CN104250320B - A kind of catalyst system for olefinic polyreaction - Google Patents
A kind of catalyst system for olefinic polyreaction Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst system and catalyzing for olefinic polyreaction, using polyol ester compounds and the adjacent benzene dicarboxylic acid ester type compound spherical solids containing titanium catalytic component as internal electron donor in olefinic polymerization time add alkylene three hydrocarbyloxysilane compound as external donor compound, on the premise of keeping original catalyst width molecular weight distribution, it is possible to improve polymer isotactic index and melt index further.
Description
Technical field
The present invention relates to a kind of catalyst system and catalyzing for olefinic polyreaction, more particularly, it relates to one includes spherical
Catalytic component, promoter and external donor compound are the catalytic systems for polymerization of olefins of alkylene three hydrocarbyloxysilane.
Background technology
It is known that be all polymerized for alpha-olefin or catalyst system in copolymerization is typically made up of three parts,
They are: add when (1) major catalyst (solid catalyst), (2) promoter (usually alkyl aluminum compounds) and (3) polymerization
The external donor compound entered.
Use one or more External Electron Donor Compound to control the stereoregular of polymer in polymerization process
Property and form are that those skilled in the art are well known.External electron donor is in addition to the stereoregularity affecting polymer, often
Also can have influence on the performance of catalyst other side to some extent.There is the multiple compounds perhaps can be as outer to electricity although known
Daughter, but specific catalyst uses different external donor compounds may produce different polymer performances.Choosing
Selecting suitable external electron donor can be the most compatible with specific catalyst, say, that find a kind of applicable outer to electronics
Body can be significantly improved polymeric articles performance in terms of some, consequently found that one group can make polymer for special catalyst
The external electron donor in some aspects with outstanding properties is very favorable.
Chinese patent CN02100896.5, CN02100900.7, CN03109781.2, CN03140565.7,
CN200410073623.8, CN200410073621.9 etc. describe use polyol ester compounds and adjacent benzene dicarboxylic acid esters
Compound compounds the catalytic component into internal electron donor, this catalytic component when propylene polymerization, use outer to electronics
Body alkyl two hydrocarbyloxysilane is current industrial conventional external electron donor, such as Cyclohexylmethyldimethoxysilane
(CHMMS) etc..Although Chinese patent CN03109781.2 also using different external electron donors as a comparison, such as except making
With outside Cyclohexylmethyldimethoxysilane, second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane are also used
(DCPMS), two (cyclobutylmethyl) dimethoxysilane etc., this catalyst system show high activity, highly directional ability and
The feature that prepared molecular weight distribution is wide.
The present inventor in research work it was unexpectedly observed that with polyol ester compounds and adjacent benzene dicarboxylic acid esters
Compound is that the spherical solid catalytic component of internal electron donor adds alkylene three hydrocarbyloxysilane compound when olefinic polymerization
As external donor compound, on the premise of keeping original catalyst width molecular weight distribution, it is possible to improve polymerization further
The isotactic index of thing；Additionally when adding hydrogen amount equally, the hydrogen response of polymer improves.
Summary of the invention
It is an object of the invention to provide a kind of catalyst system for olefinic polyreaction, this catalyst system can
Improve the isotactic index of polymer further；Additionally when adding hydrogen amount equally, the hydrogen response of polymer improves.
A kind of catalyst system and catalyzing for olefinic polyreaction of the present invention, comprises the product of following component:
(1) a kind of solids containing titanium catalytic component, this catalytic component is at logical formula I MgCl2.nRqChlorination shown in OH
Logical formula II Ti (OR it is loaded with on magnesium alcoholate granulew)4-kXkShown titanium compound and at least two electron donor compound
a、b；
R in its formula of (I)qFor the alkyl that carbon number is 1～18, n is 0.1～6；
R in its formula of (II)wBeing the alkyl of 1～20, X is Cl, Br or I, and k is the integer of 0～4；
Wherein give electricity body compound a selected from logical diol-lipid compound shown in formula III:
(III)
R in formula III1-R6、R1-R2nGroup is identical or different, for hydrogen, halogen, substituted or unsubstituted straight or branched
C1-C20Alkyl, C3-C20Cycloalkyl, C7-C20Aralkyl, C7-C20Alkaryl, C10-C20Fused ring aryl, C2-C10Alkylene；But R1
And R2It not hydrogen, R3-R6And R1-R2nOptionally comprise on group one or several hetero atom as carbon or hydrogen atom or both
Substituent, described hetero atom is selected from nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atom, R3-R6And R1-R2nIn group one or more
Selection of land connects cyclization；N is the integer of 0-10；
Wherein give electricity body compound b selected from unitary or polyhydric aliphatic race carboxylate, aromatic carboxylic acid esters or two ethers chemical combination
Thing；
(2) alkyl aluminum compound；Its formula is AlR'''3, R''' is identical or different C1-8Alkyl, one of them
Or two alkyl can be replaced by chlorine, the consumption Al/Ti mol ratio of alkyl aluminum compound is 1～1000；
(3) external donor compound, by alkylene three hydrocarbyloxysilane shown in logical formula IV,
(IV)
R in logical formula IV1、R2、R3For the alkyl of carbon number 1～20 straight or branched, cycloalkyl, aralkyl, alkane virtue
Base, fused ring aryl, alkylene, R1、R2、R3The most identical or different；R4For carbon number 1～20 alkylene.
