour, but be not limited to this.In fact, two
The length of the respective polymerization reaction time of individual step can be according to used major catalyst(Coordinate the co-catalyst)At each
Charging situation of polymerization activity performance and each raw material in step etc. is accordingly adjusted, as long as making the A stage polymers account for institute
State the 0.1-90wt% of ethene-alpha-olefin copolymer gross mass(It is preferred that 15-85wt%, more preferably 30-70wt%).
It is apparent that these foregoing embodiments are exemplary, those skilled in the art can be using this
Any mode known to field carries out the step B, and is not limited to foregoing concrete regulation, as long as the A ranks can be sufficiently reserved
The activity of section polymer.In addition, the comonomer can also the step B progress during several times addition or
Continuous addition, or the A stage polymers can also be separated afterwards again from the polymerization reaction mixture that step A is obtained
It is preferred for step B, but not.
According to the present invention, the A stage polymers are due to containing the major catalyst and co-catalysis introduced by step A
Agent, therefore show notable or effective olefin catalytic polymerization activity.In consideration of it, the step B is in the A stage polymers
In the presence of when carrying out, without extra addition major catalyst.
In general, additionally adding co-catalyst also without as step A in step B, although root sometimes
According to needing to supplement in right amount, to adjust the catalytic activity of the A stage polymers, but it is not required in that.
In general, also without extra addition solvent for polymerization in step B, although can also sometimes according to needs
Appropriate supplement, but be not required in that.
As needed, step B subsequent implementation for convenience, can be by well known in the art before step B is carried out
Method, removes the gas component of any presence from the polymerization reaction mixture that step A is obtained, and/or in step A
After end, by means commonly known in the art, the gas component of any presence is removed from the step A reactor.
, can be mixed from the reaction obtained according to method well known in the art after step B terminates according to the present invention
Desolvation etc. in compound and obtain powder, optionally further granulation and obtain pellet, be derived from solid-like(Particle or powder
Shape)Ethene-alpha-olefin copolymer.These technologies be to those skilled in the art it is obvious or known, herein no longer
Repeat.
According to the present invention, the ethene-alpha-olefin copolymer can also be by comprising the following steps A' and B' manufacturer
Method B is manufactured.
Specifically, the present invention relates to a kind of manufacture method B of ethene-alpha-olefin copolymer, it is characterised in that including with
Lower step:
Step A':Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from alumina
At least one of alkane, alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt are as co-catalyst, in polymerization
0.1 ~ 2.0MPa of reaction stagnation pressure, hydrogen and ethylene partial pressure compare 0.01-0.5:1st, 20 ~ 120 DEG C of polymeric reaction temperature and comonomer
Addition be 0.01 ~ 0.3 gram/milligram major catalyst under conditions of, make ethene with selected from C3-C12 alpha-olefins at least one α-
Alkene(Referred to as comonomer)Copolymerization, obtains A' stage polymers.
According to the present invention, the step A' polymerisation stagnation pressure is generally 0.1 ~ 2.0MPa, preferably 0.2 ~ 1.0MPa, most
It is preferred that 0.3-0.6MPa.
According to the present invention, the step A' hydrogen and ethylene partial pressure ratio is generally 0.01-0.5:1, preferably 0.02-0.4:
1, most preferably 0.03-0.3:1.
According to the present invention, the step A' polymeric reaction temperature is generally 20 ~ 120 DEG C, preferably 60 ~ 100 DEG C, more preferably
75~95℃。
According to the present invention, the step A' comonomer addition is generally 0.01 ~ 0.3 gram/milligram major catalyst, excellent
Select 0.015 ~ 0.25 gram/milligram major catalyst, more preferably 0.02 ~ 0.2 gram/milligram major catalyst.
According to the present invention, the step A' can be carried out according to conventionally known in the art any mode, not special
Restriction.As its embodiment, such as it can enumerate and solvent for polymerization is added to slurry polymerization reactor(Such as
Polymerization autoclave)In, the major catalyst and co-catalyst of predetermined volume are then added into the reactor, disposable add makes a reservation for
The comonomer of consumption, adds hydrogen to predetermined hydrogen partial pressure, being finally continually fed into ethene makes polymerisation stagnation pressure constant
In predetermined value, while keeping predetermined polymeric reaction temperature to carry out the copolyreaction of ethene and comonomer, that is, the A' is obtained
Stage polymer.
It is apparent that the embodiment is exemplary, those skilled in the art can use known in the art
Any mode carry out the step A', and be not limited to foregoing concrete regulation.Such as, the comonomer can also be in the step
Addition several times or continuous addition during rapid A' is carried out.
Step B':Using slurry polymerization process, in the presence of the A' stage polymers, polymerisation stagnation pressure 0.2 ~
2.0MPa, hydrogen and ethylene partial pressure compare 0.01-1:1st, ethylene homo is made under conditions of 20 ~ 120 DEG C of polymeric reaction temperature, so as to obtain
Obtain ethene-alpha-olefin copolymer of the invention.
According to the present invention, the step B' polymerisation stagnation pressure is generally 0.2 ~ 2.0MPa, preferably 0.3 ~ 1.5MPa, most
It is preferred that 0.4-0.8MPa.
According to the present invention, the step B' hydrogen and ethylene partial pressure ratio is generally 0.01-1:1, preferably 0.02-0.8:1,
Most preferably 0.03-0.5:1.
According to the present invention, the step B' polymeric reaction temperature is generally 20 ~ 120 DEG C, preferably 60 ~ 100 DEG C, more preferably
75~95℃。
As the non-limiting embodiment of the step B', such as it can enumerate after the step A' terminates,
The polymerization reaction mixture that the step that do not discharge A' is obtained(Contain the A' stage polymers)In the case of i.e. to step A' institute
State and hydrogen is added in reactor to hydrogen partial pressure predetermined step B', finally adjusting and being continually fed into ethene makes polymerisation stagnation pressure
The constant predetermined value in step B', while keeping the predetermined polymeric reaction temperatures of step B' to carry out the homopolymerization of ethene, that is, obtains this
The ethene-alpha-olefin copolymer of invention.Or, reactor of the polymerization reaction mixture that step A' is obtained from step A'
(Now it is referred to as first reactor)Middle discharging, is added to(Second)Slurry polymerization reactor(Such as polymerization autoclave)In, so
Hydrogen is added in the backward second reactor to hydrogen partial pressure predetermined step B', being finally continually fed into ethene makes polymerisation total
The constant predetermined value in step B' is pressed, while keeping the predetermined polymeric reaction temperatures of step B' to carry out the homopolymerization of ethene, that is, is obtained
Obtain ethene-alpha-olefin copolymer of the invention.
According to the present invention, according to actual needs, the copolyreaction of the step A' typically carries out 0.2 ~ 4 hour, preferably 0.5
~ 2 hours, the homopolymerization of the step B' was typically carried out 2 ~ 8 hours, preferably 3 ~ 5 hours, but be not limited to this.In fact, two
The length of the respective polymerization reaction time of individual step can be according to used major catalyst(Coordinate the co-catalyst)At each
Charging situation of polymerization activity performance and each raw material in step etc. is accordingly adjusted, as long as making the A' stage polymers account for institute
State the 10-99.9wt% of ethene-alpha-olefin copolymer gross mass(It is preferred that 15-85wt%, more preferably 30-70wt%).
It is apparent that these foregoing embodiments are exemplary, those skilled in the art can be using this
Any mode known to field carries out the step B', and is not limited to foregoing concrete regulation, as long as the A' can be sufficiently reserved
The activity of stage polymer.In addition, the A' stage polymers can also from step ' A obtain polymerization reaction mixture
In separate after be used further to step B', it is but not preferred.
According to the present invention, the A' stage polymers are due to containing the major catalyst and co-catalysis introduced by step A'
Agent, therefore show notable or effective olefin catalytic polymerization activity.In consideration of it, the step B' is in the A' stage polymers
In the presence of when carrying out, without extra addition major catalyst.
In general, additionally adding co-catalyst also without as step A' in step B', although sometimes
It can also in right amount supplement, to adjust the catalytic activity of the A' stage polymers, but be not required in that as needed.
In general, also without extra addition solvent for polymerization in step B', although also may be used sometimes according to needs
To supplement in right amount, but it is not required in that.
As needed, step B' subsequent implementation for convenience, can be by known in this field before step B' is carried out
Method, the gas component of any presence is removed from the polymerization reaction mixture that step A' is obtained, and/or in step
After rapid A' terminates, by means commonly known in the art, the gas group of any presence is removed from the step A' reactor
Point.
, can be mixed from the reaction obtained according to method well known in the art after step B' terminates according to the present invention
Desolvation etc. in compound and obtain powder, optionally further granulation and obtain pellet, be derived from solid-like(Particle or powder
Shape)Ethene-alpha-olefin copolymer.These technologies be to those skilled in the art it is obvious or known, herein no longer
Repeat.
According to the present invention, in foregoing manufacture method A and manufacture method B, the C3-C12 alpha-olefins more preferably C4-
C8 alpha-olefins.As alpha-olefin used herein, such as it can enumerate propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- heptene, 1-
Octene, 4-methyl-1-pentene, 1- laurylenes, 4- methyl isophthalic acids-hexene etc., preferably 1- butylene, 1- hexenes, 4-methyl-1-pentene,
1- octenes, more preferably 1- hexenes, 4-methyl-1-pentene, 1- octenes.These alpha-olefins can be used alone, or can be by them
In two or more be applied in combination.
According to the present invention, in foregoing manufacture method A and manufacture method B, it is catalyzed as the load type non-metallocene
Agent, preferably uses the load type non-metallocene catalyst that method manufacture is prepared by the following procedure.
According to the present invention, the preparation method of the load type non-metallocene catalyst comprises the following steps:Make magnesium compound
It is dissolved in the presence of an alcohol in the first solvent, the step of obtaining magnesium compound solution;Make porous carrier and the magnesium compound
Solution is mixed, the step of obtaining the first mixed serum;Precipitating reagent is added into first mixed serum or described the is dried
One mixed serum, the step of obtaining complex carrier;Make the complex carrier and formula(X)Silicon compound and selected from IV B races metal
The chemical treatments contact of compound, the step of obtaining modification complex carrier;Nonmetallocene complex and the modification are multiple with making
Close carrier to contact in the presence of the second solvent, the step of obtaining the load type non-metallocene catalyst.
The magnesium compound is specifically described below.
According to the present invention, term " magnesium compound " uses the common concept in this area, refers to poly- as load-type alkene
Close the conventional use of organic or inorganic solid water-free magnesium-containing compound of carrier of catalyst.
According to the present invention, as the magnesium compound, such as can enumerate magnesium halide, Alkoxymagnesium halides, alkoxyl magnesium,
Alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium.
Specifically, as the magnesium halide, such as magnesium chloride can be enumerated(MgCl2), magnesium bromide(MgBr2), magnesium iodide
(MgI2)And magnesium fluoride(MgF2)Deng wherein it is preferred that magnesium chloride.
As the Alkoxymagnesium halides, such as it can enumerate methoxy magnesium chloride(Mg(OCH3)Cl), ethyoxyl chlorination
Magnesium(Mg(OC2H5)Cl), propoxyl group magnesium chloride(Mg(OC3H7)Cl), n-butoxy magnesium chloride(Mg(OC4H9)Cl), isobutoxy
Magnesium chloride(Mg(i-OC4H9)Cl), methoxyl group magnesium bromide(Mg(OCH3)Br), ethyoxyl magnesium bromide(Mg(OC2H5)Br), propoxyl group
Magnesium bromide(Mg(OC3H7)Br), n-butoxy magnesium bromide(Mg(OC4H9)Br), isobutoxy magnesium bromide(Mg(i-OC4H9)Br)、
Methoxyl group magnesium iodide(Mg(OCH3)I), ethyoxyl magnesium iodide(Mg(OC2H5)I), propoxyl group magnesium iodide(Mg(OC3H7)I), positive fourth
Epoxide magnesium iodide(Mg(OC4H9)I)With isobutoxy magnesium iodide(Mg(i-OC4H9)I)Deng wherein it is preferred that methoxy magnesium chloride, second
Epoxide magnesium chloride and isobutoxy magnesium chloride.
As the alkoxyl magnesium, such as it can enumerate magnesium methoxide(Mg(OCH3)2), magnesium ethylate(Mg(OC2H5)2)、
Propoxyl group magnesium(Mg(OC3H7)2), butoxy magnesium(Mg(OC4H9)2), isobutoxy magnesium(Mg(i-OC4H9)2)With 2- ethyl hexyl oxies
Magnesium(Mg(OCH2CH(C2H5)C4H)2)Deng wherein it is preferred that magnesium ethylate and isobutoxy magnesium.
As the alkyl magnesium, such as it can enumerate methyl magnesium(Mg(CH3)2), magnesium ethide(Mg(C2H5)2), propyl group magnesium(Mg
(C3H7)2), normal-butyl magnesium(Mg(C4H9)2)With isobutyl group magnesium(Mg(i-C4H9)2)Deng wherein it is preferred that magnesium ethide and normal-butyl magnesium.
As the alkyl halide magnesium, such as it can enumerate methyl-magnesium-chloride(Mg(CH3)Cl), ethylmagnesium chloride(Mg
(C2H5)Cl), propyl group magnesium chloride(Mg(C3H7)Cl), n-butylmagnesium chloride magnesium(Mg(C4H9)Cl), isobutyl group magnesium chloride(Mg(i-
C4H9)Cl), methyl-magnesium-bromide(Mg(CH3)Br), ethylmagnesium bromide(Mg(C2H5)Br), propyl group magnesium bromide(Mg(C3H7)Br), just
Butyl magnesium bromide(Mg(C4H9)Br), selenium alkynide(Mg(i-C4H9)Br), methylpyridinium iodide magnesium(Mg(CH3)I), ethyl phosphonium iodide
Magnesium(Mg(C2H5)I), propyl group magnesium iodide(Mg(C3H7)I), normal-butyl magnesium iodide(Mg(C4H9)I)With isobutyl group magnesium iodide(Mg(i-
C4H9)I)Deng wherein it is preferred that methyl-magnesium-chloride, ethylmagnesium chloride and isobutyl group magnesium chloride.
As the alkyl alkoxy magnesium, such as it can enumerate methyl methoxy base magnesium(Mg(OCH3)(CH3)), methylethoxy
Base magnesium(Mg(OC2H5)(CH3)), methyl propoxyl group magnesium(Mg(OC3H7)(CH3)), methyl n-butoxy magnesium(Mg(OC4H9)
(CH3)), methyl tert-butyl epoxide magnesium(Mg(i-OC4H9)(CH3)), ethyl magnesium methoxide(Mg(OCH3)(C2H5)), ethyl ethyoxyl
Magnesium(Mg(OC2H5)(C2H5)), ethylpropoxy magnesium(Mg(OC3H7)(C2H5)), ethyl n-butoxy magnesium(Mg(OC4H9)
(C2H5)), ethyl isobutyl epoxide magnesium(Mg(i-OC4H9)(C2H5)), propylmethoxy magnesium(Mg(OCH3)(C3H7)), propyl group ethoxy
Base magnesium(Mg(OC2H5)(C3H7)), propyl group propoxyl group magnesium(Mg(OC3H7)(C3H7)), propyl group n-butoxy magnesium(Mg(OC4H9)
(C3H7)), propyl group isobutoxy magnesium(Mg(i-OC4H9)(C3H7)), normal-butyl magnesium methoxide(Mg(OCH3)(C4H9)), normal-butyl
Magnesium ethylate(Mg(OC2H5)(C4H9)), normal-butyl propoxyl group magnesium(Mg(OC3H7)(C4H9)), normal-butyl n-butoxy magnesium(Mg
(OC4H9)(C4H9)), normal-butyl isobutoxy magnesium(Mg(i-OC4H9)(C4H9)), isobutyl group magnesium methoxide(Mg(OCH3)(i-
C4H9)), isobutyl group magnesium ethylate(Mg(OC2H5) (i-C4H9)), isobutyl group propoxyl group magnesium(Mg(OC3H7) (i-C4H9)), it is different
Butyl n-butoxy magnesium(Mg(OC4H9) (i-C4H9))With isobutyl group isobutoxy magnesium(Mg(i-OC4H9) (i-C4H9))Deng it
In preferred butyl magnesium ethylate.
These magnesium compounds can be used alone one kind, a variety of can also be used in mixed way, is not particularly limited.
In the form of a variety of mixing in use, mole between two kinds of magnesium compounds in the magnesium compound mixture
Frequently as being 0.25~4:1, preferably 0.5~3:1, more preferably 1~2:1.
Below to obtaining magnesium compound solution the step of, is specifically described.
According to the step, magnesium compound is set to be dissolved in the first solvent in the presence of an alcohol(Magnesium is otherwise referred to as dissolved below
Compound solvent)In, so as to obtain the magnesium compound solution.
As first solvent, such as it can enumerate C6-12Aromatic hydrocarbon, halo C6-12Aromatic hydrocarbon, ester and ether equal solvent.
It is used as the C6-12Aromatic hydrocarbon, such as can enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene.
It is used as the halo C6-12Aromatic hydrocarbon, such as can enumerate chlorotoluene, chloro ethylbenzene, bromotoluene, bromo second
Benzene etc..
As the ester, such as can enumerate methyl formate, Ethyl formate, propyl formate, butyl formate, methyl acetate,
Ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, butyl butyrate etc..
As the ether, such as it can enumerate ether, ethyl methyl ether, tetrahydrofuran etc..
Wherein, preferably C6-12Aromatic hydrocarbon and tetrahydrofuran, most preferably tetrahydrofuran.
These solvents can be used alone one kind, can also be used in mixed way so that arbitrary ratio is a variety of.
According to the present invention, term " alcohol " refers to hydrocarbon chain(Such as C1-30Hydrocarbon)On at least one hydrogen atom be optionally substituted by a hydroxyl group
And the compound obtained.
As the alcohol, such as it can enumerate C1-30Fatty alcohol(It is preferred that C1-30Aliphatic monobasic alcohol)、C6-30Aromatic alcohol(It is excellent
Select C6-30Aromatic monoalcohols)And C4-30Alicyclic ring alcohol(It is preferred that C4-30Alicyclic monohydric alcohol), wherein it is preferred that C1-30Aliphatic monobasic alcohol
Or C2-8Aliphatic monobasic alcohol, more preferably ethanol and butanol.In addition, the alcohol can optionally be selected from halogen atom or C1-6Alkoxy
Substituent substitution.
It is used as the C1-30Fatty alcohol, such as can enumerate methanol, ethanol, propyl alcohol, 2- propyl alcohol, butanol, amylalcohol, 2- methyl
Amylalcohol, 2- ethylpentanols, 2- hexyls butanol, hexanol and 2-Ethylhexyl Alcohol etc., wherein preferred alcohol, butanol and 2-Ethylhexyl Alcohol.
It is used as the C6-30Aromatic alcohol, such as can enumerate phenmethylol, benzyl carbinol and methylbenzyl alcohol etc., wherein it is preferred that benzene
Ethanol.
It is used as the C4-30Alicyclic ring alcohol, such as can enumerate cyclohexanol, cyclopentanol, Lotka-Volterra circle system, methylcyclopentanol, ethyl ring
Amylalcohol, 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 it is preferred that cyclohexanol and methyl cyclohexanol.
As the alcohol replaced by halogen atom, such as trichlorine methanol, ethapon and three Mecorals etc. can be enumerated, its
In preferred trichlorine methanol.
As the alcohol replaced by alkoxy, such as it can enumerate glycol-ether, ethylene glycol-n-butyl ether and 1- fourths
Epoxide -2- propyl alcohol etc., wherein it is preferred that glycol-ether.
These alcohol can be used alone one kind, a variety of can also be used in mixed way.In the form of a variety of mixing in use, institute
The ratio stated between any two kinds of alcohol in alcohol mixture can be arbitrarily determined, and be not particularly limited.
In order to prepare the magnesium compound solution, the magnesium compound can be added to by first solvent and described
The in the mixed solvent of alcohol formation is dissolved, or the magnesium compound is added in first solvent, and simultaneously or with
Addition alcohol is dissolved afterwards, but is not limited to this.
To the preparation time of the magnesium compound solution(The dissolution time of i.e. described magnesium compound)There is no particular limitation,
But generally 0.5~24h, preferably 4~24h.In the preparation process, it is possible to use stir to promote the molten of the magnesium compound
Solution.The stirring can use any form, such as agitating paddle(Rotating speed is generally 10~1000 revs/min)Deng.As needed, have
When can pass through appropriate heating(But maximum temperature have to be lower than the boiling point of first solvent and the alcohol)To promote dissolving.
According to the present invention, porous carrier is mixed with the magnesium compound solution, obtain the first mixed serum.
The porous carrier is specifically described below.
According to the present invention, as the porous carrier, such as it can enumerate this area and be urged in manufacture load type olefin polymerization
During agent as carrier those conventional use of organic or inorganic porosu solids.
