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CN104610475A - Catalyst for olefin polymerization reaction - Google Patents

Catalyst for olefin polymerization reaction Download PDF

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Publication number
CN104610475A
CN104610475A CN201310540985.2A CN201310540985A CN104610475A CN 104610475 A CN104610475 A CN 104610475A CN 201310540985 A CN201310540985 A CN 201310540985A CN 104610475 A CN104610475 A CN 104610475A
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titanium
component
catalyzer
compound
olefinic polyreaction
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CN104610475B (en
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夏先知
张天一
万真
郭正阳
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The present invention relates to a catalyst for an olefin polymerization reaction. According to the present invention, a granular solid catalyst component adopting a carboxylic ester compound as an internal electron donor is added with an alkenyl trialkoxy silane compound adopted as an external electron donor, such that the high activity and the high directional capability of the catalyst can be maintained, the hydrogen response of the catalyst is substantially improved, especially in the case of requirement of direct polymerization to obtain the high melt index polymer, and the polymerization method is simple and can be used separately.

Description

A kind of catalyzer for olefinic polyreaction
Technical field
The present invention relates to a kind of catalyzer for olefinic polyreaction, more particularly, relating to a kind of take carboxylicesters as the olefin polymerization catalysis of the titaniferous granulated ingredient of solid catalyst of internal electron donor, promotor and external donor compound alkylene three hydrocarbyloxysilane, belongs to field of olefin polymerisation.
Background technology
Generally be made up of three parts for the catalyst system in the polyreaction of alpha-olefin and composition thereof, they are: (1) Primary Catalysts (solid catalyst), (2) promotor (being generally aluminum alkyls compounds) and (3) polymerization time the external donor compound that adds.
In polymerization process, use one or more external electronic donor compounds to control the taxis of polymkeric substance and form is that those skilled in the art are in common knowledge.External electron donor is except the taxis affecting polymkeric substance, the performance of the other sides such as the activity of catalyzer and hydrogen response can be had influence on to some extent toward contact, but while the effect that its impact is played often in one aspect, then can play side effect in other respects.Although there will be a known multiple compounds perhaps can as external electron donor, specific catalyzer uses different external donor compounds may produce different polymer performances.Select suitable external electron donor can be compatible especially with specific catalyst component.That is, find a kind of applicable external electron donor can improve some performance of polymeric articles significantly as activity, degree of isotacticity, molecular weight distribution and hydrogen response etc., and other performance do not affected simultaneously or affect very little, therefore finding one group, to be particularly suitable for the external electron donor that specific catalyst component can make polymkeric substance have fine over-all properties be very favorable.
In European patent EP 385765A, describe a kind of catalyst system, this system is made up of the Ziegler-Natta catalyst mixed with two kinds of silane external electron donors, and a kind of embodiment of concrete external electron donor mixture is dicyclopentyl dimethoxyl silane and propyl-triethoxysilicane.In US Patent No. 5,100, in 981, disclose a kind of catalyst system, it is made up of the mixture of Primary Catalysts and two kinds of external electron donors, and described external electron donor is CHMMS and phenyl triethoxysilane.In Japanese Patent JP19820199728, also illustrate a kind of catalyst system, this system uses the Ziegler-Natta catalyst of two kinds of silane external electron donor mixing to form, mention in patent and methyl benzoate and tetraethoxysilane can be used as Mixed electron donor, but the activity of polymkeric substance and degree of isotacticity are all lower; Japanese Patent JP19820174495; In JP19920331459, also using tetraethoxysilane as external electron donor, but net effect is all bad.
Chinese patent CN85100997 and CN981263852 uses phthalic ester as internal electron donor, coordinates dimethoxydiphenylsilane to obtain the catalyzer making polymer directional ability higher as external electron donor.Chinese patent CN201010548601.8(NX) and CN200910177286.X on the basis of CN981263852, introduce halohydrocarbon and tetraalkoxysilane as the integral part of catalyzer, obtain the catalyzer that polymerization activity is higher.But from the general status of the commercialized catalyst existing market, expect that the catalyzer making orientation property and hydrogen response all superior is still more difficult.
How keeping with carboxylic acid ester compound the feature of the catalyst system being internal electron donor, improve the hydrogen response of this catalyst system simultaneously, thus improve the over-all properties of catalyst system, is the important technological problems needing to solve.