Particular compound is such as: vinyltrimethoxy silane, VTES, vinyl tripropoxy silicon
Alkane, vinyltributoxysilane, vinyl three cyclopentyloxy silane, vinyl three cyclohexyloxy silane, vinyl triphen oxygen
Base silane, acrylic trimethoxy silane, acrylic triethoxysilane, acrylic tripropoxy silane, acrylic three fourth oxygen
Base silane, acrylic three cyclopentyloxy silane, acrylic three cyclohexyloxy silane, acrylic triple phenoxyl silane, cyclobutenyl three
Methoxy silane, cyclobutenyl triethoxysilane, cyclobutenyl tripropoxy silane, cyclobutenyl three butoxy silane, cyclobutenyl three
Cyclopentyloxy silane, cyclobutenyl three cyclohexyloxy silane, cyclobutenyl triple phenoxyl silane, styryl trimethoxy silane, benzene
VTES, styryl tripropoxy silane, styryl three butoxy silane, styryl three ring penta oxygen
Base silane, styryl three cyclohexyloxy silane, styryl triple phenoxyl silane, cinnamyl group trimethoxy silane, phenylpropyl alcohol
Thiazolinyl triethoxysilane, cinnamyl group tripropoxy silane, cinnamyl group three butoxy silane, cinnamyl group three cyclopentyloxy
Silane, cinnamyl group three cyclohexyloxy silane, cinnamyl group triple phenoxyl silane, benzene cyclobutenyl trimethoxy silane, benzene fourth third
Thiazolinyl triethoxysilane, benzene cyclobutenyl tripropoxy silane, benzene cyclobutenyl three butoxy silane, benzene cyclobutenyl three cyclopentyloxy
Silane, benzene cyclobutenyl three cyclohexyloxy silane, benzene cyclobutenyl triple phenoxyl silane, allene base trimethoxy silane, allene
Ethyl triethoxy silicane alkane, allene base tripropoxy silane, allene base three butoxy silane, allene base three cyclopentyloxy silicon
Alkane, allene base three cyclohexyloxy silane, allene base triple phenoxyl silane, butadienyl trimethoxy silane, butadienyl
Triethoxysilane, butadienyl tripropoxy silane, butadienyl three butoxy silane, butadienyl three cyclopentyloxy silicon
Alkane, butadienyl three cyclohexyloxy silane, butadienyl triple phenoxyl silane etc.；Preferred vinyl trimethoxy silane, ethylene
Ethyl triethoxy silicane alkane, vinyl tripropoxy silane, vinyltributoxysilane, allyltrimethoxysilanis, allyl
One in ethyl triethoxy silicane alkane, pi-allyl tripropoxy silane, pi-allyl three butoxy silane.
Logical alkylene three hydrocarbyloxysilane shown in formula IV, can use conventional synthetic method in laboratory system
Standby, it is possible to chemistry product purchasing way by, buying on the market.
Instant component (1) is given the compound of electricity body compound a preferred formula (V)；
(V)
(V) R in formula1-R6、R1-R2For hydrogen that is identical or that differ, halogen atom, the C of straight or branched1-C20Alkyl, C3-
C20Cycloalkyl, C7-C20Aralkyl or C6-C20Aryl.
Further preferably lead to the compound shown in formula VI instant component (1) to electricity body compound a；
(VI)
(VI) R in1-R6、R1-R2For identical or different hydrogen, halogen atom, the C of straight or branched1-C20Alkyl, C3-C20Ring
Alkyl, C7-C20Aralkyl or C6-C20Aryl；R ' is identical or different hydrogen, halogen atom, the C of straight or branched1-C20Alkyl,
C3-C20Cycloalkyl, C7-C20Aralkyl or C6-C20Aryl.
Particular compound is such as: 2-isopropyl-2-isopentyl-1,3-propylene glycol dibenzoate, 2,4-PD hexichol first
Double (benzoyloxy methyl) fluorenes of acid esters, 3,5-heptandiol dibenzoate, 4-ethyl-3,5-heptandiol dibenzoate, 9,9-
Deng.