Specifically, as the Porous-Organic solid, such as olefin homo or copolymer, polyvinyl alcohol can be enumerated
Or its copolymer, cyclodextrin,(Altogether)Polyester,(Altogether)Polyamide, ryuron or copolymer, Voncoat R 3310 or common
Polymers, methacrylate homopolymer or copolymer, and styrene homopolymers or copolymer etc., and these homopolymers or common
The partial cross-linked form of polymers, wherein it is preferred that partial cross-linked(The such as degree of cross linking is at least 2% but less than 100%)Styrene polymerization
Thing.
According to yet other embodiments, carry and such as select preferably on the surface of the Porous-Organic solid
It is mono-substituted from hydroxyl, primary amino radical, secondary amino group, sulfonic group, carboxyl, amide groups, the mono-substituted amide groups of N-, sulfoamido, N-
The active function groups of any one or more in sulfoamido, sulfydryl, acylimino and hydrazide group, wherein it is preferred that carboxyl and hydroxyl
At least one of base.
According to an embodiment of the invention, using it is preceding the Porous-Organic solid is carried out thermal activation treatment and/or
Chemical activation processing.
According to the present invention, the Porous-Organic solid can only carry out thermal activation treatment before use, or before use
It can also only carry out chemical activation processing, or according to arbitrary built-up sequence successively can carry out the thermal activation using preceding
Processing and chemical activation processing, are not particularly limited.
The thermal activation treatment can be carried out in usual way.To described such as at reduced pressure conditions or under inert atmosphere
Porous-Organic solid is heated.Inert atmosphere mentioned here refers to only contain extremely micro in gas or not contained
Component that can be with the Porous-Organic solid reaction.As the inert atmosphere, such as it can enumerate nitrogen or rare gas gas
Atmosphere, preferably nitrogen atmosphere.Due to the poor heat resistance of Porous-Organic solid, therefore the thermal activation process is described organic more not destroy
The structure of hole solid in itself and it basic composition is premise.Usually, the temperature of the thermal activation be 50~400 DEG C, preferably 100~
250 DEG C, and the thermal activation time is 1~24h, preferably 2~12h.
After thermal activation/chemical activation processing, malleation is saved backup the Porous-Organic solid needs under an inert atmosphere.
As the inorganic porous solids, such as it can enumerate the difficulty of the A of the periodic table of elements II, III A, IVA or Group IVB metal
Molten oxide(Such as silica(Also known as silica or silica gel), aluminum oxide, magnesia, titanium oxide, zirconium oxide or thorium oxide
Deng), or these metals any infusibility composite oxides(Such as oxidation sial, oxidation magnalium, titanium oxide silicon, titanium oxide magnesium
With titanium oxide aluminium etc.), and clay, molecular sieve(Such as ZSM-5 and MCM-41), mica, montmorillonite, bentonite and diatomite
Deng.As the inorganic porous solids, it can also enumerate and pyrohydrolysis is passed through by gaseous metal halide or gaseous silicon compound
And the oxide generated, such as the silica gel obtained by silicon tetrachloride pyrohydrolysis, or obtained by alchlor pyrohydrolysis
Aluminum oxide etc..
It is used as the inorganic porous solids, preferably silica, aluminum oxide, magnesia, oxidation sial, oxidation magnalium, oxygen
Change titanium silicon, titanium dioxide, molecular sieve and montmorillonite etc., particularly preferred silica.
According to the present invention, suitable silica can be manufactured by conventional method, or can be arbitrary commercially available
Commercial product, such as can enumerate the Grace 955, Grace 948, Grace SP9-351, Grace of Grace companies
SP9-485, Grace SP9-10046, Davsion Syloid 245 and ES70 of Aerosil812, Ineos company, ES70X,
ES70Y, ES70W, ES757, EP10X and EP11, and Pq Corp. CS-2133 and MS-3040.
According to yet other embodiments, with hydroxyl etc. preferably on the surface of the inorganic porous solids
Active function groups.
According to the present invention, in one embodiment, thermal activation treatment is being carried out to the inorganic porous solids using preceding
And/or chemical activation processing.
According to the present invention, the inorganic porous solids can only carry out thermal activation treatment before use, or before use
It can also only carry out chemical activation processing, or according to arbitrary built-up sequence successively can carry out the thermal activation using preceding
Processing and chemical activation processing, are not particularly limited.
The thermal activation treatment can be carried out in usual way, such as to described at reduced pressure conditions or under inert atmosphere
Inorganic porous solids are heated.Inert atmosphere mentioned here refers to only contain extremely micro in gas or not contained
The component that can be reacted with the inorganic porous solids.As the inert atmosphere, such as it can enumerate nitrogen or rare gas gas
Atmosphere, preferably nitrogen atmosphere.Usually, the temperature of the thermal activation be 200-800 DEG C, preferably 400~700 DEG C, most preferably 400~
650 DEG C, the heat time is such as 0.5~24h, most preferably preferably 2~12h, 4~8h.
After thermal activation/chemical activation processing, malleation is saved backup the inorganic porous solids needs under an inert atmosphere.
According to the present invention, at the chemical activation that the Porous-Organic solid or the inorganic porous solids are carried out
Reason can be carried out in usual way.Such as, it can enumerate using chemical activating agent come to the Porous-Organic solid or institute
State the method that inorganic porous solids carry out chemical activation processing.
The chemical activating agent is specifically described first below.
According to the present invention, the chemical activating agent is used as using Group IVB metallic compound.
As the Group IVB metallic compound, such as it can enumerate selected from Group IVB metal halide, Group IVB metal alkyl
Compound, Group IVB metal alkoxide, Group IVB metal alkyl halides and Group IVB metal alkoxide halide are at least
It is a kind of.
It is used as the Group IVB metal halide, the Group IVB metal alkyl compound, the Group IVB metal alkoxide
Compound, the Group IVB metal alkyl halides and the Group IVB metal alkoxide halide, such as can enumerate below formula
The compound of structure:
M(OR1)mXnR2 4-m-n
Wherein:
M is 0,1,2,3 or 4;
N is 0,1,2,3 or 4;
M is Group IVB 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
R1And R2It is each independently selected from C1-10Alkyl, such as methyl, ethyl, propyl group, normal-butyl, isobutyl group etc., R1And R2
Can be with identical, can also be different.
Specifically, as the Group IVB metal halide, such as titanium tetrafluoride can be enumerated(TiF4), titanium tetrachloride
(TiCl4), titanium tetrabromide(TiBr4), titanium tetra iodide(TiI4);
Zirconium tetrafluoride(ZrF4), zirconium chloride(ZrCl4), tetrabormated zirconium(ZrBr4), zirconium tetraiodide(ZrI4);
Tetrafluoride hafnium(HfF4), hafnium tetrachloride(HfCl4), hafnium(HfBr4), tetraiodide hafnium(HfI4).
As the Group IVB metal alkyl compound, such as it can enumerate tetramethyl titanium(Ti(CH3)4), tetraethyl titanium(Ti
(CH3CH2)4), four isobutyl group titaniums(Ti(i-C4H9)4), tetra-n-butyl titanium(Ti(C4H9)4), triethyl methyl titanium(Ti(CH3)
(CH3CH2)3), diethyl-dimethyl titanium(Ti(CH3)2(CH3CH2)2), trimethylethyl titanium(Ti(CH3)3(CH3CH2)), it is three different
Butyl methyl titanium(Ti(CH3)(i-C4H9)3), diisobutyl dimethyl titanium(Ti(CH3)2(i-C4H9)2), trimethyl isobutyl group titanium
(Ti(CH3)3(i-C4H9)), triisobutyl ethyl titanium(Ti(CH3CH2)(i-C4H9)3), diisobutyl diethyl titanium(Ti
(CH3CH2)2(i-C4H9)2), triethyl group isobutyl group titanium(Ti(CH3CH2)3(i-C4H9)), three normal-butyl methyltitaniums(Ti(CH3)
(C4H9)3), di-n-butyl dimethyl titanium(Ti(CH3)2(C4H9)2), trimethyl normal-butyl titanium(Ti(CH3)3(C4H9)), three positive fourths
Ylmethyl titanium(Ti(CH3CH2)(C4H9)3), di-n-butyl diethyl titanium(Ti(CH3CH2)2(C4H9)2), triethyl group normal-butyl titanium
(Ti(CH3CH2)3(C4H9))Deng;
Tetramethyl zirconium(Zr(CH3)4), tetraethyl zirconium(Zr(CH3CH2)4), four isobutyl group zirconiums(Zr(i-C4H9)4), four positive fourths
Base zirconium(Zr(C4H9)4), triethyl methyl zirconium(Zr(CH3)(CH3CH2)3), diethyl-dimethyl zirconium(Zr(CH3)2(CH3CH2)2)、
Trimethylethyl zirconium(Zr(CH3)3(CH3CH2)), triisobutyl methylcyclopentadienyl zirconium(Zr(CH3)(i-C4H9)3), diisobutyl zirconium dimethyl
(Zr(CH3)2(i-C4H9)2), trimethyl isobutyl group zirconium(Zr(CH3)3(i-C4H9)), triisobutyl ethyl zirconium(Zr(CH3CH2)(i-
C4H9)3), diisobutyl diethyl zirconium(Zr(CH3CH2)2(i-C4H9)2), triethyl group isobutyl group zirconium(Zr(CH3CH2)3(i-
C4H9)), three normal-butyl methylcyclopentadienyl zirconiums(Zr(CH3)(C4H9)3), di-n-butyl zirconium dimethyl(Zr(CH3)2(C4H9)2), trimethyl just
Butyl zirconium(Zr(CH3)3(C4H9)), three normal-butyl methylcyclopentadienyl zirconiums(Zr(CH3CH2)(C4H9)3), di-n-butyl diethyl zirconium(Zr
(CH3CH2)2(C4H9)2), triethyl group normal-butyl zirconium(Zr(CH3CH2)3(C4H9))Deng;
Tetramethyl hafnium(Hf(CH3)4), tetraethyl hafnium(Hf(CH3CH2)4), four isobutyl group hafniums(Hf(i-C4H9)4), four positive fourths
Base hafnium(Hf(C4H9)4), triethyl methyl hafnium(Hf(CH3)(CH3CH2)3), diethyl-dimethyl hafnium(Hf(CH3)2(CH3CH2)2)、
Trimethylethyl hafnium(Hf(CH3)3(CH3CH2)), triisobutyl methylcyclopentadienyl hafnium(Hf(CH3)(i-C4H9)3), diisobutyl dimethyl hafnium
(Hf(CH3)2(i-C4H9)2), trimethyl isobutyl group hafnium(Hf(CH3)3(i-C4H9)), triisobutyl ethyl hafnium(Hf(CH3CH2)(i-
C4H9)3), diisobutyl diethyl hafnium(Hf(CH3CH2)2(i-C4H9)2), triethyl group isobutyl group hafnium(Hf(CH3CH2)3(i-
C4H9)), three normal-butyl methylcyclopentadienyl hafniums(Hf(CH3)(C4H9)3), di-n-butyl dimethyl hafnium(Hf(CH3)2(C4H9)2), trimethyl just
Butyl hafnium(Hf(CH3)3(C4H9)), three normal-butyl methylcyclopentadienyl hafniums(Hf(CH3CH2)(C4H9)3), di-n-butyl diethyl hafnium(Hf
(CH3CH2)2(C4H9)2), triethyl group normal-butyl hafnium(Hf(CH3CH2)3(C4H9))Deng.
As the Group IVB metal alkoxide, such as it can enumerate titanium tetramethoxide(Ti(OCH3)4), four ethoxies
Base titanium(Ti(OCH3CH2)4), four isobutoxy titaniums(Ti(i-OC4H9)4), four titanium n-butoxides(Ti(OC4H9)4), triethoxy
Methoxyl group titanium(Ti(OCH3)(OCH3CH2)3), diethoxy dimethoxy titanium(Ti(OCH3)2(OCH3CH2)2), trimethoxy second
Epoxide titanium(Ti(OCH3)3(OCH3CH2)), three isobutoxy methoxyl group titaniums(Ti(OCH3)(i-OC4H9)3), two isobutoxy diformazans
Epoxide titanium(Ti(OCH3)2(i-OC4H9)2), trimethoxy isobutoxy titanium(Ti(OCH3)3(i-OC4H9)), three isobutoxy second
Epoxide titanium(Ti(OCH3CH2)(i-OC4H9)3), two isobutoxy diethoxy titaniums(Ti(OCH3CH2)2(i-OC4H9)2), three ethoxies
Base isobutoxy titanium(Ti(OCH3CH2)3(i-OC4H9)), three n-butoxy methoxyl group titaniums(Ti(OCH3)(OC4H9)3), two positive fourths
Epoxide dimethoxy titanium(Ti(OCH3)2(OC4H9)2), trimethoxy titanium n-butoxide(Ti(OCH3)3(OC4H9)), three positive fourth oxygen
Ylmethoxy titanium(Ti(OCH3CH2)(OC4H9)3), two n-butoxy diethoxy titaniums(Ti(OCH3CH2)2(OC4H9)2), three ethoxies
Base titanium n-butoxide(Ti(OCH3CH2)3(OC4H9))Deng;
Tetramethoxy zirconium(Zr(OCH3)4), tetraethoxy zirconium(Zr(OCH3CH2)4), four isobutoxy zirconiums(Zr(i-OC4H9
)4), four n-butoxy zirconiums(Zr(OC4H9)4), triethoxy methoxyl group zirconium(Zr(OCH3)(OCH3CH2)3), diethoxy dimethoxy
Base zirconium(Zr(OCH3)2(OCH3CH2)2), trimethoxy ethyoxyl zirconium(Zr(OCH3)3(OCH3CH2)), three isobutoxy methoxyl groups
Zirconium(Zr(OCH3)(i-OC4H9)3), two isobutoxy dimethoxy zirconiums(Zr(OCH3)2(i-OC4H9)2), trimethoxy isobutyl oxygen
Base zirconium(Zr(OCH3)3(i-C4H9)), three isobutoxy ethyoxyl zirconiums(Zr(OCH3CH2)(i-OC4H9)3), two isobutoxy diethyls
Epoxide zirconium(Zr(OCH3CH2)2(i-OC4H9)2), triethoxy isobutoxy zirconium(Zr(OCH3CH2)3(i-OC4H9)), three positive fourth oxygen
Ylmethoxy zirconium(Zr(OCH3)(OC4H9)3), two n-butoxy dimethoxy zirconiums(Zr(OCH3)2(OC4H9)2), trimethoxy just
Butoxy zirconium(Zr(OCH3)3(OC4H9)), three n-butoxy methoxyl group zirconiums(Zr(OCH3CH2)(OC4H9)3), two n-butoxies two
Ethyoxyl zirconium(Zr(OCH3CH2)2(OC4H9)2), triethoxy n-butoxy zirconium(Zr(OCH3CH2)3(OC4H9))Deng;
Tetramethoxy hafnium(Hf(OCH3)4), tetraethoxy hafnium(Hf(OCH3CH2)4), four isobutoxy hafniums(Hf(i-OC4H9
)4), four n-butoxy hafniums(Hf(OC4H9)4), triethoxy methoxyl group hafnium(Hf(OCH3)(OCH3CH2)3), diethoxy dimethoxy
Base hafnium(Hf(OCH3)2(OCH3CH2)2), trimethoxy ethyoxyl hafnium(Hf(OCH3)3(OCH3CH2)), three isobutoxy methoxyl groups
Hafnium(Hf(OCH3)(i-OC4H9)3), two isobutoxy dimethoxy hafniums(Hf(OCH3)2(i-OC4H9)2), trimethoxy isobutyl oxygen
Base hafnium(Hf(OCH3)3(i-OC4H9)), three isobutoxy ethyoxyl hafniums(Hf(OCH3CH2)(i-OC4H9)3), two isobutoxies two
Ethyoxyl hafnium(Hf(OCH3CH2)2(i-OC4H9)2), triethoxy isobutoxy hafnium(Hf(OCH3CH2)3(i-C4H9)), three positive fourths
Oxymethoxy hafnium(Hf(OCH3)(OC4H9)3), two n-butoxy dimethoxy hafniums(Hf(OCH3)2(OC4H9)2), trimethoxy
N-butoxy hafnium(Hf(OCH3)3(OC4H9)), three n-butoxy methoxyl group hafniums(Hf(OCH3CH2)(OC4H9)3), two n-butoxies
Diethoxy hafnium(Hf(OCH3CH2)2(OC4H9)2), triethoxy n-butoxy hafnium(Hf(OCH3CH2)3(OC4H9))Deng.
As the Group IVB metal alkyl halides, such as it can enumerate trimethyl ammonia chloride titanium(TiCl(CH3)3), three second
Base titanium chloride(TiCl(CH3CH2)3), triisobutyl titanium chloride(TiCl(i-C4H9)3), three n-butylmagnesium chloride titaniums(TiCl
(C4H9)3), dimethyl titanium chloride(TiCl2(CH3)2), diethyl titanium chloride(TiCl2(CH3CH2)2), diisobutyl dichloro
Change titanium(TiCl2(i-C4H9)2), three n-butylmagnesium chloride titaniums(TiCl(C4H9)3), methyl titanium trichloride(Ti(CH3)Cl3), ethyl three
Titanium chloride(Ti(CH3CH2)Cl3), isobutyl group titanium trichloride(Ti(i-C4H9)Cl3), normal-butyl titanium trichloride(Ti(C4H9)Cl3);
Trimethyl titanium bromide(TiBr(CH3)3), triethyl group titanium bromide(TiBr(CH3CH2)3), triisobutyl titanium bromide
(TiBr(i-C4H9)3), three normal-butyl titanium bromides(TiBr(C4H9)3), dimethyl dibrominated titanium(TiBr2(CH3)2), diethyl two
Titanium bromide(TiBr2(CH3CH2)2), diisobutyl dibrominated titanium(TiBr2(i-C4H9)2), three normal-butyl titanium bromides(TiBr
(C4H9)3), methyl titanium tribromide(Ti(CH3)Br3), ethyl titanium tribromide(Ti(CH3CH2)Br3), isobutyl group titanium tribromide(Ti
(i-C4H9)Br3), normal-butyl titanium tribromide(Ti(C4H9)Br3);
Trimethyl ammonia chloride zirconium(ZrCl(CH3)3), triethyl group zirconium chloride(ZrCl(CH3CH2)3), triisobutyl zirconium chloride
(ZrCl(i-C4H9)3), three n-butylmagnesium chloride zirconiums(ZrCl(C4H9)3), dimethyl zirconium dichloride(ZrCl2(CH3)2), diethyl two
Zirconium chloride(ZrCl2(CH3CH2)2), diisobutyl zirconium dichloride(ZrCl2(i-C4H9)2), three n-butylmagnesium chloride zirconiums(ZrCl
(C4H9)3), methyl tri-chlorination zirconium(Zr(CH3)Cl3), ethyl tri-chlorination zirconium(Zr(CH3CH2)Cl3), isobutyl group tri-chlorination zirconium(Zr
(i-C4H9)Cl3), normal-butyl tri-chlorination zirconium(Zr(C4H9)Cl3);
Trimethyl zirconium bromide(ZrBr(CH3)3), triethyl group zirconium bromide(ZrBr(CH3CH2)3), triisobutyl zirconium bromide
(ZrBr(i-C4H9)3), three normal-butyl zirconium bromides(ZrBr(C4H9)3), dimethyl dibrominated zirconium(ZrBr2(CH3)2), diethyl two
Zirconium bromide(ZrBr2(CH3CH2)2), diisobutyl dibrominated zirconium(ZrBr2(i-C4H9)2), three normal-butyl zirconium bromides(ZrBr
(C4H9)3), methyl tribromide zirconium(Zr(CH3)Br3), ethyl tribromide zirconium(Zr(CH3CH2)Br3), isobutyl group tribromide zirconium(Zr
(i-C4H9)Br3), normal-butyl tribromide zirconium(Zr(C4H9)Br3);
Trimethyl ammonia chloride hafnium(HfCl(CH3)3), triethyl group hafnium chloride(HfCl(CH3CH2)3), triisobutyl hafnium chloride
(HfCl(i-C4H9)3), three n-butylmagnesium chloride hafniums(HfCl(C4H9)3), dimethyl hafnium dichloride(HfCl2(CH3)2), diethyl two
Hafnium chloride(HfCl2(CH3CH2)2), diisobutyl hafnium dichloride(HfCl2(i-C4H9)2), three n-butylmagnesium chloride hafniums(HfCl
(C4H9)3), methyl tri-chlorination hafnium(Hf(CH3)Cl3), ethyl tri-chlorination hafnium(Hf(CH3CH2)Cl3), isobutyl group tri-chlorination hafnium(Hf
(i-C4H9)Cl3), normal-butyl tri-chlorination hafnium(Hf(C4H9)Cl3);
Trimethyl bromination hafnium(HfBr(CH3)3), triethyl group bromination hafnium(HfBr(CH3CH2)3), triisobutyl bromination hafnium
(HfBr(i-C4H9)3), three normal-butyl bromination hafniums(HfBr(C4H9)3), dimethyl dibrominated hafnium(HfBr2(CH3)2), diethyl two
Bromination hafnium(HfBr2(CH3CH2)2), diisobutyl dibrominated hafnium(HfBr2(i-C4H9)2), three normal-butyl bromination hafniums(HfBr
(C4H9)3), methyl tribromide hafnium(Hf(CH3)Br3), ethyl tribromide hafnium(Hf(CH3CH2)Br3), isobutyl group tribromide hafnium(Hf
(i-C4H9)Br3), normal-butyl tribromide hafnium(Hf(C4H9)Br3).