The present inventor is surprised to find that in research work, with carboxylic acid ester compound be the granulated ingredient of solid catalyst of internal electron donor in olefinic polymerization time add alkylene three hydrocarbyloxysilane compound as external donor compound, this catalyzer greater activity, high orientation property can not only be kept, make the hydrogen response of catalyzer greatly improve simultaneously, especially direct polymerization is needed to obtain the situation of high fusion index polymkeric substance, and polymerization process is simple, can be used alone.
Summary of the invention
The object of the present invention is to provide a kind of catalyzer for olefinic polyreaction, this catalyzer has high polymerization activity, the degree of isotacticity that the polymkeric substance tool obtained is higher, and the hydrogen response of catalyzer improves greatly simultaneously.
A kind of catalyzer for olefinic polyreaction of the present invention, comprises the reaction product of following component:
(1) a solids containing titanium catalyst component, this catalyst component comprise titanium, magnesium, chlorine and give electric body compound carboxylicesters; This solids containing titanium catalyst component is prepared by the following method:
1) magnesium halide is dissolved in organic epoxy compound thing, organo phosphorous compounds forms homogeneous solution, under precipitation additive exists with after titanium compound, carboxylicesters effect, obtain solids containing titanium catalyst component;
2) reacted under the existence of halogenating agent by MAGNESIUM METAL and alcohol and prepare spherical particle dialkoxy magnesium; Then with this dialkoxy magnesium for carrier, in inert diluent, make itself and titanium compound and electron donor compound contact reacts, the solids containing titanium catalyst component obtained;
Wherein the general formula of titanium compound is: Ti (OR w) 4-kx k, wherein R wbe the alkyl of 1 ~ 20, X is Cl, Br or I, and k is the integer of 0 ~ 4;
Carbonate is selected from unitary or polyhydric aliphatic race carboxylicesters, aromatic carboxylic acid ester cpds;
Precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone;
(2) alkylaluminium cpd, its general formula is AlR''' 3, R''' is identical or not identical C 1-8alkyl, wherein one or two alkyl can be replaced by chlorine, and optional one or more the aluminum alkyls that adopts is used in combination, and wherein the aluminium in component (2) and the titanium mol ratio in component (1) are 1 ~ 1000;
(3) external donor compound is alkylene three hydrocarbyloxysilane shown in general formula (I),
R in general formula (I) 1, R 2, R 3for carbonatoms 1 ~ 20 straight or branched alkyl, cycloalkyl, aralkyl, alkaryl, fused ring aryl or alkylene, R 1, R 2, R 3optionally identical or different; R 4for the alkylene of carbonatoms 1 ~ 20.
Particular compound is as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, vinyltributoxysilane, vinyl three cyclopentyloxy silane, vinyl three cyclohexyloxy silane, vinyltriphenoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, allyl group tripropoxy silane, allyl group three butoxy silane, allyl group three cyclopentyloxy silane, allyl group three cyclohexyloxy silane, allyl group triple phenoxyl silane, butenyl Trimethoxy silane, butenyl triethoxyl silane, butenyl tripropoxy silane, butenyl three butoxy silane, butenyl three cyclopentyloxy silane, butenyl three cyclohexyloxy silane, butenyl triple phenoxyl silane, styryl Trimethoxy silane, styryl triethoxyl silane, styryl tripropoxy silane, styryl three butoxy silane, styryl three cyclopentyloxy silane, styryl three cyclohexyloxy silane, styryl triple phenoxyl silane, cinnamyl Trimethoxy silane, cinnamyl triethoxyl silane, cinnamyl tripropoxy silane, cinnamyl three butoxy silane, cinnamyl three cyclopentyloxy silane, cinnamyl three cyclohexyloxy silane, cinnamyl triple phenoxyl silane, benzene butenyl Trimethoxy silane, benzene butylene propyl-triethoxysilicane, benzene butenyl tripropoxy silane, benzene butenyl three butoxy silane, benzene butenyl three cyclopentyloxy silane, benzene butenyl three cyclohexyloxy silane, benzene butenyl triple phenoxyl silane, propadiene base Trimethoxy silane, propadiene ethyl triethoxy silicane alkane, propadiene base tripropoxy silane, propadiene base three butoxy silane, propadiene base three cyclopentyloxy silane, propadiene base three cyclohexyloxy silane, propadiene base triple phenoxyl silane, butadienyl Trimethoxy silane, butadienyl triethoxyl silane, butadienyl tripropoxy silane, butadienyl three butoxy silane, butadienyl three cyclopentyloxy silane, butadienyl three cyclohexyloxy silane, butadienyl triple phenoxyl silane etc.One in preferred vinyl Trimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, vinyltributoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, allyl group tripropoxy silane, allyl group three butoxy silane.