In the component (1) of the present invention, another electron donor compound b is unitary or polyhydric aliphatic race carboxylate, fragrance
Race's carboxylate or diether compound.Such as: benzoate, phthalic acid ester, malonate, succinate, glutarate
Deng.Concrete the most such as: ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate,
Diisooctyl phthalate, dinoctyl phthalate, diethyl malonate, malonic acid di-tert-butyl ester, 2,3-diisopropyl
Diethyl succinate, 2,3-diisopropyl di-iso-octyl succinate, 2,3-diisopropyl dibutyl succinate, 2,3-diisopropyl
Base succinic acid dimethyl esters, 2,2-dimethyl succinate diisobutyl ester, 2-Ethyl-2-Methyl di-iso-octyl succinate, 2-ethyl-
2-methyl succinic diethyl phthalate, diethylene adipate, dibutyl adipate, ethyl sebacate, dibutyl sebacate, maleic
Diethyl adipate, maleic acid n-butyl, naphthalene dicarboxylic acids diethylester, naphthalene dicarboxylic acids dibutyl ester, triethyl trimellitate, partially
Benzenetricarboxylic acid tributyl, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tributyl, PMA tetra-ethyl ester, PMA four butyl ester etc..
Wherein give 1,3 2 ethers shown in diether compound preferred formula (VII) described in electricity body compound b
Compound,
(VII)
Wherein RI、RII、RIII、RIV、RVAnd RVIIdentical or different, selected from hydrogen, halogen atom, the C of straight or branched1-C20Alkane
Base, C3-C20Cycloalkyl, C7-C20Aralkyl, C6-C20One in aryl, RVIIAnd RVIIIIdentical or different mutually, selected from straight chain or
The C of side chain1-C20Alkyl, C3-C20Cycloalkyl, C7-C20Aralkyl, C6-C20One in aryl；RI-RVIGroup between can keyed jointing
Cyclization.Preferably RVIIAnd RVIIISelected from C1-C4The 1,3-diether of alkyl.
In the present invention above-mentioned 1,3-diether compound be disclosed in Chinese patent CN1020448C, CN100348624C and
In CN1141285A.Disclosed in it, related content is all incorporated herein by reference.
In component (1), the formula of described titanium compound is: Ti (ORw)4-kXk, wherein RwBeing the alkyl of 1～20, X is
Cl, Br or I, k is the integer of 0～4.Specifically can be selected for titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, four ethoxies
A kind of in base titanium, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium, trichlorine one ethanolato-titanium, titanous chloride. or theirs is mixed
Compound, preferably titanium tetrachloride.
Component (1) catalytic component of the present invention can be urged according to solid disclosed in Chinese patent CN93102795.0
The preparation method of agent is prepared, MgCl of the present invention2.nRqOH alcohol adduct be disclosed in Chinese patent CN1091748,
In CN1330086A and CN101050245, related content disclosed in it is all incorporated herein by reference.
The concrete preparation method of magnesium halide alcohol adduct carrier is anhydrous magnesium halide and low-carbon alcohols to be mixed, temperature reaction
Generating magnesium halide alcohol adduct melt, reaction temperature is 90～140 DEG C, puts into cooling in disperse medium after high shear forces
In inert media, form spherical magnesium halide alcohol polymer granule, scrubbed, obtain ball type carrier after drying.High shear forces can be adopted
Obtain by conventional method, as high-speed mixing method (such as CN1330086), nebulization (such as US6020279) and hypergravity rotate
Bed (such as CN1580136A) and mulser method (CN1463990A) etc..Dispersant system uses hydro carbons atent solvent, such as kerosene, in vain
Oil, silicone oil, paraffin oil, vaseline oil etc..Cooling medium is selected from pentane, hexane, heptane, petroleum ether, raffinates oil.
The synthetic method of instant component (1) catalytic component is that magnesium halide alcohol adduct obtained above is suspended in pre-cooling
Titanium compound or titanium compound and atent solvent mixture in, atent solvent such as hexane, heptane, octane, decane, toluene
Deng, temperature is-30 DEG C～0 DEG C, preferably-20 DEG C～-10 DEG C；Then said mixture is heated to 80 DEG C～130 DEG C, is heating up
During add electron donor compound a and electron donor compound b.Then add titanium compound and process one or many.Finally,
Repeatedly wash with atent solvent and obtain ingredient of solid catalyst.
In the preparation process of the catalytic component of the present invention, the addition of electron donor a and b order in no particular order.At this
In invention component (1) catalytic component preparation process, wherein in terms of every mole of magnesium, electron donor compound a is 0.001～0.5
Mole, preferably 0.001～0.1 mole；Electron donor compound b is 0.01～5 mole, preferably 0.05～1 mole.
Can be used in conjunction with to electricity body compound a and electron donor compound b in many ways, the two can be asynchronous
Rapid neutralization uses under different condition, it is also possible to be simultaneously introduced.