As the Group IVB metal alkoxide halide, such as it can enumerate trimethoxy titanium chloride(TiCl(OCH3)3)、
Triethoxy titanium chloride(TiCl(OCH3CH2)3), three isobutoxy titanium chlorides(TiCl(i-OC4H9)3), three n-butoxy chlorinations
Titanium(TiCl(OC4H9)3), dimethoxy titanium chloride(TiCl2(OCH3)2), diethoxy titanium chloride(TiCl2
(OCH3CH2)2), two isobutoxy titanium chloride(TiCl2(i-OC4H9)2), three n-Butoxyl titanium-chlorides(TiCl(OC4H9)3)、
Methoxytitanium trichloride(Ti(OCH3)Cl3), ethyoxyl titanium trichloride(Ti(OCH3CH2)Cl3), isobutoxy titanium trichloride(Ti
(i-C4H9)Cl3), nbutoxytitanium trichloride(Ti(OC4H9)Cl3);
Trimethoxy titanium bromide(TiBr(OCH3)3), triethoxy titanium bromide(TiBr(OCH3CH2)3), three isobutoxy bromines
Change titanium(TiBr(i-OC4H9)3), three n-butoxy titanium bromides(TiBr(OC4H9)3), dimethoxy dibrominated titanium(TiBr2
(OCH3)2), diethoxy dibrominated titanium(TiBr2(OCH3CH2)2), two isobutoxy dibrominated titaniums(TiBr2(i-OC4H9)2)、
Three n-butoxy titanium bromides(TiBr(OC4H9)3), methoxyl group titanium tribromide(Ti(OCH3)Br3), ethyoxyl titanium tribromide(Ti
(OCH3CH2)Br3), isobutoxy titanium tribromide(Ti(i-C4H9)Br3), n-butoxy titanium tribromide(Ti(OC4H9)Br3);
Trimethoxy zirconium chloride(ZrCl(OCH3)3), triethoxy zirconium chloride(ZrCl(OCH3CH2)3), three isobutoxy chlorine
Change zirconium(ZrCl(i-OC4H9)3), three n-butoxy zirconium chlorides(ZrCl(OC4H9)3), dimethoxy zirconium dichloride(ZrCl2
(OCH3)2), diethoxy zirconium dichloride(ZrCl2(OCH3CH2)2), two isobutoxy zirconium dichlorides(ZrCl2(i-OC4H9)2)、
Three n-butoxy zirconium chlorides(ZrCl(OC4H9)3), methoxyl group tri-chlorination zirconium(Zr(OCH3)Cl3), ethyoxyl tri-chlorination zirconium(Zr
(OCH3CH2)Cl3), isobutoxy tri-chlorination zirconium(Zr(i-C4H9)Cl3), n-butoxy tri-chlorination zirconium(Zr(OC4H9)Cl3);
Trimethoxy zirconium bromide(ZrBr(OCH3)3), triethoxy zirconium bromide(ZrBr(OCH3CH2)3), three isobutoxy bromines
Change zirconium(ZrBr(i-OC4H9)3), three n-butoxy zirconium bromides(ZrBr(OC4H9)3), dimethoxy dibrominated zirconium(ZrBr2
(OCH3)2), diethoxy dibrominated zirconium(ZrBr2(OCH3CH2)2), two isobutoxy dibrominated zirconiums(ZrBr2(i-OC4H9)2)、
Three n-butoxy zirconium bromides(ZrBr(OC4H9)3), methoxyl group tribromide zirconium(Zr(OCH3)Br3), ethyoxyl tribromide zirconium(Zr
(OCH3CH2)Br3), isobutoxy tribromide zirconium(Zr(i-C4H9)Br3), n-butoxy tribromide zirconium(Zr(OC4H9)Br3);
Trimethoxy hafnium chloride(HfCl(OCH3)3), triethoxy hafnium chloride(HfCl(OCH3CH2)3), three isobutoxy chlorine
Change hafnium(HfCl(i-OC4H9)3), three n-butoxy hafnium chlorides(HfCl(OC4H9)3), dimethoxy hafnium dichloride(HfCl2
(OCH3)2), diethoxy hafnium dichloride(HfCl2(OCH3CH2)2), two isobutoxy hafnium dichlorides(HfCl2(i-OC4H9)2)、
Three n-butoxy hafnium chlorides(HfCl(OC4H9)3), methoxyl group tri-chlorination hafnium(Hf(OCH3)Cl3), ethyoxyl tri-chlorination hafnium(Hf
(OCH3CH2)Cl3), isobutoxy tri-chlorination hafnium(Hf(i-C4H9)Cl3), n-butoxy tri-chlorination hafnium(Hf(OC4H9)Cl3);
Trimethoxy bromination hafnium(HfBr(OCH3)3), triethoxy bromination hafnium(HfBr(OCH3CH2)3), three isobutoxy bromines
Change hafnium(HfBr(i-OC4H9)3), three n-butoxy bromination hafniums(HfBr(OC4H9)3), dimethoxy dibrominated hafnium(HfBr2
(OCH3)2), diethoxy dibrominated hafnium(HfBr2(OCH3CH2)2), two isobutoxy dibrominated hafniums(HfBr2(i-OC4H9)2)、
Three n-butoxy bromination hafniums(HfBr(OC4H9)3), methoxyl group tribromide hafnium(Hf(OCH3)Br3), ethyoxyl tribromide hafnium(Hf
(OCH3CH2)Br3), isobutoxy tribromide hafnium(Hf(i-C4H9)Br3), n-butoxy tribromide hafnium(Hf(OC4H9)Br3).
It is used as the Group IVB metallic compound, preferably described Group IVB metal halide, more preferably TiCl4、TiBr4、
ZrCl4、ZrBr4、HfCl4And HfBr4, most preferably TiCl4And ZrCl4。
These Group IVB metallic compounds can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
, can be by having what the chemical activating agent to be utilized was activated when the chemical activating agent is at normal temperatures liquid
The mode that the chemical activating agent of scheduled volume is directly added dropwise in Porous-Organic solid or inorganic porous solids uses the chemistry
Activator.
When the chemical activating agent at normal temperatures be solid-state when, in order to measure with it is easy to operate for the sake of, preferably with solution
Form uses the chemical activating agent.Certainly, when the chemical activating agent is at normal temperatures liquid, also may be used sometimes according to needs
To use the chemical activating agent as a solution, it is not particularly limited.
When preparing the solution of the chemical activating agent, to now used solvent, there is no particular limitation, as long as its
The chemical activating agent can be dissolved.
Specifically, C can be enumerated5-12Alkane, C5-12Cycloalkane, halo C5-12Alkane, halo C5-12Cycloalkane, C6-12Virtue
Hydrocarbon or halo C6-12Aromatic hydrocarbons etc., such as can enumerate pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, ring
Pentane, hexamethylene, cycloheptane, cyclooctane, toluene, ethylbenzene, dimethylbenzene, chloro-pentane, chloro-hexane, chloro heptane, chloro are pungent
Alkane, chloro nonane, chloro decane, chloro hendecane, chlorinated dodecane, chlorocyclohexane, chlorotoluene, chloro ethylbenzene and chloro
Dimethylbenzene etc., wherein it is preferred that pentane, hexane, decane, hexamethylene and toluene, most preferably hexane and toluene.
These solvents can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
In addition, to concentration of the chemical activating agent in its solution, there is no particular limitation, can be appropriate as needed
Selection, as long as it can realize the chemical activating agent with scheduled volume to implement the chemical activation.As it was previously stated, such as
Fruit chemical activating agent is liquid, directly can carry out the activation using chemical activating agent, but it is also possible to be modulated into
Used after chemical activation agent solution.
It is expedient to, molar concentration of the chemical activating agent in its solution is usually set to 0.01 ~ 1.0mol/L, but
It is not limited to this.
It as the method for carrying out the chemical activation, such as can enumerate, be solid-state in chemical activating agent(Such as four chlorinations
Zirconium)In the case of, the solution of the chemical activating agent is prepared first, then to Porous-Organic solid or inorganic porous to be activated
Added in solid(It is preferred that being added dropwise)The solution of the chemical activating agent containing scheduled volume, to carry out chemical activation reaction.
It is liquid in chemical activating agent(Such as titanium tetrachloride)In the case of, directly the chemical activating agent of scheduled volume can be added
(It is preferred that being added dropwise)In Porous-Organic solid to be activated or inorganic porous solids, to carry out chemical activation reaction, or should
Chemical activating agent is prepared into after solution, is added into Porous-Organic solid to be activated or inorganic porous solids(It is preferred that being added dropwise)
The solution of the chemical activating agent containing scheduled volume, to carry out chemical activation reaction.
In general, at -30 ~ 60 DEG C(It is preferred that -20 ~ 30 DEG C)Reaction temperature under react the chemical activation(It is necessary
When by stirring)Carry out 0.5~24 hour, preferably 1~8 hour, more preferably 2~6 hours.
After chemical activation reaction terminates, by being filtered, washed and dried, you can obtain by the organic many of chemical activation
Hole solid or inorganic porous solids.
According to the present invention, described be filtered, washed and dried can be carried out using conventional method, and wherein washer solvent can be with
Identical solvent used during using with dissolving the chemical activating agent.As needed, the washing typically carries out 1~8 time, preferably 2
~6 times, most preferably 2~4 times.
The drying can be carried out using conventional method, such as under inert gas seasoning, boulton process or vacuum
Heat drying method, preferably inert gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum seasoning.It is described dry
Dry temperature range is generally normal temperature to 140 DEG C, and drying time is generally 2-20 hours, but is not limited to this.
According to the present invention, be used as the consumption of the chemical activating agent so that the porous carrier with Group IVB metallic element
The ratio of the chemical activating agent of meter is 1g:1-100mmol, preferably 1g:2-50mmol, more preferably 1g:10-25mmol.
According to the present invention, to the surface area of the porous carrier, there is no particular limitation, but generally 10~1000m2/g
(BET method is determined), preferably 100~600m2/g;The pore volume of the porous carrier(Determination of nitrogen adsorption)Generally 0.1~4cm3/
G, preferably 0.2~2cm3/ g, and its average grain diameter(Laser particle analyzer is determined)It is preferred that 1~500mm, more preferably 1~100mm.
According to the present invention, the porous carrier can be arbitrary form, such as micropowder, granular, spherical, aggregation or
Other forms.
By making the porous carrier(Optionally pass through thermal activation and/or chemical activation)It is mixed with the magnesium compound solution
Close, be derived from the first mixed serum.
According to the present invention, the mixed process of the porous carrier and the magnesium compound solution can use usual way
Carry out, there is no particular limitation.It can such as enumerate, under the preparation temperature of normal temperature to the magnesium compound solution, to described
The metered porous carrier in magnesium compound solution, or the metered magnesium compound is molten into the porous carrier
Liquid, mixes 0.1~8h, preferably 0.5~4h, optimal 1~2h(If necessary by stirring).
According to the present invention, the consumption of the porous carrier is used as so that the magnesium compound(With the magnesium compound solution
In the magnesium compound solid meter that contains)1 is reached with the mass ratio of the porous carrier:0.1-20, preferably 1:0.5-10, more preferably
1:1-5.
Now, the first mixed serum obtained is a kind of system of pulpous state.Although not necessarily, in order to ensure system
Uniformity, first mixed serum is preferred after preparation to carry out certain time(2~48h, preferably 4~24h, most preferably 6~
18h)Closed standing.
According to the present invention, by the way that to the first mixed serum convection drying, a kind of consolidating for good fluidity can be obtained
Body product, i.e. complex carrier of the invention.
Now, the convection drying can be carried out using conventional method, such as dry, vacuum atmosphere under inert gas atmosphere
Heat drying etc. under lower drying or vacuum atmosphere, wherein it is preferred that heat drying under vacuum atmosphere.Drying temperature is generally 30 ~
160 DEG C, preferably 60 ~ 130 DEG C, drying time is generally 2~24h, but is not limited to this sometimes.
Or, according to the present invention, by the metered precipitating reagent into first mixed serum, make solid matter from this
It is precipitated out in first mixed serum, is derived from complex carrier.
The precipitating reagent is specifically described below.
According to the present invention, term " precipitating reagent " uses the common concept in this area, refers to that solid content solute can be reduced
(Than magnesium compound as mentioned, porous carrier, Nonmetallocene part or Nonmetallocene complex etc.)Dissolving in its solution
Spend the chemical inertness liquid for simultaneously and then making it be separated out in solid form from the solution.
According to the present invention, as the precipitating reagent, such as it can enumerate for solid content solute to be precipitated(It is such as described
Magnesium compound, porous carrier, Nonmetallocene part or Nonmetallocene complex etc.)For be poor solvent, and for for
Dissolve the solid content solute(Such as magnesium compound)The solvent for be good solvent solvent, such as can enumerate C5-12
Alkane, C5-12Cycloalkane, halo C1-10Alkane and halo C5-12Cycloalkane.
It is used as the C5-12Alkane, such as can enumerate pentane, hexane, heptane, octane, nonane and decane etc., wherein excellent
Select hexane, heptane and decane, most preferably hexane.
It is used as the C5-12Cycloalkane, such as can enumerate hexamethylene, pentamethylene, cycloheptane, cyclodecane and cyclononane etc.,
Most preferably hexamethylene.
It is used as the halo C1-10Alkane, such as can enumerate dichloromethane, dichloro hexane, two chloroheptanes, chloroform,
Trichloroethanes, three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane and three NBBs etc..
It is used as the halo C5-12Cycloalkane, such as can enumerate chlorocyclopentane, chlorocyclohexane, chloro cycloheptane,
Chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo cycloheptane, bromo cyclooctane,
Bromo cyclononane and bromo cyclodecane etc..
These precipitating reagents can be used alone one kind, can also be used in mixed way so that arbitrary ratio is a variety of.
The feed postition of precipitating reagent can be added or be added dropwise to be disposable, preferably disposable to add.In the precipitation process
In, it is possible to use stir to promote the scattered of precipitating reagent, and be conducive to the final precipitation of solid product.The stirring can use any
Form(Such as agitating paddle), and rotating speed is generally 10~1000 revs/min etc..
To the consumption of the precipitating reagent, there is no particular limitation, but it is general by volume, the precipitating reagent dissolves with being used for
The ratio of the solvent of the magnesium compound is 1:0.2~5, preferably 1:0.5~2, more preferably 1:0.8~1.5.
To the temperature of the precipitating reagent, also there is no particular limitation, but generally preferably normal temperature is to any molten less than used
The temperature of the boiling point of agent and precipitating reagent(It is preferred that 20-80 DEG C, more preferably 40-60 DEG C), but this is not limited to sometimes.Moreover, this is heavy
Shallow lake process is general it is also preferred that in the temperature of normal temperature to the boiling point of any solvent and precipitating reagent less than used in(It is preferred that 20-80 DEG C,
More preferably 40-60 DEG C)Lower progress 0.3-12 hours, but this is not limited to sometimes, and be substantially completely precipitated as with solid product
It is accurate.
Completely after precipitation, the solid product obtained is filtered, washed and dried.For it is described filtering, washing and
Dry method is not particularly limited, and those commonly used in the art can be used as needed.
As needed, the washing is general is carried out 1 ~ 6 time, preferably 3 ~ 4 times.Wherein, washer solvent is preferably used and sunk
Shallow lake agent identical solvent, but it is also possible to different.
The drying can be carried out using conventional method, such as under inert gas seasoning, boulton process or vacuum
Heat drying method, preferably inert gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum seasoning.
The temperature range of the drying is generally normal temperature to 140 DEG C.Drying time is generally 2-20 hours, but can also
It is different according to the specifically used solvent case for being used to dissolve the magnesium compound.Such as, tetrahydrofuran conduct is being used
During solvent for dissolving the magnesium compound, drying temperature is generally 80 DEG C or so, is dried under vacuum 2 ~ 12 hours,
And when using toluene as solvent for dissolving the magnesium compound, drying temperature is generally 100 DEG C or so, under vacuo
Dry 4 ~ 24 hours.
According to the present invention, by the complex carrier and formula that make foregoing acquisition(X)Silicon compound and chemical treatments contact,
It is derived from modifying complex carrier.
Below to the formula(X)Silicon compound be specifically described.
Si(OR)mX4-mFormula(X)
Wherein, each R is identical or different, is each independently selected from C1-8Straight or branched alkyl, such as methyl, ethyl, positive third
It is base, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, different pungent
Base etc.;
M is 0,1,2,3 or 4 integer;
Each X is identical or different, is each independently selected from halogen.
According to the present invention, as the halogen, such as fluorine, chlorine, bromine and iodine can be enumerated, wherein it is preferred that chlorine.
According to the present invention, each R is preferably identical or different, is each independently selected from C1-4Straight or branched alkyl, preferably
For ethyl.
It is used as the formula(X)Silicon compound, can enumerate but be not limited to compound in detail below:
Tetramethoxy-silicane, tetraethoxy-silicane, four positive propoxy silicon, tetraisopropoxide silicon, four n-butoxy silicon, four isobutyl oxygen
Base silicon, four n-pentyloxy silicon, tetraisoamoxy-silicane, four n-octyloxy silicon, four different octyloxy silicon, a methoxy ethyl triethoxy silicane,
Dimethoxy diethoxy silicon, the ethyoxyl silicon of trimethoxy one, the n-propyl epoxide silicon of a methoxyl group three, positive third oxygen of dimethoxy two
Base silicon, the positive propoxy silicon of trimethoxy one, a methoxyl group triisopropyl epoxide silicon, dimethoxy diisopropoxy silicon, trimethoxy
The isopropoxy silicon of base one, the normal-butyl epoxide silicon of a methoxyl group three, the n-butoxy silicon of dimethoxy two, the n-butoxy of trimethoxy one
Silicon, a methoxyl group triisobutyl epoxide silicon, the isobutoxy silicon of dimethoxy two, the isobutoxy silicon of trimethoxy one, an ethyoxyl
Three n-propyl epoxide silicon, the positive propoxy silicon of diethoxy two, the positive propoxy silicon of triethoxy one, an ethyoxyl triisopropyl epoxide
Silicon, diethoxy diisopropoxy silicon, the isopropoxy silicon of triethoxy one, the normal-butyl epoxide silicon of an ethyoxyl three, diethoxy
Two n-butoxy silicon, the n-butoxy silicon of triethoxy one, an ethyoxyl triisobutyl epoxide silicon, the isobutoxy of diethoxy two
Four C such as silicon, the isobutoxy silicon of triethoxy one1-8Straight or branched alkoxyl silicon, wherein it is preferred that tetramethoxy-silicane, tetraethoxy
Silicon, tetraisobutoxy-silicane, more preferably tetraethoxy-silicane;
Trimethoxy chloro silicon, dimethoxy chloro silicon, a methoxyl group chloro silicon, triethoxy chloro silicon, diethoxy
Chloro silicon, an ethyoxyl chloro silicon, three isobutoxy chloro silicon, two isobutoxy chloro silicon, an isobutoxy chloro silicon, front three
Epoxide bromo silicon, dimethoxy bromo silicon, a methoxyl group bromo silicon, triethoxy bromo silicon, diethoxy bromo silicon, an ethoxy
Bromide is for C such as silicon, three isobutoxy bromo silicon, two isobutoxy bromo silicon, an isobutoxy bromo silicon1-8Straight or branched alkane
Epoxide halo silicon, wherein it is preferred that trimethoxy chloro silicon, dimethoxy chloro silicon, triethoxy chloro silicon, diethoxy chloro
Silicon, more preferably triethoxy chloro silicon;
Ocratation, silicon tetrachloride, silicon bromide, silicon tetraiodide, the silicon tetrahalogen such as tribromo silicon chloride, trichlorine silicon bromide,
Wherein preferred silicon tetrachloride.
These silicon compounds can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
The chemical treatments are specifically described below.
According to the present invention, the chemical treatments are used as using Group IVB metallic compound.
As the Group IVB metallic compound, such as it can enumerate selected from Group IVB metal halide, Group IVB metal alkyl
Compound, Group IVB metal alkoxide, Group IVB metal alkyl halides and Group IVB metal alkoxide halide are at least
It is a kind of.
It is used as the Group IVB metal halide, the Group IVB metal alkyl compound, the Group IVB metal alkoxide
Compound, the Group IVB metal alkyl halides and the Group IVB metal alkoxide halide, such as can enumerate below formula
The compound of structure:
M(OR1)mXnR2 4-m-n
Wherein:
M is 0,1,2,3 or 4;
N is 0,1,2,3 or 4;
M is Group IVB 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
R1And R2It is each independently selected from C1-10Alkyl, such as methyl, ethyl, propyl group, normal-butyl, isobutyl group etc., R1And R2
Can be with identical, can also be different.