The consumption of alkylene three hydrocarbyloxysilane that general formula is (I) is every mole aluminum compound 0.001 ~ 5 mole, preferably every mole aluminum compound 0.001 ~ 1 mole.
Alkylene three hydrocarbyloxysilane shown in general formula (I), can adopt conventional synthetic method to be prepared in laboratory, also by general chemical product purchasing way, can buy on the market.
As follows to the detailed description of the invention below:
A kind of catalyzer for olefinic polyreaction of the present invention, comprises the reaction product of following component:
(1) a solids containing titanium catalyst component, this catalyst component comprise titanium, magnesium, chlorine and give electric body compound carboxylicesters; This solids containing titanium catalyst component is prepared by the following method:
1) magnesium halide is dissolved in organic epoxy compound thing, organo phosphorous compounds forms homogeneous solution, under precipitation additive exists with after titanium compound, carboxylicesters effect, obtain solids containing titanium catalyst component;
2) reacted under the existence of halogenating agent by MAGNESIUM METAL and alcohol and prepare spherical particle dialkoxy magnesium; Then with this dialkoxy magnesium for carrier, in inert diluent, make itself and titanium compound and electron donor compound contact reacts, the solids containing titanium catalyst component obtained;
Wherein the general formula of titanium compound is: Ti (OR w) 4-kx k, wherein R wbe the alkyl of 1 ~ 20, X is Cl, Br or I, and k is the integer of 0 ~ 4;
Carbonate is selected from unitary or polyhydric aliphatic race carboxylicesters, aromatic carboxylic acid ester cpds;
Precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone;
In the 1st of preparation component (1)), the 3rd) magnesium halide described in kind method is magnesium dihalide, the water of magnesium dihalide or alcohol complex, in magnesium dihalide molecular formula one of them halogen atom by-oxyl or halogen-oxyl the one in the derivative of replacing, or their mixture.Above-mentioned magnesium dihalide is specially: magnesium dichloride, dibrominated magnesium, diiodinating magnesium, preferred magnesium dichloride.
Described organic epoxy compound thing is selected from and comprises carbonatoms at the aliphatics alkene of 2 ~ 8, oxide compound, the compound such as glycidyl ether and inner ether of diolefine or halogenated aliphatic alkene or diolefine.Concrete as oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF) etc.
Described organo phosphorous compounds is selected from hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, such as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, phosphorous acid benzene methyl etc.
Can to add in dissolution system during dissolving or not with inert diluent, inert diluent can adopt benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound, wherein with toluene, dimethylbenzene for the best.
In the 1st of preparation component (1)) in kind method, solids containing titanium catalyst component is prepared according to the preparation method of solid catalyst disclosed in Chinese patent CN201010548601.8 and CN98126385.2, and associated viscera disclosed in it all introduces the present invention as a reference.
In the 2nd of preparation component (1)) in kind method, solids containing titanium catalyst component is prepared according to the preparation method of solid catalyst disclosed in Chinese patent CN201110172225, and associated viscera disclosed in it all introduces the present invention as a reference.
The general formula of titanium compound is: Ti (OR w) 4-kx k, wherein R wbe the alkyl of 1 ~ 20, X is Cl, Br or I, and k is the integer of 0 ~ 4; Specifically can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium, titanous chloride or their mixture, preferred titanium tetrachloride.
Electron donor compound is unitary or polyhydric aliphatic race carboxylicesters, aromatic carboxylic acid esters's compound.Such as benzoic ether, phthalic ester, malonic ester, succinate, glutarate etc.Concrete as ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate, dinoctyl phthalate, diethyl malonate, butyl ethyl malonate, 2, 3-di-isopropyl ethyl succinate, 2, 3-di-isopropyl di-iso-octyl succinate, 2, 3-di-isopropyl dibutyl succinate, 2, 3-di-isopropyl succsinic acid dimethyl esters, 2, 2-dimethyl succinate diisobutyl ester, 2-Ethyl-2-Methyl di-iso-octyl succinate, 2-Ethyl-2-Methyl ethyl succinate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, diethyl maleate, maleic acid n-butyl, naphthalene dicarboxylic acids diethyl ester, naphthalene dicarboxylic acids dibutylester, triethyl trimellitate, tributyl trimellitate, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tri-n-butyl, pyromellitic acid tetra-ethyl ester, pyromellitic acid four butyl ester etc.Preferred ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate or dinoctyl phthalate.