Specifically, as the Group IVB metal halide, such as titanium tetrafluoride can be enumerated(TiF4), titanium tetrachloride
(TiCl4), titanium tetrabromide(TiBr4), titanium tetra iodide(TiI4);
Zirconium tetrafluoride(ZrF4), zirconium chloride(ZrCl4), tetrabormated zirconium(ZrBr4), zirconium tetraiodide(ZrI4);
Tetrafluoride hafnium(HfF4), hafnium tetrachloride(HfCl4), hafnium(HfBr4), tetraiodide hafnium(HfI4).
As the Group IVB metal alkyl compound, such as it can enumerate tetramethyl titanium(Ti(CH3)4), tetraethyl titanium(Ti
(CH3CH2)4), four isobutyl group titaniums(Ti(i-C4H9)4), tetra-n-butyl titanium(Ti(C4H9)4), triethyl methyl titanium(Ti(CH3)
(CH3CH2)3), diethyl-dimethyl titanium(Ti(CH3)2(CH3CH2)2), trimethylethyl titanium(Ti(CH3)3(CH3CH2)), it is three different
Butyl methyl titanium(Ti(CH3)(i-C4H9)3), diisobutyl dimethyl titanium(Ti(CH3)2(i-C4H9)2), trimethyl isobutyl group titanium
(Ti(CH3)3(i-C4H9)), triisobutyl ethyl titanium(Ti(CH3CH2)(i-C4H9)3), diisobutyl diethyl titanium(Ti
(CH3CH2)2(i-C4H9)2), triethyl group isobutyl group titanium(Ti(CH3CH2)3(i-C4H9)), three normal-butyl methyltitaniums(Ti(CH3)
(C4H9)3), di-n-butyl dimethyl titanium(Ti(CH3)2(C4H9)2), trimethyl normal-butyl titanium(Ti(CH3)3(C4H9)), three positive fourths
Ylmethyl titanium(Ti(CH3CH2)(C4H9)3), di-n-butyl diethyl titanium(Ti(CH3CH2)2(C4H9)2), triethyl group normal-butyl titanium
(Ti(CH3CH2)3(C4H9))Deng;
Tetramethyl zirconium(Zr(CH3)4), tetraethyl zirconium(Zr(CH3CH2)4), four isobutyl group zirconiums(Zr(i-C4H9)4), four positive fourths
Base zirconium(Zr(C4H9)4), triethyl methyl zirconium(Zr(CH3)(CH3CH2)3), diethyl-dimethyl zirconium(Zr(CH3)2(CH3CH2)2)、
Trimethylethyl zirconium(Zr(CH3)3(CH3CH2)), triisobutyl methylcyclopentadienyl zirconium(Zr(CH3)(i-C4H9)3), diisobutyl zirconium dimethyl
(Zr(CH3)2(i-C4H9)2), trimethyl isobutyl group zirconium(Zr(CH3)3(i-C4H9)), triisobutyl ethyl zirconium(Zr(CH3CH2)(i-
C4H9)3), diisobutyl diethyl zirconium(Zr(CH3CH2)2(i-C4H9)2), triethyl group isobutyl group zirconium(Zr(CH3CH2)3(i-
C4H9)), three normal-butyl methylcyclopentadienyl zirconiums(Zr(CH3)(C4H9)3), di-n-butyl zirconium dimethyl(Zr(CH3)2(C4H9)2), trimethyl just
Butyl zirconium(Zr(CH3)3(C4H9)), three normal-butyl methylcyclopentadienyl zirconiums(Zr(CH3CH2)(C4H9)3), di-n-butyl diethyl zirconium(Zr
(CH3CH2)2(C4H9)2), triethyl group normal-butyl zirconium(Zr(CH3CH2)3(C4H9))Deng;
Tetramethyl hafnium(Hf(CH3)4), tetraethyl hafnium(Hf(CH3CH2)4), four isobutyl group hafniums(Hf(i-C4H9)4), four positive fourths
Base hafnium(Hf(C4H9)4), triethyl methyl hafnium(Hf(CH3)(CH3CH2)3), diethyl-dimethyl hafnium(Hf(CH3)2(CH3CH2)2)、
Trimethylethyl hafnium(Hf(CH3)3(CH3CH2)), triisobutyl methylcyclopentadienyl hafnium(Hf(CH3)(i-C4H9)3), diisobutyl dimethyl hafnium
(Hf(CH3)2(i-C4H9)2), trimethyl isobutyl group hafnium(Hf(CH3)3(i-C4H9)), triisobutyl ethyl hafnium(Hf(CH3CH2)(i-
C4H9)3), diisobutyl diethyl hafnium(Hf(CH3CH2)2(i-C4H9)2), triethyl group isobutyl group hafnium(Hf(CH3CH2)3(i-
C4H9)), three normal-butyl methylcyclopentadienyl hafniums(Hf(CH3)(C4H9)3), di-n-butyl dimethyl hafnium(Hf(CH3)2(C4H9)2), trimethyl just
Butyl hafnium(Hf(CH3)3(C4H9)), three normal-butyl methylcyclopentadienyl hafniums(Hf(CH3CH2)(C4H9)3), di-n-butyl diethyl hafnium(Hf
(CH3CH2)2(C4H9)2), triethyl group normal-butyl hafnium(Hf(CH3CH2)3(C4H9))Deng.
As the Group IVB metal alkoxide, such as it can enumerate titanium tetramethoxide(Ti(OCH3)4), four ethoxies
Base titanium(Ti(OCH3CH2)4), four isobutoxy titaniums(Ti(i-OC4H9)4), four titanium n-butoxides(Ti(OC4H9)4), triethoxy
Methoxyl group titanium(Ti(OCH3)(OCH3CH2)3), diethoxy dimethoxy titanium(Ti(OCH3)2(OCH3CH2)2), trimethoxy second
Epoxide titanium(Ti(OCH3)3(OCH3CH2)), three isobutoxy methoxyl group titaniums(Ti(OCH3)(i-OC4H9)3), two isobutoxy diformazans
Epoxide titanium(Ti(OCH3)2(i-OC4H9)2), trimethoxy isobutoxy titanium(Ti(OCH3)3(i-OC4H9)), three isobutoxy second
Epoxide titanium(Ti(OCH3CH2)(i-OC4H9)3), two isobutoxy diethoxy titaniums(Ti(OCH3CH2)2(i-OC4H9)2), three ethoxies
Base isobutoxy titanium(Ti(OCH3CH2)3(i-OC4H9)), three n-butoxy methoxyl group titaniums(Ti(OCH3)(OC4H9)3), two positive fourths
Epoxide dimethoxy titanium(Ti(OCH3)2(OC4H9)2), trimethoxy titanium n-butoxide(Ti(OCH3)3(OC4H9)), three positive fourth oxygen
Ylmethoxy titanium(Ti(OCH3CH2)(OC4H9)3), two n-butoxy diethoxy titaniums(Ti(OCH3CH2)2(OC4H9)2), three ethoxies
Base titanium n-butoxide(Ti(OCH3CH2)3(OC4H9))Deng;
Tetramethoxy zirconium(Zr(OCH3)4), tetraethoxy zirconium(Zr(OCH3CH2)4), four isobutoxy zirconiums(Zr(i-OC4H9
)4), four n-butoxy zirconiums(Zr(OC4H9)4), triethoxy methoxyl group zirconium(Zr(OCH3)(OCH3CH2)3), diethoxy dimethoxy
Base zirconium(Zr(OCH3)2(OCH3CH2)2), trimethoxy ethyoxyl zirconium(Zr(OCH3)3(OCH3CH2)), three isobutoxy methoxyl groups
Zirconium(Zr(OCH3)(i-OC4H9)3), two isobutoxy dimethoxy zirconiums(Zr(OCH3)2(i-OC4H9)2), trimethoxy isobutyl oxygen
Base zirconium(Zr(OCH3)3(i-C4H9)), three isobutoxy ethyoxyl zirconiums(Zr(OCH3CH2)(i-OC4H9)3), two isobutoxy diethyls
Epoxide zirconium(Zr(OCH3CH2)2(i-OC4H9)2), triethoxy isobutoxy zirconium(Zr(OCH3CH2)3(i-OC4H9)), three positive fourth oxygen
Ylmethoxy zirconium(Zr(OCH3)(OC4H9)3), two n-butoxy dimethoxy zirconiums(Zr(OCH3)2(OC4H9)2), trimethoxy just
Butoxy zirconium(Zr(OCH3)3(OC4H9)), three n-butoxy methoxyl group zirconiums(Zr(OCH3CH2)(OC4H9)3), two n-butoxies two
Ethyoxyl zirconium(Zr(OCH3CH2)2(OC4H9)2), triethoxy n-butoxy zirconium(Zr(OCH3CH2)3(OC4H9))Deng;
Tetramethoxy hafnium(Hf(OCH3)4), tetraethoxy hafnium(Hf(OCH3CH2)4), four isobutoxy hafniums(Hf(i-OC4H9
)4), four n-butoxy hafniums(Hf(OC4H9)4), triethoxy methoxyl group hafnium(Hf(OCH3)(OCH3CH2)3), diethoxy dimethoxy
Base hafnium(Hf(OCH3)2(OCH3CH2)2), trimethoxy ethyoxyl hafnium(Hf(OCH3)3(OCH3CH2)), three isobutoxy methoxyl groups
Hafnium(Hf(OCH3)(i-OC4H9)3), two isobutoxy dimethoxy hafniums(Hf(OCH3)2(i-OC4H9)2), trimethoxy isobutyl oxygen
Base hafnium(Hf(OCH3)3(i-OC4H9)), three isobutoxy ethyoxyl hafniums(Hf(OCH3CH2)(i-OC4H9)3), two isobutoxies two
Ethyoxyl hafnium(Hf(OCH3CH2)2(i-OC4H9)2), triethoxy isobutoxy hafnium(Hf(OCH3CH2)3(i-C4H9)), three positive fourths
Oxymethoxy hafnium(Hf(OCH3)(OC4H9)3), two n-butoxy dimethoxy hafniums(Hf(OCH3)2(OC4H9)2), trimethoxy
N-butoxy hafnium(Hf(OCH3)3(OC4H9)), three n-butoxy methoxyl group hafniums(Hf(OCH3CH2)(OC4H9)3), two n-butoxies
Diethoxy hafnium(Hf(OCH3CH2)2(OC4H9)2), triethoxy n-butoxy hafnium(Hf(OCH3CH2)3(OC4H9))Deng.
As the Group IVB metal alkyl halides, such as it can enumerate trimethyl ammonia chloride titanium(TiCl(CH3)3), three second
Base titanium chloride(TiCl(CH3CH2)3), triisobutyl titanium chloride(TiCl(i-C4H9)3), three n-butylmagnesium chloride titaniums(TiCl
(C4H9)3), dimethyl titanium chloride(TiCl2(CH3)2), diethyl titanium chloride(TiCl2(CH3CH2)2), diisobutyl dichloro
Change titanium(TiCl2(i-C4H9)2), three n-butylmagnesium chloride titaniums(TiCl(C4H9)3), methyl titanium trichloride(Ti(CH3)Cl3), ethyl three
Titanium chloride(Ti(CH3CH2)Cl3), isobutyl group titanium trichloride(Ti(i-C4H9)Cl3), normal-butyl titanium trichloride(Ti(C4H9)Cl3);
Trimethyl titanium bromide(TiBr(CH3)3), triethyl group titanium bromide(TiBr(CH3CH2)3), triisobutyl titanium bromide
(TiBr(i-C4H9)3), three normal-butyl titanium bromides(TiBr(C4H9)3), dimethyl dibrominated titanium(TiBr2(CH3)2), diethyl two
Titanium bromide(TiBr2(CH3CH2)2), diisobutyl dibrominated titanium(TiBr2(i-C4H9)2), three normal-butyl titanium bromides(TiBr
(C4H9)3), methyl titanium tribromide(Ti(CH3)Br3), ethyl titanium tribromide(Ti(CH3CH2)Br3), isobutyl group titanium tribromide(Ti
(i-C4H9)Br3), normal-butyl titanium tribromide(Ti(C4H9)Br3);
Trimethyl ammonia chloride zirconium(ZrCl(CH3)3), triethyl group zirconium chloride(ZrCl(CH3CH2)3), triisobutyl zirconium chloride
(ZrCl(i-C4H9)3), three n-butylmagnesium chloride zirconiums(ZrCl(C4H9)3), dimethyl zirconium dichloride(ZrCl2(CH3)2), diethyl two
Zirconium chloride(ZrCl2(CH3CH2)2), diisobutyl zirconium dichloride(ZrCl2(i-C4H9)2), three n-butylmagnesium chloride zirconiums(ZrCl
(C4H9)3), methyl tri-chlorination zirconium(Zr(CH3)Cl3), ethyl tri-chlorination zirconium(Zr(CH3CH2)Cl3), isobutyl group tri-chlorination zirconium(Zr
(i-C4H9)Cl3), normal-butyl tri-chlorination zirconium(Zr(C4H9)Cl3);
Trimethyl zirconium bromide(ZrBr(CH3)3), triethyl group zirconium bromide(ZrBr(CH3CH2)3), triisobutyl zirconium bromide
(ZrBr(i-C4H9)3), three normal-butyl zirconium bromides(ZrBr(C4H9)3), dimethyl dibrominated zirconium(ZrBr2(CH3)2), diethyl two
Zirconium bromide(ZrBr2(CH3CH2)2), diisobutyl dibrominated zirconium(ZrBr2(i-C4H9)2), three normal-butyl zirconium bromides(ZrBr
(C4H9)3), methyl tribromide zirconium(Zr(CH3)Br3), ethyl tribromide zirconium(Zr(CH3CH2)Br3), isobutyl group tribromide zirconium(Zr
(i-C4H9)Br3), normal-butyl tribromide zirconium(Zr(C4H9)Br3);
Trimethyl ammonia chloride hafnium(HfCl(CH3)3), triethyl group hafnium chloride(HfCl(CH3CH2)3), triisobutyl hafnium chloride
(HfCl(i-C4H9)3), three n-butylmagnesium chloride hafniums(HfCl(C4H9)3), dimethyl hafnium dichloride(HfCl2(CH3)2), diethyl two
Hafnium chloride(HfCl2(CH3CH2)2), diisobutyl hafnium dichloride(HfCl2(i-C4H9)2), three n-butylmagnesium chloride hafniums(HfCl
(C4H9)3), methyl tri-chlorination hafnium(Hf(CH3)Cl3), ethyl tri-chlorination hafnium(Hf(CH3CH2)Cl3), isobutyl group tri-chlorination hafnium(Hf
(i-C4H9)Cl3), normal-butyl tri-chlorination hafnium(Hf(C4H9)Cl3);
Trimethyl bromination hafnium(HfBr(CH3)3), triethyl group bromination hafnium(HfBr(CH3CH2)3), triisobutyl bromination hafnium
(HfBr(i-C4H9)3), three normal-butyl bromination hafniums(HfBr(C4H9)3), dimethyl dibrominated hafnium(HfBr2(CH3)2), diethyl two
Bromination hafnium(HfBr2(CH3CH2)2), diisobutyl dibrominated hafnium(HfBr2(i-C4H9)2), three normal-butyl bromination hafniums(HfBr
(C4H9)3), methyl tribromide hafnium(Hf(CH3)Br3), ethyl tribromide hafnium(Hf(CH3CH2)Br3), isobutyl group tribromide hafnium(Hf
(i-C4H9)Br3), normal-butyl tribromide hafnium(Hf(C4H9)Br3).
As the Group IVB metal alkoxide halide, such as it can enumerate trimethoxy titanium chloride(TiCl(OCH3)3)、
Triethoxy titanium chloride(TiCl(OCH3CH2)3), three isobutoxy titanium chlorides(TiCl(i-OC4H9)3), three n-butoxy chlorinations
Titanium(TiCl(OC4H9)3), dimethoxy titanium chloride(TiCl2(OCH3)2), diethoxy titanium chloride(TiCl2
(OCH3CH2)2), two isobutoxy titanium chloride(TiCl2(i-OC4H9)2), three n-Butoxyl titanium-chlorides(TiCl(OC4H9)3)、
Methoxytitanium trichloride(Ti(OCH3)Cl3), ethyoxyl titanium trichloride(Ti(OCH3CH2)Cl3), isobutoxy titanium trichloride(Ti
(i-C4H9)Cl3), nbutoxytitanium trichloride(Ti(OC4H9)Cl3);
Trimethoxy titanium bromide(TiBr(OCH3)3), triethoxy titanium bromide(TiBr(OCH3CH2)3), three isobutoxy bromines
Change titanium(TiBr(i-OC4H9)3), three n-butoxy titanium bromides(TiBr(OC4H9)3), dimethoxy dibrominated titanium(TiBr2
(OCH3)2), diethoxy dibrominated titanium(TiBr2(OCH3CH2)2), two isobutoxy dibrominated titaniums(TiBr2(i-OC4H9)2)、
Three n-butoxy titanium bromides(TiBr(OC4H9)3), methoxyl group titanium tribromide(Ti(OCH3)Br3), ethyoxyl titanium tribromide(Ti
(OCH3CH2)Br3), isobutoxy titanium tribromide(Ti(i-C4H9)Br3), n-butoxy titanium tribromide(Ti(OC4H9)Br3);
Trimethoxy zirconium chloride(ZrCl(OCH3)3), triethoxy zirconium chloride(ZrCl(OCH3CH2)3), three isobutoxy chlorine
Change zirconium(ZrCl(i-OC4H9)3), three n-butoxy zirconium chlorides(ZrCl(OC4H9)3), dimethoxy zirconium dichloride(ZrCl2
(OCH3)2), diethoxy zirconium dichloride(ZrCl2(OCH3CH2)2), two isobutoxy zirconium dichlorides(ZrCl2(i-OC4H9)2)、
Three n-butoxy zirconium chlorides(ZrCl(OC4H9)3), methoxyl group tri-chlorination zirconium(Zr(OCH3)Cl3), ethyoxyl tri-chlorination zirconium(Zr
(OCH3CH2)Cl3), isobutoxy tri-chlorination zirconium(Zr(i-C4H9)Cl3), n-butoxy tri-chlorination zirconium(Zr(OC4H9)Cl3);
Trimethoxy zirconium bromide(ZrBr(OCH3)3), triethoxy zirconium bromide(ZrBr(OCH3CH2)3), three isobutoxy bromines
Change zirconium(ZrBr(i-OC4H9)3), three n-butoxy zirconium bromides(ZrBr(OC4H9)3), dimethoxy dibrominated zirconium(ZrBr2
(OCH3)2), diethoxy dibrominated zirconium(ZrBr2(OCH3CH2)2), two isobutoxy dibrominated zirconiums(ZrBr2(i-OC4H9)2)、
Three n-butoxy zirconium bromides(ZrBr(OC4H9)3), methoxyl group tribromide zirconium(Zr(OCH3)Br3), ethyoxyl tribromide zirconium(Zr
(OCH3CH2)Br3), isobutoxy tribromide zirconium(Zr(i-C4H9)Br3), n-butoxy tribromide zirconium(Zr(OC4H9)Br3);
Trimethoxy hafnium chloride(HfCl(OCH3)3), triethoxy hafnium chloride(HfCl(OCH3CH2)3), three isobutoxy chlorine
Change hafnium(HfCl(i-OC4H9)3), three n-butoxy hafnium chlorides(HfCl(OC4H9)3), dimethoxy hafnium dichloride(HfCl2
(OCH3)2), diethoxy hafnium dichloride(HfCl2(OCH3CH2)2), two isobutoxy hafnium dichlorides(HfCl2(i-OC4H9)2)、
Three n-butoxy hafnium chlorides(HfCl(OC4H9)3), methoxyl group tri-chlorination hafnium(Hf(OCH3)Cl3), ethyoxyl tri-chlorination hafnium(Hf
(OCH3CH2)Cl3), isobutoxy tri-chlorination hafnium(Hf(i-C4H9)Cl3), n-butoxy tri-chlorination hafnium(Hf(OC4H9)Cl3);
Trimethoxy bromination hafnium(HfBr(OCH3)3), triethoxy bromination hafnium(HfBr(OCH3CH2)3), three isobutoxy bromines
Change hafnium(HfBr(i-OC4H9)3), three n-butoxy bromination hafniums(HfBr(OC4H9)3), dimethoxy dibrominated hafnium(HfBr2
(OCH3)2), diethoxy dibrominated hafnium(HfBr2(OCH3CH2)2), two isobutoxy dibrominated hafniums(HfBr2(i-OC4H9)2)、
Three n-butoxy bromination hafniums(HfBr(OC4H9)3), methoxyl group tribromide hafnium(Hf(OCH3)Br3), ethyoxyl tribromide hafnium(Hf
(OCH3CH2)Br3), isobutoxy tribromide hafnium(Hf(i-C4H9)Br3), n-butoxy tribromide hafnium(Hf(OC4H9)Br3).
It is used as the Group IVB metallic compound, preferably described Group IVB metal halide, more preferably TiCl4、TiBr4、
ZrCl4、ZrBr4、HfCl4And HfBr4, most preferably TiCl4And ZrCl4。
These Group IVB metallic compounds can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
When the chemical treatments are at normal temperatures liquid, the chemistry directly can be carried out using the chemical treatments
Processing reaction.When the chemical treatments at normal temperatures be solid-state when, in order to measure with it is easy to operate for the sake of, preferably with solution
Form uses the chemical treatments.Certainly, when the chemical treatments are at normal temperatures liquid, also may be used sometimes according to needs
To use the chemical treatments as a solution, it is not particularly limited.
When preparing the solution of the chemical treatments, to now used solvent, there is no particular limitation, as long as its
The chemical treatments can be dissolved and do not destroyed(Such as dissolve)The existing carrier structure of the complex carrier.
Specifically, C can be enumerated5-12Alkane, C5-12Cycloalkane, halo C5-12Alkane and halo C5-12Cycloalkane etc., than
Pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, pentamethylene, hexamethylene, cycloheptane, ring can such as be enumerated
Octane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro hendecane, chloro ten
Dioxane and chlorocyclohexane etc., wherein it is preferred that pentane, hexane, decane and hexamethylene, most preferably hexane.
These solvents can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
In addition, to concentration of the chemical treatments in its solution, there is no particular limitation, can be appropriate as needed
Selection, as long as it can realize with the chemical treatments of scheduled volume to carry out the chemical treatment reaction.Such as preceding institute
State, if chemical treatments are liquid, directly can carry out the processing using chemical treatments, but it is also possible to adjusted
Used after the solution that chemical treatments are made.
In general, molar concentration of the chemical treatments in its solution is usually set to 0.01 ~ 1.0mol/L, but
It is not limited to this.
According to the present invention, as the ways of carrying out of the chemical treatment reaction, such as can enumerate makes the complex carrier
With the silicon compound and the chemical treatments in solvent(Also referred to as chemical treatment solvent)In the presence of contacted
Mode.
According to the present invention, to the chemical treatment, with solvent, there is no particular limitation, as long as it can dissolve the silication
Compound and the chemical treatments, and do not destroy(Such as dissolve)The existing carrier structure of the complex carrier.
Specifically, as the chemical treatment solvent, C can be enumerated5-12Alkane, C5-12Cycloalkane, halo C5-12Alkane
Hydrocarbon and halo C5-12Cycloalkane etc., such as can enumerate pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane,
Pentamethylene, hexamethylene, cycloheptane, cyclooctane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro
Decane, chloro hendecane, chlorinated dodecane and chlorocyclohexane etc., wherein it is preferred that pentane, hexane, decane and hexamethylene, optimal
Select hexane.
These solvents can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
According to the present invention, the consumption of the chemical treatment solvent is used as so that the complex carrier is relative to describedization
It is 1g with the ratio of solvent to learn processing:1-100ml, preferably 1g:2-40ml, but this is not limited to sometimes.In addition, before such as
It is described as a solution use chemical treatments when, the chemical treatment solvent can be suitably reduced according to actual conditions
Consumption, but be not particularly limited.
According to the present invention, be used as the consumption of the silicon compound so that the complex carrier in terms of Mg elements with Si
The mol ratio of the silicon compound of element meter reaches 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.05-0.25.
According to the present invention, be used as the consumption of the chemical treatments so that the complex carrier in terms of Mg elements with
The mol ratio of the chemical treatments of Group IVB elemental metal reaches 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:
0.10-0.30。
It is known that when being chemically treated carrier using Group IVB metallic compound, can be immobilized a certain amount of on this carrier
Group IVB metallic compound.The present inventor is had found by studying, in the immobilized Group IVB metallic compound, is had quite
A big part is rendered as inactive state, i.e. this part Group IVB metallic compound is for the loaded catalyst that finally manufactures
Olefinic polymerization catalysis activity do not contribute.Therefore, the present inventor further investigation revealed that, if used
During Group IVB metallic compound chemical treatment carrier and with the foregoing specific silicon compound of the present invention, the nothing can be significantly decreased
The ratio of active part or the supported quantity for significantly decreasing the Group IVB metallic compound on carrier, so as to correspondingly improve
The load capacity of Nonmetallocene complex or the load percentage relative to Group IVB metallic compound.As a result, with not having and described in
The situation of silicon compound is compared, and the present invention can significantly improve the support type finally obtained non-when the silicon compound
The olefinic polymerization catalysis activity of metallocene catalyst.In addition, present inventor has further discovered that, closed by and with the silication
Thing, can also realize the polymer molecular weight distribution that narrows, improve mechanical properties of polymer, and make comonomer in the polymer
Sequence distribution more regular function.These discoveries are Promethean in the art.
According to the present invention, do not have to the engagement sequence of the complex carrier and the silicon compound and the chemical treatments
Special to limit, such as this three can contact simultaneously, can also successively be contacted according to arbitrary order.
According to one preferred embodiment of the invention, in the presence of the chemical treatment solvent, make described compound
Carrier is first contacted with the silicon compound(First contact procedure), then add the chemical treatments and further connect
Touch(Second contact procedure), thus carry out described chemical treatment reaction.
As the ways of carrying out of first contact procedure, such as can enumerate under agitation, by the complex carrier and
The silicon compound is added in the chemical treatment solvent simultaneously or successively, at 0-100 DEG C(It is preferred that 20-80 DEG C)Under continue to stir
Mix and react and formed the mode of slurry.To the reaction time now, there is no particular limitation, such as can enumerate 0-6h,
It is preferred that 0.5-4h.
After slurry is obtained as previously described, the slurry is set further to be contacted with the chemical treatments(The
Two contact procedures).
It as the ways of carrying out of second contact procedure, such as can enumerate under agitation, be added into the slurry
(It is preferred that being added dropwise)The solution of the chemical treatments or the chemical treatments, and after the addition terminates, at 0-100 DEG C
(It is preferred that 20-80 DEG C)The lower mode for continuing to stir and react.To the reaction time now, there is no particular limitation, such as can lift
Go out 0.5-8h, preferably 1-4h.
After the chemical treatment reaction terminates, by being filtered, washed and dried, you can obtain and pass through chemically treated production
Thing(Modify complex carrier).
According to the present invention, described be filtered, washed and dried can be carried out using conventional method, and wherein washer solvent can be with
Using with chemical treatment solvent identical solvent.As needed, the general progress of the washing 1~8 time, preferably 2~6 times,
Most preferably 2~4 times.
The drying can be carried out using conventional method, such as under inert gas seasoning, boulton process or vacuum
Heat drying method, preferably inert gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum seasoning.It is described dry
Dry temperature range is generally normal temperature to 140 DEG C, and drying time is generally 2-20 hours, but is not limited to this.
According to the present invention, by making Nonmetallocene complex be connect with the modification complex carrier in the presence of the second solvent
Touch, be derived from the load type non-metallocene catalyst.
According to the present invention, term " Nonmetallocene complex " is a kind of single centre alkene for metallocene catalyst
Do not contain cyclopentadienyl groups such as luxuriant ring, fluorenes ring or indenes ring or derivatives thereof in polymerized hydrocarbon catalyst, structure, and with co-catalysis
Agent(Such as those described below)The metallo-organic compound of olefinic polymerization catalysis activity is can show that during combination(Therefore institute
State Nonmetallocene complex and be also sometimes referred to as non-metallocene olefin polymerization complex).The compound is former comprising central metal
Son and at least one multidentate ligand combined with the central metal atom with coordinate bond(It is preferred that tridentate ligand or more tooth is matched somebody with somebody
Body), and term " Nonmetallocene part " is foregoing multidentate ligand.
According to the present invention, the Nonmetallocene complex is selected from the compound with following chemical structural formula:
。
According to the chemical structural formula, include n group X and m with the part of central metal atom M formation coordinate bonds multiple tooth
Part(Structural formula in bracket).According to the chemical structural formula of the multidentate ligand, group A, D and E(Coordination group)Pass through
Coordination atom contained by these groups(The hetero atoms such as such as N, O, S, Se and P)It is coordinated with central metal atom M formation
Key.
According to the present invention, all parts(Including the group X and the multidentate ligand)Institute's band negative electrical charge sum it is exhausted
It is identical with the absolute value that the central metal atom M is positively charged to being worth.
In one more specifically embodiment, the Nonmetallocene complex is selected from following chemical structural formula
Compound(A)And compound(B).
With
(A) (B)。
In one more specifically embodiment, the Nonmetallocene complex is selected from following chemical structural formula
Compound(A-1)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 all of above chemical structural formula,
Q is 0 or 1;
D is 0 or 1;
M is 1,2 or 3;
M is the central metal atom selected from periodic table of elements III-th family to XI races metallic atom, preferably the IVth B races gold
Belong to atom, such as can enumerate Ti (IV), Zr (IV), Hf (IV), Cr (III), Fe (III), Ni (II), Pd (II) or Co (II);
N is 1,2,3 or 4, depending on the valence state of the central metal atom M;
X is selected from halogen, hydrogen atom, C1- C30Alkyl, the C of substitution1- C30Alkyl, oxy radical, nitrogen-containing group, containing sulfenyl
Group, boron-containing group, group containing aluminium base, phosphorus-containing groups, silicon-containing group, germanic group or containing tin group, multiple X can also may be used with identical
, can also bonding or cyclization each other with difference;
A be selected from oxygen atom, sulphur atom, selenium atom,、-NR23R24、-N(O)R25R26、、-PR28R29、-P(O)
R30OR31, sulfuryl, sulfoxide group or-Se (O) R39, wherein N, O, S, Se and P be respectively coordination atom;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C1- C30Alkyl;
D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C1- C30Alkyl,
Sulfuryl or sulfoxide group, wherein N, O, S, Se and P are respectively coordination atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group(-CN), wherein N, O,
S, Se and P are respectively coordination atom;
F be 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 respectively coordination atom;
G is selected from C1- C30Alkyl, the C of substitution1- C30Alkyl or safing function group;
Y be selected from oxygen atom, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S,
Se and P are respectively coordination atom;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group(-CN), such as can be with
Enumerate-NR23R24、-N(O)R25R26、-PR28R29、-P(O)R30R31、-OR34、-SR35、-S(O)R36、-SeR38Or-Se (O) R39,
Wherein N, O, S, Se and P are respectively coordination atom;
Represent singly-bound or double bond;
- represent covalent bond or ionic bond;
Represent coordinate bond, covalent bond or ionic bond.
R1To R4、R6To R36、R38And R39It is each independently selected from hydrogen, C1- C30Alkyl, the C of substitution1- C30Alkyl(Wherein
It is preferred that halohydrocarbyl, such as-CH2Cl and-CH2CH2Cl)Or safing function group.Above-mentioned group to each other can be with identical
With difference, wherein adjacent group such as R1With R2, R6With R7, R7With R8, R8With R9, R13With R14, R14With R15, R15With R16, R18With
R19, R19With R20, R20With R21, R23With R24, or R25With R26Etc. can combine togather bonding or cyclization, it is preferably formed as
Aromatic ring, such as unsubstituted phenyl ring or by 1-4 C1- C30Alkyl, the C of substitution1- C30Alkyl(Wherein preferred halogenated hydrocarbons
Base, such as-CH2Cl and-CH2CH2Cl)Or the phenyl ring of safing function substituent group, and
R5Lone pair electrons, hydrogen, C on nitrogen1- C30Alkyl, the C of substitution1- C30Alkyl, oxy radical, sulfur-containing group,
Nitrogen-containing group, containing seleno group or phosphorus-containing groups.Work as R5For oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorous-containigroups groups
During group, R5In N, O, S, P and Se can be used as coordination atom(It is coordinated with the central metal atom M).
In the context of the present invention, the safing function group can such as be enumerated selected from halogen, oxy radical, contained
Nitrogen groups, silicon-containing group, germanic group, sulfur-containing group, containing tin group, C1- C10Ester group or nitro(-NO2)At least one
Deng, but do not include C generally1- C30Alkyl and the C of substitution1- C30Alkyl.
In the context of the present invention, limited by the chemical constitution of multidentate ligand of the present invention, the safing function
Group has the characteristics that:
(1)Described group A, D, E, F, Y or Z and the central metal atom M complexation process are not disturbed, and
(2)It is less than described A, D, E, F, Y and Z group with the coordination ability of the central metal atom M, and does not replace this
The coordination of a little groups and the central metal atom M.
It is as the case may be, any adjacent two or more in foregoing all chemical structural formulas according to the present invention
Group, such as R21With group Z, or R13With group Y, can combine togather cyclization, be preferably formed as comprising coming from institute
State group Z or Y heteroatomic C6- C30Heteroaromatic, such as pyridine ring etc., wherein the heteroaromatic is optionally by 1
Or it is multiple selected from C1- C30Alkyl, the C of substitution1- C30The substituent substitution of alkyl and safing function group.
In the context of the present invention, the halogen is selected from F, Cl, Br or I.The nitrogen-containing group is selected from、-
NR23R24、-T-NR23R24Or-N (O) R25R26.The phosphorus-containing groups are selected from、-PR28R29、-P(O)R30R31Or-P (O) R32
(OR33).The oxy radical is selected from hydroxyl ,-OR34With-T-OR34.The sulfur-containing group is selected from-SR35、-T-SR35、-S(O)R36
Or-T-SO2R37.The group containing seleno is selected from-SeR38、-T-SeR38、-Se(O)R39Or-T-Se (O) R39.The group T is selected from
C1- C30Alkyl, the C of substitution1- C30Alkyl or safing function group.The R37Selected from hydrogen, C1- C30Alkyl, substitution
C1- C30Alkyl or safing function group.
In the context of the present invention, the C1- C30Alkyl is selected from C1- C30Alkyl(It is preferred that C1- C6Alkyl, such as it is different
Butyl)、C7- C30Alkaryl(Such as tolyl, xylyl, diisobutyl phenyl etc.)、C7- C30Aralkyl(Such as benzyl
Base)、C3- C30Cyclic alkyl, C2- C30Alkenyl, C2- C30Alkynyl, C6- C30Aryl(Such as phenyl, naphthyl, anthryl etc.)、
C8- C30Condensed ring radical or C4- C30Heterocyclic radical, wherein the heterocyclic radical, which contains 1-3, is selected from nitrogen-atoms, oxygen atom or sulphur atom
Hetero atom, such as pyridine radicals, pyrrole radicals, furyl or thienyl etc..
It is in the context of the present invention, described according to the concrete condition to its related group combined according to the present invention
C1- C30Alkyl is sometimes referred to as C1- C30Hydrocarbon diyl(Divalent group, or referred to as C1- C30Alkylene)Or C1- C30The base of hydrocarbon three
(Trivalent radical), this is obvious to those skilled in the art.
In the context of the present invention, the substituted C1- C30Alkyl refers to carrying one or more inert substituents
C1- C30Alkyl.So-called inert substituent, refers to these substituents to aforementioned coordinative group(Refer to foregoing group A,
D, E, F, Y and Z, or also optionally include group R5)There is no substantial dry with the complexation process of the central metal atom M
Disturb;In other words, limited by the chemical constitution of multidentate ligand of the present invention, these substituents have no ability to or had no chance
(Such as influenceed by steric hindrance etc.)Occur complexation reaction with the central metal atom M and form coordinate bond.In general, institute
State inert substituent and be such as selected from halogen or C1- C30Alkyl(It is preferred that C1- C6Alkyl, such as isobutyl group).
In the context of the present invention, the boron-containing group is selected from BF4 -、(C6F5)4B-Or (R40BAr3)-;It is described to contain aluminium base
Group is selected from alkyl aluminum, AlPh4 -、AlF4 -、AlCl4 -、AlBr4 -、AlI4 -Or R41AlAr3 -;The silicon-containing group be selected from-
SiR42R43R44Or-T-SiR45;The germanic group is selected from-GeR46R47R48Or-T-GeR49;It is described containing tin group be selected from-
SnR50R51R52、-T-SnR53Or-T-Sn (O) R54, wherein Ar represents C6- C30Aryl.R40To R54Be each independently selected from hydrogen, it is preceding
The C stated1- C30Alkyl, foregoing substituted C1- C30Alkyl or foregoing safing function group, above-mentioned group to each other may be used
With it is identical can also be different, wherein adjacent group can combine togather bonding or cyclization.Wherein, group T definition is same
Before.
As the Nonmetallocene complex, such as it can enumerate following compound:
、 、 、
、 、 、
、 、 、
、 、 、
、 、 、
、 、 、
、 、 、
、 、 、
、 、 、
、 、 、
、 、
With。
The Nonmetallocene complex is preferably selected from following compound:
、 、 、
、 、 、
、 With。
The Nonmetallocene complex is further preferably selected from following compound:
、 、 、
、 With。
The Nonmetallocene complex is more preferably selected from following compound:
With。
These Nonmetallocene complexs can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
According to the present invention, the multidentate ligand in the Nonmetallocene complex be not in this area as electronics to
The usually used diether compounds of body compound.
The Nonmetallocene complex or the multidentate ligand can be according to any methods well known by persons skilled in the art
Manufactured.On the particular content of its manufacture method, such as it can be found in WO03/010207 and Chinese patent
ZL01126323.7 and ZL02110844.7 etc., this specification introduces the full text of these documents as reference with regard to this.
According to the present invention, in order to measure with it is easy to operate, the Nonmetallocene complex is when necessary as a solution
Use.
When preparing the solution of the Nonmetallocene complex, to solvent now used, there is no particular limitation, as long as
The Nonmetallocene complex can be dissolved.As the solvent, such as it can enumerate C6-12Aromatic hydrocarbon, halo C6-12Virtue
Fragrant hydrocarbon, halo C1-10One or more in alkane, ester and ether.Specifically it can such as enumerate toluene, dimethylbenzene, trimethylbenzene, second
Benzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene, bromo ethylbenzene, dichloromethane, dichloroethanes, ethyl acetate and four
Hydrogen furans etc..Wherein, preferably C6-12Aromatic hydrocarbon, dichloromethane and tetrahydrofuran.
These solvents can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
, can be as needed using stirring when dissolving the Nonmetallocene complex(The rotating speed of the stirring is generally 10
~500 revs/min).
According to the present invention, it is convenient that, the Nonmetallocene complex is generally 0.02 relative to the ratio of the solvent
~0.30 grams per milliliter, preferably 0.05~0.15 grams per milliliter, but this is not limited to sometimes.
It is used as the side for making the Nonmetallocene complex be contacted with the modification complex carrier in the presence of the second solvent
Formula, such as can enumerate following manner.
First, the modification complex carrier is made to be contacted with the Nonmetallocene complex in the presence of the second solvent(Connect
Touch reaction), obtain the second mixed serum.
When manufacturing second mixed serum, to the modification complex carrier and the Nonmetallocene complex(And
Second solvent)The way of contact and engagement sequence etc. there is no particular limitation, such as can enumerate makes the modification compound
Carrier is first mixed with the Nonmetallocene complex, then adds the scheme of second solvent thereto again;Or make described
Nonmetallocene complex is dissolved in second solvent, thus manufactures Nonmetallocene complex solution, and described repair then is made again
Scheme that decorations complex carrier is mixed with the Nonmetallocene complex solution etc., wherein it is preferred that the latter.
In addition, in order to manufacture second mixed serum, such as can be in normal temperature to less than used any solvent
At a temperature of boiling point, make contact of the modification complex carrier with the Nonmetallocene complex in the presence of second solvent
Reaction(If necessary by stirring)Carry out 0.5~24 hour, preferably 1~8 hour, more preferably 2~6 hours.
Now, the second mixed serum obtained is a kind of system of pulpous state.Although not necessarily, in order to ensure system
Uniformity, second mixed serum is preferred after preparation to carry out certain time(2~48h, preferably 4~24h, most preferably 6~
18h)Closed standing.
According to the present invention, when manufacturing second mixed serum or carrying out the contact, to second solvent(With
Lower sometimes referred to as dissolving Nonmetallocene complex solvent)There is no particular limitation, as long as it can dissolve the Nonmetallocene
Complex.As second solvent, such as it can enumerate C6-12Aromatic hydrocarbon, halo C6-12Aromatic hydrocarbon, halo C1-10Alkane
With the one or more in ether.Specifically it can such as enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chlorine
For ethylbenzene, bromotoluene, bromo ethylbenzene, dichloromethane, dichloroethanes and tetrahydrofuran etc..Wherein, preferably C6-12Aromatic hydrocarbon, two
Chloromethanes and tetrahydrofuran, most preferably dichloromethane.
These solvents can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
, can be as needed using stirring when manufacturing second mixed serum or the Nonmetallocene complex solution
(The rotating speed of the stirring is generally 10~500 revs/min).
According to the present invention, there is no any restriction to the consumption of second solvent, as long as it is enough to realize the modification
The amount that complex carrier is fully contacted with the Nonmetallocene complex.Such as, it is convenient that, the Nonmetallocene complex
Ratio relative to second solvent is generally 0.01~0.25 grams per milliliter, preferably 0.05~0.16 grams per milliliter, but sometimes
It is not limited to this.
Then, by the way that to the second mixed serum convection drying, a kind of solid product of good fluidity can be obtained,
That is load type non-metallocene catalyst of the invention.