In instant component (1) catalyst component preparation process, wherein in every mole of magnesium, carboxylicesters internal electron donor compound is 0.01 ~ 5 mole, preferably 0.05 ~ 1 mole.
Precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone; Preferred diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried or MALEIC ANHYDRIDE.
Component of the present invention (2) alkylaluminium cpd, its general formula is AlR''' 3, R''' is identical or not identical C 1-8alkyl, wherein one or two alkyl can be replaced by chlorine, and one or more aluminum alkyls can be selected used in combination, preferred triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, chlorination aluminum alkyls, Al (n-C 6h 13) 3, Al (n-C 8h 17) 3, AlEt 2cl etc. are generally 1 ~ 1000 use abovementioned alkyl aluminum compound with Al/Ti mol ratio.
Component (2) alkylaluminium cpd and component (3) external donor compound can separately or as the mixture of two kinds of compositions and component (1) catalyst component contact reactss.
Above-mentioned catalyst system is suitable for alkene CH 2=CHR y(wherein R ythe alkyl or aryl of hydrogen or 1 ~ 6 carbon) and the polyreaction of mixture containing (if necessary) a small amount of diolefine.
The polymerization of alkene is carried out according to currently known methods, in liquid monomer or monomer the solution in inert solvent liquid phase in, or in the gas phase, or operated by the polymerization mix technique in liquid phase.Polymerization temperature is generally 0 DEG C ~ 150 DEG C, preferably 60 DEG C ~ 100 DEG C.Polymerization pressure is normal pressure or higher.
Embodiment
Provide following examples better the present invention to be described, be not used for limiting the scope of the invention.
Testing method:
1, melt index: measure according to ASTM D1238-99.
2, polymkeric substance degree of isotacticity: adopt normal heptane extraction process to measure (normal heptane boiling extracting 6 hours), namely the polymer samples of 2g drying is got, be placed in extractor boiling heptane extracting 6 hours, afterwards, residuum is dried to constant weight, resulting polymers weight (g) with 2 ratio be degree of isotacticity.
Embodiment 1
The preparation (preparing according to Chinese patent CN201010548601.8 embodiment 1) of solid catalyst A (Primary Catalysts)
In the reactor of fully replacing through high pure nitrogen, add magnesium chloride 4.8g successively, toluene 70ml, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5ml, 1.0ml tetraethoxysilane, be warming up to 60 DEG C under stirring, and maintain 1.0 hours, solid dissolves completely.Add Tetra hydro Phthalic anhydride 1.4g and 30ml toluene, continue maintenance 1 hour.Solution is cooled to less than-28 DEG C, TiCl456ml(5ml/min is dripped) in 1 hour, slowly be warming up to 85 DEG C (5 DEG C/min), solids is separated out gradually in temperature-rise period, add n-butyl phthalate 1.1ml, maintain 85 DEG C of temperature 1 hour, after filtration, use toluene wash secondary, obtain solid sediment.Then add toluene 72ml, TiCl448ml, be warmed up to 110 DEG C, process 0.5 hour, after venting filtrate, with hexanes wash five times, vacuum-drying obtains solids containing titanium catalyst component A.
The preparation (preparing with reference to Chinese patent CN98126385.2 embodiment 1) of solid catalyst B (Primary Catalysts)
In the reactor of fully replacing through high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95ml, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5ml, is warming up to 50 DEG C under stirring, and maintains 2.5 hours, solid dissolves completely, adds Tetra hydro Phthalic anhydride 1.4g, continues maintenance 1 hour.Solution is cooled to less than-25 DEG C, in 1 hour, drips TiCl456ml, be slowly warming up to 80 DEG C, in temperature-rise period, separate out solids gradually, add diisobutyl phthalate 2.7ml, maintain 80 DEG C of temperature 1 hour, after filtration, add toluene 70ml, washing secondary, obtains solid sediment.Then add toluene 60ml, TiCl440ml, be warmed up to 100 DEG C, process 2 hours, after venting filtrate, then add toluene 60ml, TiCl440ml, be warmed up to 100 DEG C, process 2 hours, venting filtrate.Add toluene 60ml, boiling state washs three times, then adds hexane 60ml, after boiling state washing secondary, obtains solids containing titanium catalyst component B.