Now, the convection drying can be carried out using conventional method, such as dry, vacuum atmosphere under inert gas atmosphere
Heat drying etc. under lower drying or vacuum atmosphere, wherein it is preferred that heat drying under vacuum atmosphere.The drying is general than institute
State the temperature of 5~15 DEG C of the low boiling point of any solvent contained in mixed serum(Generally 30~160 DEG C, preferably 60~130
℃)It is lower to carry out, and drying time is generally 2~24h, but this is not limited to sometimes.
According to the present invention, as needed, be optionally additionally included in makes the preparation method of the load type non-metallocene catalyst
Before the complex carrier is contacted with the silicon compound and the chemical treatments, with selected from aikyiaiurnirsoxan beta, alkyl aluminum or its
The step of helping the chemical treatments pretreatment complex carrier of meaning combination(Pre-treatment step).
In the context of the present specification, unless specifically stated otherwise it is or substantially unreasonable, without exception by by the pretreatment
Complex carrier is also referred to as complex carrier.
Chemical treatments are helped to be specifically described to described below.
According to the present invention, chemical treatments are helped as described, such as can enumerate aikyiaiurnirsoxan beta and alkyl aluminum.
As the aikyiaiurnirsoxan beta, such as it can enumerate following formulas(I)Shown linear alumoxanes:(R)(R)Al-(Al
(R)-O)n- O-Al (R) (R), and following formulas(II)Shown Cyclic aluminoxane:-(Al(R)-O-)n+2-。
(I)(II)
In aforementioned formula, group R is same to each other or different to each other(It is preferred that identical), it is each independently selected from C1-C8Alkyl, it is excellent
Select methyl, ethyl and isobutyl group, most preferable;N is any in the range of the arbitrary integer in the range of 1-50, preferably 10~30
Integer.
As the aikyiaiurnirsoxan beta, preferably MAO, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta,
Further preferred MAO and isobutyl aluminium alkoxide.
These aikyiaiurnirsoxan betas can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
As the alkyl aluminum, such as it can enumerate the compound shown in below formula:
Al(R)3
Wherein, group R is same to each other or different to each other(It is preferred that identical), and it is each independently selected from C1-C8Alkyl, preferably first
Base, ethyl and isobutyl group, most preferable.
Specifically, as the alkyl aluminum, such as trimethyl aluminium can be enumerated(Al(CH3)3), triethyl aluminum(Al
(CH3CH2)3), tri-n-n-propyl aluminum(Al(C3H7)3), triisopropylaluminiuand(Al(i-C3H7)3), triisobutyl aluminium(Al(i-C4H9)3)、
Three n-butylaluminums(Al(C4H9)3), triisopentyl aluminium(Al(i-C5H11)3), three n-pentyl aluminium(Al(C5H11)3), tri-n-hexyl aluminum
(Al(C6H13)3), three isohesyl aluminium(Al(i-C6H13)3), diethylmethyl aluminium(Al(CH3)(CH3CH2)2)And dimethyl ethyl
Aluminium(Al(CH3CH2)(CH3)2)Deng wherein it is preferred that trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, most preferably three
Aluminium ethide and triisobutyl aluminium.
These alkyl aluminums can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
According to the present invention, chemical treatments are helped as described, it is possible to use only the aikyiaiurnirsoxan beta, can also be only with described
Alkyl aluminum, but it is also possible to using the aikyiaiurnirsoxan beta and any mixture of the alkyl aluminum.Moreover, to each component in the mixture
Ratio there is no particular limitation, can arbitrarily select as needed.
It is described to help what chemical treatments were usually used as a solution according to the present invention.Chemistry is being helped described in preparation
During the solution of inorganic agent, to now used solvent, there is no particular limitation, as long as it, which can dissolve this, helps chemical treatments
And do not destroy(Such as dissolve)The existing carrier structure of the complex carrier.
Specifically, C can be enumerated5-12Alkane, C5-12Cycloalkane, halo C5-12Alkane and halo C5-12Cycloalkane etc., than
Pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, pentamethylene, hexamethylene, cycloheptane, ring can such as be enumerated
Octane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro hendecane, chloro ten
Dioxane and chlorocyclohexane etc., wherein it is preferred that pentane, hexane, decane and hexamethylene, most preferably hexane.
These solvents can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
In addition, to the concentration for helping chemical treatments in its solution, there is no particular limitation, can fit as needed
Work as selection, as long as it can realize to help chemical treatments to carry out the pre-treatment step described in scheduled volume.
It as the method for carrying out the pre-treatment step, such as can enumerate, prepare described help chemical treatments first
Solution, then to intending with metered in the complex carrier for helping chemical treatments pretreatment(It is preferred that being added dropwise)It is described
Help chemical treatment agent solution(Wherein containing helping chemical treatments described in scheduled volume), or to described help chemical treatment agent solution
In the metered complex carrier, be consequently formed reaction mixture.Now, reaction temperature is generally -40 ~ 60 DEG C, preferably -30
~ 30 DEG C, the reaction time is generally 1 ~ 8h, most preferably preferably 2 ~ 6h, 3 ~ 4h(If necessary by stirring).Then, by filtering, washing
Wash and dry, the complex carrier by pretreatment is isolated from the reaction mixture.Then, using answering that the process is pre-processed
Carrier is closed, according to describing exact same way before, the contact with silicon compound and chemical treatments is carried out.
According to the present invention, described be filtered, washed and dried can be carried out using conventional method, and wherein washer solvent can be with
Identical solvent used during using with helping chemical treatments described in dissolving.As needed, the general progress of the washing 1~8 time, preferably
2~6 times, most preferably 2~4 times.The drying can be carried out using conventional method, such as inert gas seasoning, vacuum drying
Method or heating under vacuum seasoning, preferably inert gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum
Seasoning.The temperature range of the drying is generally normal temperature to 140 DEG C, and drying time is generally 2-20 hours, but is not limited to
This.
According to the present invention, the consumption of first solvent is used as so that the ratio of the magnesium compound and first solvent
Example is 1mol:75~400ml, preferably 1mol:150~300ml, more preferably 1mol:200~250ml.
According to the present invention, the consumption of the alcohol is used as so that the magnesium compound in terms of Mg elements rubs with the alcohol
You are than being 1:0.02~4.00, preferably 1:0.05~3.00, more preferably 1:0.10~2.50.
According to the present invention, the consumption of the porous carrier is used as so that the magnesium compound in terms of magnesium compound solid
Mass ratio with the porous carrier is 1:0.1-20, preferably 1:0.5-10.
According to the present invention, the consumption of the precipitating reagent is used as so that the volume ratio of the precipitating reagent and first solvent
For 1:0.2~5, preferably 1:0.5~2, more preferably 1:0.8~1.5.
According to the present invention, be used as the consumption of the silicon compound so that the complex carrier in terms of Mg elements with Si
The mol ratio of the silicon compound of element meter is 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.05-0.25.
According to the present invention, be used as the consumption of the chemical treatments so that the complex carrier in terms of Mg elements with
The mol ratio of the chemical treatments of Group IVB elemental metal is 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:
0.10-0.30。
According to the present invention, the consumption of the Nonmetallocene complex is used as so that the complex carrier in terms of Mg elements
Mol ratio with the Nonmetallocene complex is 1:0.01-1, preferably 1:0.04-0.4, more preferably 1:0.08-0.2.
According to the present invention, be used as the consumption for helping chemical treatments so that the complex carrier in terms of Mg elements with
To help the mol ratio of chemical treatments as 1 described in Al elements are counted:0-1.0, preferably 1:0-0.5, more preferably 1:0.1-0.5.
Known to those skilled in the art to be, foregoing all method and steps are preferably in the bar of substantially anhydrous and oxygen-free
Carried out under part.Substantially anhydrous and oxygen-free mentioned here refers to the content of system reclaimed water and oxygen continuously less than 100ppm.Moreover,
The load type non-metallocene catalyst of the present invention usually requires pressure-fired inert gas in confined conditions after preparation(Such as nitrogen
Gas, argon gas, helium etc.)In the presence of save backup.
According to the present invention, in foregoing manufacture method A and manufacture method B, the co-catalyst is selected from aikyiaiurnirsoxan beta, alkane
At least one of base aluminium, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, are preferably selected from aikyiaiurnirsoxan beta and alkyl aluminum
At least one of.
As the aikyiaiurnirsoxan beta, such as it can enumerate formula (R) (R) Al- (Al (R)-O)nLine shown in-O-Al (R) (R)
Type aikyiaiurnirsoxan beta, or formula-(Al (R)-O-)n+2- shown Cyclic aluminoxane.
In aforementioned formula, group R is same to each other or different to each other(It is preferred that identical), it is each independently selected from C1-C8Alkyl, it is excellent
Select methyl, ethyl and isobutyl group, most preferable.N is any in the range of the arbitrary integer in the range of 1-50, preferably 10~30
Integer.
As the aikyiaiurnirsoxan beta, preferably MAO, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta,
Further preferred MAO and isobutyl aluminium alkoxide, and most preferable aikyiaiurnirsoxan beta.
These aikyiaiurnirsoxan betas can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
As the alkyl aluminum, such as it can enumerate the compound shown in below formula:
Al(R)3
Wherein, group R is same to each other or different to each other(It is preferred that identical), and it is each independently selected from C1-C8Alkyl, preferably first
Base, ethyl and isobutyl group, most preferable.
Specifically, as the alkyl aluminum, such as trimethyl aluminium can be enumerated(Al(CH3)3), triethyl aluminum(Al
(CH3CH2)3), tri-n-n-propyl aluminum(Al(C3H7)3), triisobutyl aluminium(Al(i-C4H9)3), three n-butylaluminums(Al(C4H9)3), three
Isopentyl aluminium(Al(i-C5H11)3), three n-pentyl aluminium(Al(C5H11)3), tri-n-hexyl aluminum(Al(C6H13)3), three isohesyl aluminium
(Al(i-C6H13)3), diethylmethyl aluminium(Al(CH3)(CH3CH2)2)With dimethyl ethyl aluminium(Al(CH3CH2)(CH3)2)Deng,
Wherein preferred trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum and triisobutyl aluminium, further preferred triethyl aluminum and triisobutyl
Aluminium, and most preferably triethyl aluminum.
These alkyl aluminums can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
As the haloalkyl aluminium, such as it can enumerate the compound shown in below formula:
Al(R)nX3-n
Wherein, group R is same to each other or different to each other(It is preferred that identical), and it is each independently selected from C1-C8Alkyl, preferably first
Base, ethyl and isobutyl group, most preferable.Group X is halogen, preferably chlorine.N is 1 or 2.
Specifically, as the haloalkyl aluminium, such as a Chlorodimethyl aluminium can be enumerated(Al(CH3)2Cl), dichloro
Aluminium methyl(Al(CH3)Cl2)), aluminium diethyl monochloride(Al(CH3CH2)2Cl), ethyl aluminum dichloride(Al(CH3CH2)Cl2), a chlorine two
Propyl group aluminium(Al(C3H7)2Cl), two chloropropyl aluminium(Al(C3H7)Cl2)), a chlorine di-n-butyl aluminium(Al(C4H9)2Cl), dichloro just
Butyl aluminium(Al(C4H9)Cl2), a chloro-di-isobutyl aluminum(Al(i-C4H9)2Cl), dichloro aluminium isobutyl(Al(i-C4H9)Cl2), one
The n-pentyl aluminium of chlorine two(Al(C5H11)2Cl), dichloro n-pentyl aluminium(Al(C5H11)Cl2), a chlorine diisoamyl aluminium(Al(i-C5H11)2Cl), dichloro isopentyl aluminium(Al(i-C5H11)Cl2), a chlorine di-n-hexyl aluminium(Al(C6H13)2Cl), dichloro n-hexyl aluminium(Al
(C6H13)Cl2), the isohesyl aluminium of a chlorine two(Al(i-C6H13)2Cl), dichloro isohesyl aluminium(Al(i-C6H13)Cl2)、
Chloromethyl aluminium ethide(Al(CH3) (CH3CH2)Cl), chloromethyl propyl group aluminium(Al(CH3) (C3H7)Cl), one
Chloromethyl n-butylaluminum(Al(CH3) (C4H9)Cl), chloromethyl aluminium isobutyl(Al(CH3) (i-C4H9)Cl), a chloroethyl
Propyl group aluminium(Al(CH2CH3) (C3H7)Cl), a chloroethyl n-butylaluminum(AlCH2CH3)(C4H9)Cl), chloromethyl aluminium isobutyl
(AlCH2CH3)(i-C4H9)Cl)Deng, wherein it is preferred that aluminium diethyl monochloride, ethyl aluminum dichloride, a chlorine di-n-butyl aluminium, dichloro just
Butyl aluminium, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl, a chlorine di-n-hexyl aluminium, dichloro n-hexyl aluminium, further preferred chlorine two
Aluminium ethide, ethyl aluminum dichloride and a chlorine di-n-hexyl aluminium, and most preferably aluminium diethyl monochloride.
These haloalkyl aluminium can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
, can be directly using commonly used in the art as the boron fluothane, the boron alkyl and the boron alkyl ammonium salt
Those, be not particularly limited.
In addition, according to the present invention, the co-catalyst can be used alone one kind, can also arbitrarily it compare as needed
A variety of foregoing co-catalysts are applied in combination in example, are not particularly limited.
,, such as can be with as the solvent for polymerization in foregoing manufacture method A and manufacture method B according to the present invention
Enumerate this area carry out slurry olefin polymerization when it is conventional use of those, be not particularly limited.Specifically, as institute
Solvent for polymerization is stated, such as can enumerate C4-10Alkane(Such as butane, pentane, hexane, heptane, octane, nonane or decane etc.)、
Halo C1-10Alkane(Such as dichloromethane)、C6-12Cycloalkane(Hexamethylene, cycloheptane, cyclooctane, cyclononane or cyclodecane)、
C6-20Aromatic hydrocarbon(Such as toluene and dimethylbenzene)Deng.Wherein, pentane, hexane, heptane or hexamethylene are preferably used as described poly-
Share solvent, most preferably hexane.
These solvent for polymerization can be used alone one kind, or be applied in combination with arbitrary ratio a variety of.
,, such as can be with as the consumption of the solvent for polymerization in described step A or step A' according to the present invention
Enumerate 10 ~ 400 liters of solvent for polymerization/gram major catalyst, preferably 20 ~ 200 liters solvent for polymerization/gram major catalysts, more preferably 50 ~
150 liters of solvent for polymerization/gram major catalysts, but this is not limited to sometimes.The step B or step B' are also required to mend as previously described
When filling solvent for polymerization, the specific consumption of its solvent for polymerization similar can also be set.
According to the present invention, in described step A or step A', as the consumption of the co-catalyst, it is general cause with
The mol ratio of the co-catalyst of aluminium or boron meter and the major catalyst in terms of the central metal atom reaches 1~
1000:1, preferably 5~500:1, more preferably 10~100:1, but this is not limited to sometimes.For example preceding institute of step B or step B'
State be also required to supplement co-catalyst when, the specific consumption of its co-catalyst similar can also be set.
In the manufacture method A and manufacture method B that state before this invention, material point can be easy to as needed using stirring
Dissipate or reaction is uniform, this can be carried out according to well known to a person skilled in the art mode.
For the manufacture method A and manufacture method B of foregoing ethene-alpha-olefin copolymer of the present invention, except this
In specification beyond the foregoing content particularly pointed out, other technology contents do not explained(Such as slurry polymerization process ways of carrying out, stir
Mix mode, polymerization type of reactor, monomer feed mode, master/co-catalyst feeding manner, copolymer product discharge method
Deng), those conventionally known in the art can be directly applicable, are not particularly limited, the description thereof will be omitted herein.
The ethene-alpha-olefin copolymer of the present invention can be total to by the ethene-alpha-olefin of foregoing manufacture method A manufactures
The polymers A or ethene-alpha-olefin copolymer B or the ethene-alpha-olefin manufactured by foregoing manufacture method B
Copolymer A and the arbitrary proportion mixture of the ethene-alpha-olefin copolymer B.
Further, the invention further relates to a kind of polymer composition, it is total to comprising the foregoing ethene-alpha-olefin of the present invention
Polymers and antioxidant.
According to the present invention, as the antioxidant, such as can enumerate it is known in the art it is any can by it is conventional close
Into or commercialization sale antioxidant, be not particularly limited.It is known that the antioxidant is usual by primary antioxidant and auxiliary
Antioxidant is constituted, but using only the primary antioxidant can also be used as the antioxidant without using auxiliary anti-oxidant sometimes.
According to the present invention, the gross weight using the polymer composition is counts, and the antioxidant is in the combination of polymers
Content in thing is generally 0.05-1.0wt%, preferably 0.1-0.5wt%, is not particularly limited.In addition, the auxiliary anti-oxidant
0~6 is generally with the mass ratio of the antioxidant:1, preferably 0.5~3:1, it is not particularly limited.
According to the present invention, the primary antioxidant is selected from least one of hindered phenol compound and aromatic amine compounds.
As the primary antioxidant, such as it can enumerate:
2,6- di-tert-butyl methyl phenols(Article number:Antioxidant BHT),
β-(4- hydroxyl -3,5- di-tert-butyl-phenyls) positive octadecanol ester of propionic acid(Article number:Antioxidant 1076),
Styrene phenol(Article number:Antioxidant SP),
2,4,6- tri-butyl-phenols(Article number:Antioxidant 246),
DBPC 2,6 ditertiary butyl p cresol(Article number:Antioxidant BHA),
Tert-butylhydroquinone (article number:Antioxidant TBHQ),
3,5- di-tert-butyl-4-hydroxyl benzyl diethyl phosphates(Article number:Antioxidant 1222),
β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid isooctanol ester(Article number:Antioxidant 1135),
2,2' methylene bis (4- methyl-6-tert-butylphenols)(Article number:Antioxidant 2246),
2,2'- thiobis (4- methyl-6-tert-butylphenols)(Article number:Antioxidant 2246 S),
4,4'- thiobis (3 methy 6 tert butyl phenol)(Article number:Antioxidant 300),
1,3,5- trimethyl -2,4,6- tri-(3,5- di-tert-butyl-4-hydroxyl benzyls)Benzene(Article number:Antioxidant
330),
4,4- thiobis(2- methyl-6-tert-butylphenols)(Article number:Antioxidant 736),
4,4' methylene bis (2,6 di t butyl phenol)(Article number:Antioxidant 4426),
4,4'- butylidenes-bis- (6- tert-butyl-m-cresols),
Four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters(Article number:Antioxidant 1010),
2,4- bis--(n-octylthiomethylene) -6- methyl-phenols(Antioxidant 1520),
2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate](Article number:Antioxidant
1035),
4- [(the pungent sulfenyl -1,3,5- triazines -2- bases of 4,6- bis-) amino] -2,6- two (1,1- Methylethyls) phenol
(Article number:Antioxidant 565),
[[3,5- bis- (1,1- dimethyl ethyls) -4- hydroxy phenyls] methyl] butylmalonic acid two (1,2,2,6,
6- pentamethyl -4- piperidyls) ester,
3- (1,1- dimethyl ethyls)-β-[3- (1,1- dimethyl ethyls) -4- hydroxyphenyls] -4- hydroxy-betas-methylbenzene first
Acid -1,2- ethylidene esters,
[[3- (1,1- the dimethylethyls) -2- hydroxy-5-methyls phenyl]-octahydro -4,7- methylene -1H- indenes of 2,6- bis-
Base] -4- methylphenols, 4,4'- thiobis (5- methyl -2-TBP),
1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6 (1H,
3H, 5H)-triketone(Article number:Antioxidant 1790),
1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) -1,3,5- triazines -2,4,6 [1H, 3H, 5H] triketone
(Article number:Antioxidant 3114),
1,3,5- trimethyls -2,4,6- three (3,5 di-tert-butyl-4-hydroxyl benzyl) benzene(Article number:Antioxidant 330),
N, N'-1,6- hexylidene two [(1,1- the dimethyl ethyls) -4- hydroxyls of 3,5- bis- hydrocinnamamide](Article number:
Antioxidant 1098),
1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane(Article number:Antioxidant CA)、
Two [3- (1,1- dimethyl ethyls) -4- hydroxy-5-methyl bases benzenpropanoic acid] three polyethylene glycol(Article number:Antioxidant
245),
3,5- bis- (1,1- dimethyl ethyls) -4- hydroxy-benzenepropanoic acid -1,6- dihexyl esters(Article number:Antioxidant
259), and
Ethyl -3,5- di-t-butyl -4- hydroxybenzylphosphonic acid ester calcium salts(Article number:Antioxidant 1425).
According to the present invention, these primary antioxidants can be used alone one kind, can also multiple combinations use.
According to the present invention, the primary antioxidant, preferably hindered phenol compound, more preferably β-(4 hydroxyls -3,5 are used as
- di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid(Article number:Antioxidant 1076), four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] pentaerythritol ester(Article number:Antioxidant 1010)Or its combination, most preferably β-(4-hydroxyl-3,5-two
Tert-butyl-phenyl) the positive octadecanol ester article number of propionic acid:Antioxidant 1076).
According to the present invention, the one kind or many of the auxiliary anti-oxidant in phosphite ester kind antioxidant and sulfur-bearing antioxidant
Kind.
As the phosphite ester kind antioxidant, such as it can enumerate:
Three nonylated phenyl phosphite esters(Article number:Antioxidant TNP P),
(2,4- di-tert-butyl-phenyls) tris phosphite(Article number:Irgasfos 168),
Four (2,4- di-tert-butylphenols) -4,4'- xenyl diphosphites (article numbers:Antioxidant P-EPQ),
Distearyl pentaerythritol diphosphite(Article number:Antioxidant 618),
Pentaerythritol bis-phosphite two (2,4- di-tert-butyl phenyl) ester (antioxidant 626), and
Double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate (article numbers:Antioxidant PEP-36).
According to the present invention, these phosphite ester kind antioxidants can be used alone one kind, can also multiple combinations use.
As the sulfur-bearing antioxidant, such as it can enumerate:
Thio-2 acid 2 stearyl ester(DSTDP),
Dilauryl thiodipropionate(DLTDP),
Double 14 esters of thio-2 acid(DMTDP),
Double 13 esters of thio-2 acid(DTDTP),
Pentaerythrite four(3- lauryl thiopropionates)(Article number:Antioxidant 412S), and
Two (octadecyl) disulphide.
According to the present invention, these sulfur-bearing antioxidant can be used alone one kind, can also multiple combinations use.
It is used as the auxiliary anti-oxidant, preferably (2,4- di-tert-butyl-phenyl) tris phosphite(Article number:Irgasfos 168)、
Thio-2 acid 2 stearyl ester(DSTDP), dilauryl thiodipropionate(DLTDP)Or its combination, most preferably thio dipropyl
Sour distearyl alcohol ester(DSTDP).
, as needed, can also be comprising this area in manufacture polymer group in the polymer composition according to the present invention
Conventional use of various additives during compound, such as age resister, fire retardant, processing aid, anti-blocking agent, lubricant, the demoulding
Agent, plasticizer, antistatic additive, pigment, halogen-absorber and filler etc..These additives can be used alone, can also be two kinds
Or multiple combinations are used, it is not particularly limited.In addition, the consumption of the additive can use the conventional use of this area
Amount, there is no particular limitation, will not be repeated here.
Especially, one kind or many in pigment and halogen-absorber can be optionally included in polymer composition of the invention
Kind.
According to the present invention, as the pigment, such as the black pigments such as carbon black or yellow uitramarine can be enumerated and orange
The color pigments such as pigment, wherein it is preferred that carbon black.These pigment can be used alone one kind, can also multiple combinations use.Make
Used time, gross weight using the polymer composition is counts, content one of the black pigment in the polymer composition
As be 15-65wt%, and content of the color pigment in the polymer composition is generally 2.0-5.0wt%, not
It is special to limit.
According to the present invention, as the halogen-absorber, such as it can enumerate any halogen commonly used in the art and inhale
Agent is received, such as can further enumerate calcium stearate or zinc stearate etc..Gross weight using the polymer composition is counts, institute
Content of the halogen-absorber in the polymer composition generally 0-0.5wt%, preferably 0-0.3wt% are stated, it is not special
Restriction.
According to the present invention, in order to manufacture the polymer composition, by by the ethene-alpha-olefin copolymer, described
Antioxidant and the foregoing various additives used as needed(Especially pigment and/or halogen-absorber), according to predetermined
Usage ratio, is mixed according to method well known in the art(Such as melting mixing)To uniform, it is not particularly limited.
According to a further embodiment of the invention, it is related to a kind of moulded products, it is by this hair of melt-processed
Bright foregoing polymer composition is simultaneously molded with.As the forming method, such as it can enumerate conventionally known in the art
Any method, such as extrude, be molded, rotational moulding and molded etc., wherein it is preferred that single or double screw extrusion molding.As described
The condition of molding of single or double screw extrusion molding, there is no particular limitation, can directly be applicable those commonly used in the art,
Such as can be extruder barrel temperature at 150 DEG C -220 DEG C, die head temperature is in 200 DEG C -220 DEG C, hauling speed 80-150cm/
Min, preferably 100-120cm/min, but it is not limited to this.Or, as the example of the rotation molding, such as can enumerate by
Polymer composition is put into rotational moulding container, the method that rotational moulding is carried out at 150-300 DEG C of mould temperature, now molding cycle condition
For:Heat time 5-30 minute, time 1--20 minute, cool time 1-20 minute are flattened, but be not limited to this.
According to the present invention, the form to the moulded products is not particularly limited, such as can enumerate film, sheet material, appearance
Device(Bucket, disk, bottle etc.), tubing, section bar etc., wherein it is preferred that tubing, bucket and film, most preferably tubing.
Embodiment
The present invention is illustrated using embodiment in further detail below, but the present invention is not limited to these embodiments.
The heap density of copolymer(Unit is g/cm3)Determine:Carried out with reference to chinese national standard GB 1636-79.
The oligomer of copolymer is determined:Take out 1 liter of solvent in the filtrate center line that filters or centrifuge out, higher than
Under the conditions of solvent boiling point or closed vacuumize fully dries remaining material gross mass after solvent.
The fine powder of copolymer(Less than 75 microns)Assay:Using sieve method, the powder of the copolymer is passed through into 200 mesh
(75 microns of aperture)Sieved through sieve, fine powder quality after sieving divided by the gross mass of copolymer are measured.
The melt index of copolymer(190℃;Load is 2.16 kilograms, or if any clear and definite, load is 5 kilograms)Determine:Ginseng
The quasi- GB T 3682-2000 of sighting target are carried out(Unit is g/10min).
The molecular weight distribution mw/mn of copolymer is determined:Using the GPC V2000 types gel chromatography point of WATERS companies of the U.S.
Analyzer is measured, from 4 Agilent PLgel Olexis type chromatographic columns, with 1,2,4- trichloro-benzenes for mobile phase, is determined
When temperature be 150 DEG C.
The density measurement of copolymer:Reference standard GB/T 1033-86 are carried out(Unit is g/cm3).
The average grain diameter of copolymer is determined:Carried out on Beckman Coulter LS230 type laser particle size analyzers, its
Particle size determination scope is 0.04 ~ 2000 micron.
The processing characteristics evaluation of copolymer:By copolymer and antioxidant 1010(Four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] pentaerythritol ester), irgasfos 168((2,4- di-tert-butyl-phenyls) tris phosphite)With calcium stearate according to matter
The ratio than 100/0.1/0.2/0.1 is measured to be well mixed.The well mixed material is passed through into parallel equidirectional two-screw extruder
(Nanjing Rhea extrusion machinery equipment Co., Ltd CTE-35 types)Simultaneously pelletizing obtains corresponding pellet for melting extrusion, water-bath cooling.
Each section of temperature setting of double screw extruder be:185℃-200℃-215℃-225℃-225℃-225℃-230℃-230℃-
220℃-220℃(Head).After obtained pellet is dried 4 hours through 70 DEG C, double screw extruder is added to(Crouse Ma Fei
OD20-63mm)In, in -240 DEG C -235 DEG C of extrusion temperature 190 DEG C -210 DEG C -220 DEG C -230 DEG C(Die head)And extrusion linear speed
Continuously extruded under conditions of about 1 m/min, obtain the mm of the diameter 63 and mm of nominal wall thickness about 5.8 tubing.Squeezed in the twin-screw
The reading for going out the main frame ammeter of machine reaches stable state(Reading changes within positive and negative 0.1A)Afterwards, the main frame electric current of record now
(Unit is A).Main frame electric current is smaller, then the processing characteristics for evaluating the copolymer is better.
The polymerization activity of major catalyst is determined:After polymerisation terminates, by the polymerizate in reactor(Ethene-
Alpha olefin copolymer)Filter and dry, then weigh the quality of the polymerizate, with the polymerizate quality divided by master used
The ratio of the quality of catalyst represents its polymerization activity(Unit is kg polymer/g catalyst or kg polymer/gCat).
Metallic element in major catalyst(Such as Ti and Mg)Assay:Using ICP-AES methods.
The assay of Nonmetallocene part or complex in major catalyst:Using elemental microanalysis method.
The evaluation of major catalyst copolymerization effect:Major catalyst is divided into equal two parts, in identical polymeric reaction condition
Under, separately carry out closing and exist the ethene of comonomer and being total to for comonomer in the absence of the ethylene homo of comonomer
Polymerization, and the polymerization activity of the major catalyst in the case of two kinds is determined respectively.The difference of two kinds of polymerization activities numerically is anti-
Reflect the copolymerization effect of the major catalyst.If activity increase, shows that copolymerization effect is good, active increased amplitude is got over after copolymerization
Greatly, then its copolymerization effect is more notable, and activity reduction, then show that copolymerization effect is poor after such as copolymerization.
The environmental stress cracking resistance of polymer(ESCR)It is public in Britain Rayran according to GB/T 1842-2008 standards
Carried out on the RR/ESC resisting environmental stress and cracking instrument of department.
Plastics simply supported beam notch impact strength is rushed according to GB/T 1043-2008 in the Italian type pendulum of Ceast companies 7611
Hit on instrument and carry out, determined at 0 DEG C of v-notch sample.
Tensile yield strength is tensile property according to Instron5965 types omnipotent examination in the U.S.'s obtained by GB/T 1040-2006
Test on machine and carry out.
Full notch creep test(FNCT)Carried out, sampled from tubing, in German IPT companies according to ISO 16770
Tested on the full notch creep test machine of V1598-0006 types.The notch depth 1.6mm in the face of sample 4.Test temperature is 80 DEG C,
And the use of 2wt% Arkopal N-110 is test(ing) medium, test stress is 4.0MPa.Record the out-of-service time.
Embodiment 1
Magnesium compound uses anhydrous magnesium chloride, and the first solvent uses tetrahydrofuran, and alcohol uses ethanol, and porous carrier uses two
Silica, i.e. silica gel, the ES757 of model Ineos companies, 4h is persistently calcined under 600 DEG C, nitrogen atmosphere first by silica gel and
Thermal activation.Silicon compound uses tetraethoxy-silicane, and Group IVB chemical treatments use titanium tetrachloride(TiCl4), the use of the second solvent
Dichloromethane, Nonmetallocene complex use structure forCompound.
5 grams of magnesium compounds are weighed, are added to after the first solvent, alcohol is added, is completely dissolved obtains magnesium chemical combination at normal temperatures
Thing solution, then adds porous carrier, after stirring 2 hours, obtains the first mixed serum, is then uniformly heated to 90 DEG C, directly
Drying is vacuumized, complex carrier is obtained.
Obtained complex carrier is added in hexane solvent, silicon compound is added dropwise and in 30 minutes in normal temperature in lower 10 minutes
Group IVB chemical treatments are added dropwise to, after being then uniformly heated to 60 DEG C of isothermal reactions 2 hours, filtering, hexane solvent is washed 3 times,
Each consumption is identical with the quantity of solvent added before, finally vacuumizes drying at 60 DEG C, obtains modifying complex carrier.
At room temperature, Nonmetallocene complex is added in the second solvent, then adds modification complex carrier, stirring 4
Hour, then closed standing directly vacuumize drying after 12 hours under normal temperature, obtain load type non-metallocene catalyst.
Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:2;It is 1 with alcohol mol ratio in terms of Mg elements:
2;Proportioning with the first solvent is 1mol:210ml;The complex carrier in terms of Mg elements with Group IVB elemental metal
The mol ratio of the chemical treatments is 1:0.20;The complex carrier and the Nonmetallocene complex in terms of Mg elements
Mol ratio is 1:0.08;The mol ratio of the complex carrier counted using Mg elements and the silicon compound counted using Si elements is 1:0.1;Non- cyclopentadienyl
Metal complex is 0.1 grams per milliliter relative to the ratio of second solvent.
Load type non-metallocene catalyst is designated as CAT-1.
Embodiment 2
It is substantially the same manner as Example 1, but be with the following changes:
Complex carrier first passes through before being contacted with the silicon compound and the chemical treatments and helps chemical treatments three
The complex carrier that aluminium ethide processing is pre-processed.
That is, complex carrier is added in hexane solvent, then is slowly added dropwise and helps chemical treatments triethyl aluminum(Concentration is
0.88mol/L, hexane solution), stirring is filtered after 2 hours at 60 DEG C, and hexane is washed 3 times, each consumption with add before it is molten
Dosage is identical, finally vacuumizes drying at 60 DEG C, the complex carrier pre-processed.Complex carrier wherein in terms of Mg elements
With counted using Al elements help the mol ratio of chemical treatments as 1:0.2.
Load type non-metallocene catalyst is designated as CAT-2.
Embodiment 3
It is substantially the same manner as Example 1, but be with the following changes:
Complex carrier first passes through before being contacted with the silicon compound and the chemical treatments and helps chemical treatments first
The complex carrier that the processing of base aikyiaiurnirsoxan beta is pre-processed.
That is, complex carrier is added in toluene solvant, then is slowly added dropwise and helps chemical treatments MAO(Concentration is
10wt%, toluene solution), stirring is filtered after 2 hours at 60 DEG C, and toluene is washed 3 times, each consumption and the quantity of solvent added before
It is identical, drying finally is vacuumized at 100 DEG C, the complex carrier pre-processed.Complex carrier wherein in terms of Mg elements with
The mol ratio of chemical treatments is helped as 1 using what Al elements were counted:0.4.
Load type non-metallocene catalyst is designated as CAT-3.
Embodiment 4
It is substantially the same manner as Example 1, but be with the following changes:
Magnesium compound is changed to isobutoxy magnesium chloride(Mg(i-OC4H9)Cl), alcohol is changed to n-butanol, and the first solvent is changed into
Toluene, porous carrier changes into TiO2, 4h is persistently calcined under 400 DEG C, nitrogen atmosphere and thermal activation.It is different that silicon compound is changed to four
Butoxy silicon, chemical treatments are changed to zirconium chloride(ZrCl4).
Nonmetallocene complex is used, the second solvent is changed to toluene, and the first mixed serum changes into addition
Precipitating reagent hexane is allowed to complete precipitation, filters and 60 DEG C are washed after three times with precipitating reagent and vacuumize drying.
Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:1;It is 1 with alcohol mol ratio in terms of Mg elements:
1;Proportioning with the first solvent is 1mol:150ml;The complex carrier in terms of Mg elements with Group IVB elemental metal
The mol ratio of the chemical treatments is 1:0.30;The complex carrier and the Nonmetallocene complex in terms of Mg elements
Mol ratio is 1:0.10;The mol ratio of the complex carrier counted using Mg elements and the silicon compound counted using Si elements is 1:0.05, sink
The volume ratio of shallow lake agent and the first solvent is 1:1;Nonmetallocene complex is 0.06 gram/milli relative to the ratio of second solvent
Rise.
Load type non-metallocene catalyst is designated as CAT-4.
Embodiment 5
It is substantially the same manner as Example 1, but be with the following changes:
Magnesium compound changes into anhydrous magnesium bromide(MgBr2), alcohol changes into 2-Ethylhexyl Alcohol, the first solvent and the second solvent
Hexane is changed into, porous carrier uses alundum (Al2O3).Alundum (Al2O3) is persistently calcined 6h under 700 DEG C, nitrogen atmosphere.Silicon
Compound is changed to triethoxy chloro silicon, and chemical treatments are changed to titanium tetrabromide(TiBr4),
Nonmetallocene complex is used.First mixed serum is changed into directly takes out true at 105 DEG C
Sky is dried.
Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:5;It is 1 with alcohol mol ratio in terms of Mg elements:
0.7;Proportioning with the first solvent is 1mol:280ml;The complex carrier in terms of Mg elements with Group IVB elemental metal
The chemical treatments mol ratio be 1:0.10;The complex carrier and the Nonmetallocene complex in terms of Mg elements
Mol ratio be 1:0.05.The mol ratio of the complex carrier counted using Mg elements and the silicon compound counted using Si elements is 1:0.25;
Nonmetallocene complex is 0.05 grams per milliliter relative to the ratio of second solvent.
Load type non-metallocene catalyst is designated as CAT-5.
Embodiment 6
It is substantially the same manner as Example 1, but be with the following changes:
Magnesium compound changes into magnesium ethylate(Mg(OC2H5)2), the first solvent changes into dimethylbenzene, and porous carrier uses two
Silica-magnesias mixed oxide(Mass ratio 1:1).By silica-magnesia mixed oxide in 600 DEG C, argon gas
4h is persistently calcined under atmosphere.
Nonmetallocene complex is used, alcohol is changed to trichlorine methanol.Silicide is changed to four chlorinations
Silicon, the chemical treatments of Group IVB metallic compound change into tetraethyl titanium(Ti(CH3CH2)4), the first mixed serum, which is changed into, to be added
Enter precipitating reagent hexamethylene and be allowed to complete precipitation, filter and 80 DEG C are washed after three times with precipitating reagent and vacuumize drying.
Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:10;It is 1 with alcohol mol ratio in terms of Mg elements:
0.7;Proportioning with the first solvent is 1mol:200ml;The complex carrier in terms of Mg elements with Group IVB elemental metal
The chemical treatments mol ratio be 1:0.15;The complex carrier and the Nonmetallocene complex in terms of Mg elements
Mol ratio be 1:0.04;The mol ratio of the complex carrier counted using Mg elements and the silicon compound counted using Si elements is 1:0.14;
The volume ratio of precipitating reagent and the first solvent is 1:1.5;Nonmetallocene complex is 0.16 relative to the ratio of second solvent
Grams per milliliter.
Load type non-metallocene catalyst is designated as CAT-6.
Embodiment 7
It is substantially the same manner as Example 1, but be with the following changes:
Magnesium compound changes into magnesium ethide(Mg(C2H5)2), the first solvent changes into diethylbenzene, and alcohol changes into benzyl carbinol, many
Hole carrier uses montmorillonite.Montmorillonite is persistently calcined 8h under 400 DEG C, nitrogen atmosphere.Silicon compound is changed to tetramethoxy-silicane,
The chemical treatments of Group IVB metallic compound change into tetra-n-butyl titanium(Ti(C4H9)4), the use of Nonmetallocene complex, the first mixed serum is changed into directly vacuumizes drying at 130 DEG C.
Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:3;It is 1 with alcohol mol ratio in terms of Mg elements:
1.5;The complex carrier counted using Mg elements with using the mol ratio of the chemical treatments of Group IVB elemental metal as 1:
0.50;Magnesium compound and the first solvent burden ratio are 1mol:400ml;The complex carrier and the non-cyclopentadienyl gold in terms of Mg elements
The mol ratio of metal complex is 1:0.01;The mol ratio of complex carrier and the silicon compound in terms of Si elements in terms of Mg elements is
1:0.45.
Load type non-metallocene catalyst is designated as CAT-7.
Embodiment 8
It is substantially the same manner as Example 1, but be with the following changes:
Magnesium compound changes into ethylmagnesium chloride(Mg(C2H5)Cl), alcohol is changed to cyclohexanol, and the first solvent changes into hexamethylene
Alkane, porous carrier is using partial cross-linked(The degree of cross linking is 30%)Polystyrene.By the polystyrene under 85 DEG C, nitrogen atmosphere
Persistently dry 12h.Nonmetallocene complex is used, silicon compound be changed to by tetraethoxy-silicane and
Silicon tetrachloride is 1 according to mol ratio:1 mixture, the chemical treatments of Group IVB metallic compound change into three isobutoxy chlorine
Change titanium(TiCl(i-OC4H9)3).
Wherein proportioning is that magnesium compound is 1 with porous carrier mass ratio:0.5;In terms of Mg elements, it is with alcohol mol ratio
1:2.5;Proportioning with the first solvent hexane is 1mol:210ml;The complex carrier in terms of Mg elements with Group IVB metal
The mol ratio of the chemical treatments of element meter is 1:0.20;The complex carrier and the Nonmetallocene in terms of Mg elements
The mol ratio of complex is 1:0.20.The mol ratio of the complex carrier counted using Mg elements and the silicon compound counted using Si elements is 1:
0.02。
Load type non-metallocene catalyst is designated as CAT-8.
Reference example A
It is substantially the same manner as Example 1, but be with the following changes:
Complex carrier is handled without silicon compound in load type non-metallocene catalyst preparation process, but is directly added dropwise
Enter Group IVB chemical treatments to be handled;
Load type non-metallocene catalyst is designated as CAT-A.
Reference example B
It is substantially the same manner as Example 1, but be with the following changes:
The mol ratio of the complex carrier counted using Mg elements and the silicon compound counted using Si elements is 1:0.05.
Load type non-metallocene catalyst is designated as CAT-B.
Reference example C
It is substantially the same manner as Example 1, but be with the following changes:
The mol ratio of the complex carrier counted using Mg elements and the silicon compound counted using Si elements is 1:0.20.
Load type non-metallocene catalyst is designated as CAT-C.
Reference example D
It is substantially the same manner as Example 1, but be with the following changes:
Catalyst not load non-metallocene metal complex;
Load type non-metallocene catalyst is designated as CAT-D.