The preparation (the method Kaolinite Preparation of Catalyst component with reference to disclosed in Chinese patent CN201110172225) of solid catalyst C (Primary Catalysts)
(1) preparation of dialkoxy-magnesium support
After replacing the 16L voltage-resistant reactor with agitator fully with nitrogen, in reactor, add ethanol 10200mL, 2-Ethylhexyl Alcohol 300mL, add iodine 12g and magnesium chloride 8g and make it to dissolve.Open after stirring and heat up, until reach the reflux temperature of reaction system; Then successively add magnesium powder 640g, reaction is carried out till no longer including hydrogen discharge.Then wash, be separated and drying.Obtain dry dialkoxy-magnesium support.
(2) preparation of catalyst component C
Get above-mentioned dialkoxy-magnesium support 650g and toluene 3250mL, that n-butyl phthalate (DNBP) 130mL is mixed with suspension is stand-by; Repeating in the withstand voltage reactor of 16L of replacing through high pure nitrogen, add toluene 2600mL and titanium tetrachloride 3900mL, be cooled to-5 DEG C, then the suspension prepared is added in still above, constant temperature is to temperature-stable, then 110 DEG C are slowly warming up to, at this temperature constant temperature 2 hours, by clean for liquid press filtration.The mixed solution adding toluene 5070mL and titanium tetrachloride 3380mL is warming up to 110 DEG C, stir process 1 hour, elimination liquid, repeats aforesaid operations once, and the solid of gained washs 3-5 time with hexane 10000ml, and elimination liquid is also dry, obtains ingredient of solid catalyst C.
Embodiment 2
Propylene polymerization
In 5 liters of autoclaves; stream of nitrogen gas is adopted to purge 1 hour at 70 DEG C; then with gas-phase propene, polymeric kettle is replaced 3 times, introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, the hexane solution (concentration of external electron donor is 0.1mmol/ml) of 1ml external electron donor, 10ml anhydrous hexane and 8 ~ 12mg solid catalyst (Primary Catalysts) under nitrogen protection.Close autoclave, introduce appropriate hydrogen and the liquid propene of 1.0 ~ 1.2Kg; Under agitation quick temperature in Fu is risen to 70 DEG C.At 70 DEG C, polyreaction is after 1 hour, stops stirring, and removes unpolymerized propylene monomer, collected polymer, vacuum-drying 2 hours at 70 DEG C, calculated activity of weighing (AC).
Embodiment 3 ~ 9
By the method for the solid catalyst A of preparation in embodiment 1 according to propylene polymerization in embodiment 2, add hydrogen, the different polymerization time of different amount respectively and use the hexane solution of different external electron donors (concentration is 0.1mmol/ml) to carry out propylene polymerization, polymerization and test result are in table one.
Embodiment 10 ~ 14
By the method for the solid catalyst B of preparation in embodiment 1 according to propylene polymerization in embodiment 2, the hexane solution (concentration is 0.1mmol/ml) adding the different hydrogen the measured external electron donor different with use respectively carries out propylene polymerization, and polymerization and test result are in table one.
Embodiment 15 ~ 16
By the method for the solid catalyst C of preparation in embodiment 1 according to propylene polymerization in embodiment 2, the hydrogen adding different amount respectively carries out propylene polymerization, and polymerization and test result are in table one.
Comparative example 1 ~ 9
Polymerization process is with embodiment 3 ~ 9, just the external electron donor added is changed into the hexane solution (concentration is 0.1mmol/ml) of 1ml Cyclohexyl Methyl Dimethoxysilane (C-donor) or 1ml dicyclopentyl dimethoxyl silane (D-donor), polymerization result is in Table table one.
Table one
Note: ATES---allyltriethoxysilane
VTES---vinyltriethoxysilane
C-donor---Cyclohexylmethyldimethoxysilane
D-donor---dicyclopentyl dimethoxyl silane
As can be seen from table one, use instant component alkylene three hydrocarbyloxysilane compounds as the catalyst system of external electron donor, after propylene polymerization, under identical hydrogen concentration condition, the polymer melt index obtained obviously is greater than and uses Cyclohexylmethyldimethoxysilane (C-donor) and dicyclopentyl dimethoxyl silane (D-donor) as the melt index of polymkeric substance during external electron donor.
As can be seen from obtained polymkeric substance over-all properties, use alkylene three hydrocarbyloxysilane compounds as the catalyst system of external electron donor, when hydrogen response improves greatly, the degree of isotacticity of the active polymkeric substance with obtaining of polymerization catalyst still remains on higher level.

Claims (12)

1. for a catalyzer for olefinic polyreaction, it is characterized in that, comprise the reaction product of following component:
(1) a solids containing titanium catalyst component, this catalyst component comprise titanium, magnesium, chlorine and give electric body compound carboxylicesters; This solids containing titanium catalyst component is prepared by the following method:
1) magnesium halide is dissolved in organic epoxy compound thing, organo phosphorous compounds forms homogeneous solution, under precipitation additive exists with after titanium compound, carboxylicesters effect, obtain solids containing titanium catalyst component;
2) reacted under the existence of halogenating agent by MAGNESIUM METAL and alcohol and prepare spherical particle dialkoxy magnesium; Then with this dialkoxy magnesium for carrier, in inert diluent, make itself and titanium compound and electron donor compound contact reacts, the solids containing titanium catalyst component obtained;
Wherein the general formula of titanium compound is: Ti (OR w) 4-kx k, wherein R wbe the alkyl of 1 ~ 20, X is Cl, Br or I, and k is the integer of 0 ~ 4;
Carbonate is selected from unitary or polyhydric aliphatic race carboxylicesters, aromatic carboxylic acid ester cpds;
Precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone;
(2) alkylaluminium cpd, its general formula is AlR''' 3, R''' is identical or not identical C 1-8alkyl, wherein one or two alkyl can be replaced by chlorine, and optional one or more the aluminum alkyls that adopts is used in combination, and wherein the aluminium in component (2) and the titanium mol ratio in component (1) are 1 ~ 1000;
(3) external donor compound is alkylene three hydrocarbyloxysilane shown in general formula (I),
R in general formula (I) 1, R 2, R 3for carbonatoms 1 ~ 20 straight or branched alkyl, cycloalkyl, aralkyl, alkaryl, fused ring aryl or alkylene, R 1, R 2, R 3optionally identical or different; R 4for the alkylene of carbonatoms 1 ~ 20.
2. the catalyzer for olefinic polyreaction according to claim 1, it is characterized in that, magnesium halide described in component (1) is magnesium dihalide, the water of magnesium dihalide or alcohol complex, in magnesium dihalide molecular formula one of them halogen atom by-oxyl or halogen-oxyl the one in the derivative of replacing, or their mixture.
3. the catalyzer for olefinic polyreaction according to claim 1, it is characterized in that, organic epoxy compound thing described in component (1) is the one in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF), or their mixture.
4. the catalyzer for olefinic polyreaction according to claim 1, it is characterized in that, organo phosphorous compounds described in component (1) is the one in ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite, phosphorous acid benzene methyl, or their mixture.
5. the catalyzer for olefinic polyreaction according to claim 1, it is characterized in that, the titanium compound described in component (1) is a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium, titanous chloride or their mixture.
6. the catalyst system for olefinic polyreaction according to claim 1, is characterized in that, described titanium compound is titanium tetrachloride.
7. the catalyzer for olefinic polyreaction according to claim 1, it is characterized in that, the carbonate described in component (1) is ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate or dinoctyl phthalate.
8. the catalyzer for olefinic polyreaction according to claim 1, is characterized in that, described precipitation additive is diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried or MALEIC ANHYDRIDE.
9. the catalyzer for olefinic polyreaction according to claim 1, is characterized in that, component (2) alkylaluminium cpd is triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, Al (n-C 8h 17) 3, AlEt 2a kind of in Cl or their mixture.
10. the catalyzer for olefinic polyreaction according to claim 1, it is characterized in that, described component (3) external donor compound alkylene three hydrocarbyloxysilane is the one in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, vinyltributoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, allyl group tripropoxy silane, allyl group three butoxy silane.
11. catalyzer for olefinic polyreaction according to claim 1, is characterized in that, the consumption of described component (3) external donor compound alkylene three hydrocarbyloxysilane is every mole aluminum compound 0.001 ~ 1.0 mole.
The application of the catalyzer for olefinic polyreaction described in 12. claim 1 ~ 11 any one in olefinic polyreaction.
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