Application Example
By obtained load type non-metallocene catalyst CAT-1~8, CAT-A~D in the embodiment of the present invention respectively following
Under the conditions of carry out vinyl polymerization in accordance with the following methods:
Polymerizing condition is:5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents polymerize stagnation pressure 0.8MPa, gather
Close 85 DEG C of temperature;First stage:Hydrogen and ethylene gas ratio according to setting add a certain amount of hydrogen, and a certain amount of hexene-
1, being continually fed into ethene makes polymerization stagnation pressure constant in 0.8MPa, reacts the gas phase that reactor is laid down after the reaction time for reaching setting
Composition, the first stage stopping of reaction;Second stage:Second stage hydrogen and ethylene gas ratio according to setting add a certain amount of
Hydrogen, a certain amount of hexene -1, being continually fed into ethene makes polymerization stagnation pressure constant in 0.8MPa, and reaction reaches the reaction time of setting
Stop reaction, the second stage stopping of reaction afterwards.After reaction terminates, gas reactor is vented, kettle interpolymer is released, claimed after drying
Measure quality.The concrete condition and polymerization evaluation result of the polymerisation are as shown in table 1.
The polymer uniform particle sizes prepared from table 1, the method provided with the present invention, molecular weight distribution is appropriate, oligomeric
Thing content is low, and fine powder content is low.
By sequence number in table 11 and 5,6 result of the test data, the consumption of alpha-olefin is increased or decreased, can flexibly be adjusted
Save the content of comonomer in polymer.
The result of the test data of sequence number 1 and 3,4,5,6 are understood in contrast table 1, by changing two stage of reaction reaction gases
Atmosphere is constituted and the reaction time, can adjust containing for comonomer in reactivity, polymer molecular weight and its distribution and polymer
Amount, so as to illustrate that preparing polymer using the method that the present invention is provided has bigger adjustable range.
Sequence number 7,8 is sequence number 1 in the experimental result that one-part form homopolymerization and copolymerization are carried out using CAT-1, contrast table 1 in table 1
Result of the test data with 7,8 understand that the polymer obtained using two-stage method polymerization methodses has broader molecular weight distribution, therefore
The processing characteristics of polymer is more preferable.
By sequence number 1 in contrast table 1 and the result of the test data of comparative example sequence number 17, it is not added with catalyst preparation process
Enter silicon compound, the active and thus obtained polymer stacks density of polymerization catalyst is reduced, polymer molecular weight distribution broadens.
Pass through sequence number 1 in contrast table 1 and the result of the test data of comparative example sequence number 20 and 21, catalyst preparation process
In increased with the increase of silicon compound addition, the polymerization activity of catalyst and thus obtained polymer stacks density
Plus, polymer molecular weight distribution narrow, thus illustrating to have present invention introduces silicon compound effectively reduces invalid in catalyst
Active metallic content, while catalyst activity and polymer stacks density are improved, the effect of the polymer molecular weight that narrows distribution.
By sequence number 1 in contrast table 1 and the result of the test data of comparative example sequence number 22, in catalyst preparation process not
Nonmetallocene complex is introduced, thus obtained catalyst belongs to Ziegler-Natta type dynamics model catalyst, polymerization activity
It is relatively low with polymer stacks density, polymer molecular weight wider distribution.
Rotation molding embodiment
Polymer P E-5 or PE-19, each with relative to the polymer be 0.2wt% antioxidant 2,6- di-t-butyls pair
Methylphenol(Article number:Antioxidant BHT)Polymeric compositions are formed after uniform mixing.The polymer composition is added to rotational moulding
Forming machine(The swing rotational molding machine of Yantai Fangda Rotational Molding Co., Ltd.)Middle carry out rotation molding.Condition of molding includes:Mould and its
The temperature of materials inside heating hot-air is 280 DEG C, the flow velocity about 10m/s of air inlet hot-air, and mold rotation speed is
10 rpm, molding time is 15min.Obtainφ1000mm × 1000mm drum product, its wall thickness about 10mm.Test the drum
The resisting environmental stress and cracking time of product(ESCR)And tensile yield strength, concrete outcome is as shown in table 2.
The rotation molding effect list of table 2.
Sequence number | Polymer | Resisting environmental stress and cracking time ESCR(F50/h) | Tensile yield strength(MPa) |
1 | PE-5 | 2500 | 18.5 |
2 | PE-19 | 1900 | 16.3 |
From the data of table 2, polymer made according to the present invention(PE-5), with polymerizeing that art methods are manufactured
Thing(PE-19)Compare,(Product)Environmental stress cracking resistance is more excellent, and(Product)Tensile yield strength is higher.
Tube forming embodiment
Polymer P E-9 or PE-18, each and antioxidant 1010(Four [β-(3,5- di-tert-butyl-hydroxy phenyls) third
Acid] pentaerythritol ester), irgasfos 168((2,4- di-tert-butyl-phenyls) tris phosphite)With calcium stearate according to mass ratio
100/0.1/0.2/0.1 ratio be well mixed.The well mixed material is passed through into parallel equidirectional two-screw extruder(Nanjing
Rhea extrusion machinery equipment Co., Ltd CTE-35 types)Simultaneously pelletizing obtains corresponding pellet for melting extrusion, water-bath cooling.Twin-screw
Each section of temperature setting of extruder be:185℃-200℃-215℃-225℃-225℃-225℃-230℃-230℃-220℃-
220℃(Head).
After obtained pellet is dried 4 hours through 70 DEG C, polyvinyl piping materials extruder is added to(Crouse horse phenanthrene OD20-
63mm)In, in -240 DEG C -235 DEG C of extrusion temperature 190 DEG C -210 DEG C -220 DEG C -230 DEG C(Die head)With about 1 meter of extrusion linear speed/
Continuously extruded under conditions of minute, obtain the mm of the diameter 63 and mm of nominal wall thickness about 5.8 tubing.During record steady extruding
The main frame electric current of extruder, and test simply supported beam notch impact strength and the FNCT out-of-service times of the tubing(For characterizing tubing
Long-Term Properties), concrete outcome is as shown in table 3.
The tube forming effect list of table 3.
Sequence number | Polymer | Main frame electric current(A) | Simply supported beam notch impact strength(J/m2) | The FNCT out-of-service times(h) |
1 | PE-9 | 26±0.1 | 22.1 | 6100 |
2 | PE-18 | 28±0.1 | 17.5 | 5100 |
From the data of table 3, polymer made according to the present invention(PE-9), with polymerizeing that art methods are manufactured
(PE-18)Thing is compared, under equal processing conditions, and main frame electric current is lower, is indicated above its processing characteristics more preferably, and(Pipe
Material)Simply supported beam notch impact strength is higher,(Tubing)Long-Term Properties are more preferably.
Although the embodiment in conjunction with the embodiments to the present invention is described in detail above, need to refer to
Go out, protection scope of the present invention is not limited to these specific embodiments, but by claims of annex Lai
It is determined that.Those skilled in the art can be carried out in the range of the technological thought and purport of the present invention is not departed to these embodiments
Appropriate change, and the embodiment after these changes is obviously also included within protection scope of the present invention.
Claims (13)
1. a kind of manufacture method of ethene-alpha-olefin copolymer, it is characterised in that comprise the following steps A and B or step A' and
B':
Step A:Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta, alkyl
At least one of aluminium, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt make in terms of aluminium or boron as co-catalyst
The mol ratio of the co-catalyst and the major catalyst in terms of central metal atom reach 1~1000:1, it is anti-in polymerization
0.2 ~ 2.0MPa of stagnation pressure is answered, hydrogen and ethylene partial pressure compare 0.01-1:1 and 20 ~ 120 DEG C of polymeric reaction temperature under conditions of, make second
Polyamino alkenyl, obtains A stage polymers, and
Step B:Using slurry polymerization process, in the presence of the A stage polymers, 0.1 ~ 2.0MPa of polymerisation stagnation pressure,
Hydrogen and ethylene partial pressure compare 0.01-0.5:1st, 20 ~ 120 DEG C of polymeric reaction temperature and comonomer addition be 0.01 ~ 0.3 gram/
Under conditions of milligram major catalyst, make ethene and at least one alpha-olefin copolymer selected from C3-C12 alpha-olefins, obtain the second
Alkene-alpha olefin copolymer;
Or
Step A':Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta, alkane
At least one of base aluminium, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt make with aluminium or boron as co-catalyst
The mol ratio of the co-catalyst of meter and the major catalyst in terms of central metal atom reaches 1~1000:1, in polymerization
0.1 ~ 2.0MPa of reaction stagnation pressure, hydrogen and ethylene partial pressure compare 0.01-0.5:1st, 20 ~ 120 DEG C of polymeric reaction temperature and comonomer
Addition be 0.01 ~ 0.3 gram/milligram major catalyst under conditions of, make ethene with selected from C3-C12 alpha-olefins at least one α-
Olefin-copolymerization, obtains A' stage polymers, and
Step B':Using slurry polymerization process, in the presence of the A' stage polymers, polymerisation stagnation pressure 0.2 ~
2.0MPa, hydrogen and ethylene partial pressure compare 0.01-1:1 and 20 ~ 120 DEG C of polymeric reaction temperature under conditions of make ethylene homo, obtain
The ethene-alpha-olefin copolymer,
Wherein described load type non-metallocene catalyst is manufactured by the preparation method comprised the following steps:
Magnesium compound is set to be dissolved in the presence of an alcohol in the first solvent, the step of obtaining magnesium compound solution;
Porous carrier is set to be mixed with the magnesium compound solution, the step of obtaining the first mixed serum;
Precipitating reagent is added into first mixed serum or first mixed serum is dried, the step of complex carrier is obtained
Suddenly;
Make the complex carrier and following formula(X)Silicon compound and selected from IV B races metallic compound chemical treatments contact, obtain
The step of complex carrier must being modified,
Si(OR)mX4-mFormula(X)
Wherein, each R is identical or different, is each independently selected from C1-4Straight or branched alkyl;M is 0,1,2,3 or 4 integer;
Each X is identical or different, is each independently selected from halogen;
Nonmetallocene complex is contacted with the modification complex carrier in the presence of the second solvent, obtain the support type non-
The step of metallocene catalyst,
The preparation method, which is optionally additionally included in, makes the complex carrier be contacted with the silicon compound and the chemical treatments
Before, the step of chemical treatments pre-process the complex carrier is helped with selected from aikyiaiurnirsoxan beta, alkyl aluminum or its any combination,
One or more of the wherein described Nonmetallocene complex in the compound with following chemical structural formula:
,
In chemical structural formula more than,
Q is 0 or 1;
D is 0 or 1;
M is 1,2 or 3;
M is selected from periodic table of elements III-th family to XI races metallic atom;
N is 1,2,3 or 4, depending on the valence state of the M;
X is selected from halogen, hydrogen atom, C1- C30Alkyl, the C of substitution1- C30Alkyl, oxy radical, nitrogen-containing group, sulfur-containing group,
Boron-containing group, group containing aluminium base, phosphorus-containing groups, silicon-containing group, germanic group or containing tin group, multiple X can be with identical, can also not
Together, can also bonding or cyclization each other;
A be selected from oxygen atom, sulphur atom, selenium atom,、-NR23R24、-N(O)R25R26、、-PR28R29、-P(O)R30OR31、
Sulfuryl, sulfoxide group or-Se (O) R39, wherein N, O, S, Se and P be respectively coordination atom;
B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C1- C30Alkyl;
D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C1- C30Alkyl, sulfuryl
Or sulfoxide group, wherein N, O, S, Se and P be respectively coordination atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group, and wherein N, O, S, Se and P is each
From for coordination atom;
G is selected from C1- C30Alkyl, the C of substitution1- C30Alkyl or safing function group;
Represent singly-bound or double bond;
- represent covalent bond or ionic bond;
Represent coordinate bond, covalent bond or ionic bond;
R1To R3It is each independently selected from hydrogen, C1- C30Alkyl, the C of substitution1- C30Alkyl or safing function group, R22To R33
And R39It is each independently selected from hydrogen, C1- C30Alkyl or substituted C1- C30Alkyl, above-mentioned group to each other can be with identical
With difference, wherein adjacent group can combine togather bonding or cyclization,
The safing function group be selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group,
Containing tin group, C1- C10Ester group or nitro,
The halogen is selected from F, Cl, Br or I;
The nitrogen-containing group is selected from、-NR23R24、-T-NR23R24Or-N (O) R25R26;
The phosphorus-containing groups are selected from、-PR28R29、-P(O)R30R31Or-P (O) R32(OR33);
The oxy radical is selected from-OR34With-T-OR34;
The sulfur-containing group is selected from-SR35、-T-SR35、-S(O)R36Or-T-SO2R37;
The group containing seleno is selected from-SeR38、-T-SeR38、-Se(O)R39Or-T-Se (O) R39;
The group T is selected from C1- C30Alkyl or substituted C1- C30Alkyl;
The R37Selected from hydrogen, C1- C30Alkyl or substituted C1- C30Alkyl;
The C1- C30Alkyl is selected from C1- C30Alkyl, C7- C30Alkaryl, C7- C30Aralkyl, C3- C30Cyclic alkyl, C2-
C30Alkenyl, C2- C30Alkynyl, C6- C30Aryl or C8- C30Condensed ring radical;
The substituted C1- C30Alkyl, which is selected from, carries one or more aforementioned halogens or foregoing C1- C30Alkyl is used as substituent
Foregoing C1- C30Alkyl;
Wherein, the boron-containing group is selected from BF4 -、(C6F5)4B-Or (R40BAr3)-;
The group containing aluminium base is selected from alkyl aluminum, AlPh4 -、AlF4 -、AlCl4 -、AlBr4 -、AlI4 -Or R41AlAr3 -;
The silicon-containing group is selected from-SiR42R43R44;
The germanic group is selected from-GeR46R47R48;
It is described to be selected from-SnR containing tin group50R51R52Or-T-Sn (O) R54, wherein the group T is as previously defined,
The Ar represents C6- C30Aryl, and
R34To R36、R38And R40To R54It is each independently selected from hydrogen, foregoing C1- C30Alkyl or foregoing substituted C1- C30Alkyl,
Wherein these groups can be the same or different to each other, wherein adjacent group can combine togather bonding or into
Ring.
2. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein:
Step A:Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta and alkane
At least one of base aluminium makes the co-catalyst in terms of aluminium or boron and the institute in terms of central metal atom as co-catalyst
The mol ratio for stating major catalyst reaches 10~100:1, in polymerisation stagnation pressure 0.4-0.8MPa, hydrogen and ethylene partial pressure ratio
0.03-0.5:1 and 75 ~ 95 DEG C of polymeric reaction temperature under conditions of, make ethylene homo, obtain A stage polymers, and
Step B:Using slurry polymerization process, in the presence of the A stage polymers, polymerisation stagnation pressure 0.3-0.6MPa,
Hydrogen and ethylene partial pressure compare 0.03-0.3:1st, 75 ~ 95 DEG C of polymeric reaction temperature and comonomer addition are 0.02 ~ 0.2 gram/milli
Under conditions of gram major catalyst, make ethene and at least one alpha-olefin copolymer selected from C4-C8 alpha-olefins, obtain the ethene-
Alpha olefin copolymer;
Or
Step A':Using slurry polymerization process, using load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta and alkane
At least one of base aluminium makes the co-catalyst in terms of aluminium or boron and the institute in terms of central metal atom as co-catalyst
The mol ratio for stating major catalyst reaches 10~100:1, in polymerisation stagnation pressure 0.3-0.6MPa, hydrogen and ethylene partial pressure ratio
0.03-0.3:1st, 75 ~ 95 DEG C of polymeric reaction temperature and the condition that comonomer addition is 0.02 ~ 0.2 gram/milligram major catalyst
Under, make ethene and at least one alpha-olefin copolymer selected from C4-C8 alpha-olefins, obtain A' stage polymers, and
Step B':Using slurry polymerization process, in the presence of the A' stage polymers, in polymerisation stagnation pressure 0.4-
0.8MPa, hydrogen and ethylene partial pressure compare 0.03-0.5:1 and 75 ~ 95 DEG C of polymeric reaction temperature under conditions of make ethylene homo, obtain
The ethene-alpha-olefin copolymer.
3. the manufacture method of the ethene-alpha-olefin copolymer of claim 1 or 2, wherein the A stage polymers account for the second
The 0.1-90wt% of alkene-alpha olefin copolymer gross mass, or the A' stage polymers account for the ethene-alpha-olefin copolymer
The 10-99.9wt% of gross mass.
4. the manufacture method of the ethene-alpha-olefin copolymer of claim 3, wherein the A stage polymers account for the ethene-α-
The 30-70wt% of olefin copolymer gross mass, or the A' stage polymers account for the ethene-alpha-olefin copolymer gross mass
30-70wt%.
5. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the porous carrier is selected from partial cross-linked benzene
In ethene polymers, silica, aluminum oxide, magnesia, oxidation sial, oxidation magnalium, titanium dioxide, molecular sieve and montmorillonite
One or more, wherein the porous carrier is optionally by thermal activation treatment and/or by the IV B races metallic compound
Chemical activation processing, one or more of the magnesium compound in magnesium halide.
6. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein first solvent is selected from C6-12Aromatic hydrocarbon, halogen
For C6-12One or more in aromatic hydrocarbon, ester and ether, second solvent is selected from C6-12Aromatic hydrocarbon, halo C6-12Aromatic hydrocarbon, halogen
For C1-10One or more in alkane and ether, and one or more of the alcohol in fatty alcohol, aromatic alcohol and alicyclic ring alcohol,
Wherein described alcohol is optionally selected from halogen atom or C1-6The substituent substitution of alkoxy.
7. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, has such as wherein the Nonmetallocene complex is selected from
The compound of lower chemical structural formula(A)And compound(B)In one or more:
With,
(A) (B)
In above all of chemical structural formula,
F is selected from nitrogen-atoms, nitrogen-containing group or phosphorus-containing groups, and wherein N and P are respectively coordination atom.
8. the manufacture method of the ethene-alpha-olefin copolymer of claim 7, has such as wherein the Nonmetallocene complex is selected from
The compound of lower chemical structural formula(A-1)To compound(A-4)And compound(B-1)To compound(B-4)In one kind or many
Kind:
、、
(A-1)(A-2)
、、
(A-3)(A-4)
、、
(B-1)(B-2)
With,
(B-3)(B-4)
In above all of chemical structural formula,
Y is selected from-NR23R24、-N(O)R25R26、-PR28R29、-OR34、-SR35、-S(O)R36、-SeR38Or-Se (O) R39, wherein N,
O, S, Se and P are respectively coordination atom;
Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano group, and wherein N, O, S, Se and P is each
From for coordination atom;
R4、R6To R21It is each independently selected from hydrogen or C1- C30Alkyl, and
R5Lone pair electrons, hydrogen, C on nitrogen1- C30Alkyl, the C of substitution1- C30Alkyl, oxy radical, sulfur-containing group, nitrogenous base
Roll into a ball, containing seleno group or phosphorus-containing groups;Work as R5For oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or during phosphorus-containing groups, R5
In N, O, S, P and Se can be coordinated as coordination with atom and the B races metallic atom of center IV.
9. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, has such as wherein the Nonmetallocene complex is selected from
One or more in the compound of lower chemical structural formula:
、、、
、With。
10. the manufacture method of the ethene-alpha-olefin copolymer of claim 9, has wherein the Nonmetallocene complex is selected from
One or more in the compound of following chemical structural formula:
With。
11. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the magnesium compound and first solvent
Ratio be 1mol:75~400ml, the magnesium compound and the mol ratio of the alcohol counted using Mg elements is 1:0.02~
4.00, the magnesium compound and the mass ratio of the porous carrier counted using magnesium compound solid is 1:0.1-20, the precipitation
The volume ratio of agent and first solvent is 1:0.2~5, the complex carrier in terms of Mg elements with described in terms of Si elements
The mol ratio of silicon compound is 1:0.01-1, the complex carrier in terms of Mg elements with described in Group IVB elemental metal
The mol ratio of chemical treatments is 1:0.01-1, the complex carrier in terms of Mg elements rubs with the Nonmetallocene complex
You are than being 1:0.01-1, and the complex carrier in terms of Mg elements with terms of Al elements described in help rubbing for chemical treatments
You are than being 1:0-1.0.
12. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the precipitating reagent be selected from alkane, cycloalkane,
One or more in halogenated alkane and halo cycloalkane.
13. the manufacture method of the ethene-alpha-olefin copolymer of claim 1, wherein the IV B races metallic compound is selected from IV B
One or more in race's metal halide, the aikyiaiurnirsoxan beta be selected from MAO, ethylaluminoxane, isobutyl aluminium alkoxide and
One or more in normal-butyl aikyiaiurnirsoxan beta, and the alkyl aluminum is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, three isobutyls
Base aluminium, three n-butylaluminums, triisopentyl aluminium, three n-pentyl aluminium, three hexyl aluminium, three isohesyl aluminium, diethylmethyl aluminium and diformazan
One or more in base aluminium ethide.
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CN101654494A (en) * | 2008-08-21 | 2010-02-24 | 中国石化扬子石油化工有限公司 | Ethane copolymer and preparation method and application thereof |
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CN101654494A (en) * | 2008-08-21 | 2010-02-24 | 中国石化扬子石油化工有限公司 | Ethane copolymer and preparation method and application thereof |
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