Component (2) alkyl aluminum compound of the present invention, its formula is AlR'''3, R''' is C that is identical or that differ1-8's
Alkyl, wherein one or two alkyl can be replaced by chlorine, and one or more alkyl aluminum can be selected to be used in mixed way, excellent
Select triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, chlorination alkyl aluminum, Al (n-C6H13)3、Al(n-C8H17
)3、AlEt2Cl etc., typically with Al/Ti mol ratio be 1～1000 use abovementioned alkyl aluminium compounds.
Component (2) alkyl aluminum compound and component (3) external donor compound can be individually or as two kinds of compositions
Mixture contacts with component (1) catalytic component.
In component (3) external donor compound, the consumption of alkylene three hydrocarbyloxysilane is every mole aluminium compound
0.001～1.0 mole.
Above-mentioned catalyst system is suitable for alkene CH2=CHRy(wherein RyIt is hydrogen or the alkyl or aryl of 1～6 carbon) with
And the polyreaction of the mixture containing (if necessary) a small amount of alkadienes.
The polymerization of alkene is carried out according to known methods, the liquid phase of the solution in atent solvent in liquid monomer or monomer
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.
Detailed description of the invention
Provide following example so that the present invention is better described, be not intended to limit the scope of the present invention.
Method of testing:
1, melt index: measure according to ASTM D1238-99.
2, polymer isotacticity: use heptane extraction process to measure (heptane boiling extracting 6 hours), i.e. take the polymerization that 2g is dried
Thing sample, is placed in extractor and extracts 6 hours with boiling heptane, afterwards, be dried by residue to constant weight, resulting polymers weight
(g) with 2 ratio be isotacticity.
3, molecular chain conformation test: polymer molecular weight and molecular weight distribution MWD(MWD=Mw/Mn) use PL-
GPC220 is with trichloro-benzenes for solvent mensuration (standard specimen: PS, flow velocity: 1.0ml/min, pillar: 3xPlgel10um at 150 DEG C
M1xED-B300x7.5nm).
Embodiment 1
The preparation of diol ester compound 2,4-PD dibenzoate
The preparation of (1) 2,4-pentanediol
The mixture of 10g2,4-pentanedione and 30ml methanol is added drop-wise to 2.5g sodium borohydride, 0.1g hydrogen-oxygen at 0～10 DEG C
Change in the mixed solution of sodium and 25ml water.Finish, removal of solvent under reduced pressure, with 40ml ethyl acetate continuous extraction 15h.Remove molten
Agent, column chromatography, obtain colourless liquid 2,4-pentanediol, yield 90%.
The preparation of (2) 2,4-glycol dibenzoate
0.03mo12,4-pentanediol adds 30ml oxolane and 0.09mol pyridine, under agitation adds 0.075mol
Benzenecarbonyl chloride., is heated to reflux 4h.Adding 20ml saturated aqueous common salt after cooling, ethyl acetate extracts, anhydrous Na2SO4It is dried, removes
Solvent.Colourless liquid 2,4-glycol dibenzoate, yield 95% are distilled to obtain in column chromatography or decompression.
1H NMR(δ, ppm, TMS): 1.3～1.4 (8H, m, methyl H)；2.0～2.1 (2H, m, methylene H)；5.2～
5.3 (2H, m, the methine H of ester group)；7.3～8.0 (10H, m, phenyl ring H).
Embodiment 2
2A, the preparation of solids containing titanium catalytic component A
In the glass reaction bottle of the 300ml band stirring being sufficiently displaced from through high pure nitrogen, add four chlorinations of 100ml
Titanium, is cooled to-20 DEG C, adds spherical magnesium chloride alcohol adduct (preparation method sees Chinese patent CN1330086A), delays stage by stage
Slowly it is warming up to 110 DEG C, temperature-rise period adds 2 prepared in embodiment 1,4-glycol dibenzoate 2.5mmol and neighbour
Phthalic acid dibutyl ester 3.9mmol, after 110 DEG C of constant temperature 0.5h, filters off liquid, adds titanium tetrachloride and processes secondary, then with
Alkane washs five times, obtains solids containing titanium catalytic component A (major catalyst) after vacuum drying.
2B, propylene polymerization
In 5 liters of autoclaves, stream of nitrogen gas is used to purge at 70 DEG C 1 hour, then will polymerization with gas-phase propene
Still replace 3 times, under nitrogen protection introduce 5ml triethyl aluminum hexane solution (concentration of triethyl aluminum is 0.5mmol/ml),
Hexane solution (concentration of external electron donor is 0.1mmol/ml), 8ml anhydrous hexane and the 8～12mg titaniferous of external electron donor are solid
Body catalyst component A (major catalyst).Close autoclave, introduce appropriate hydrogen and the liquid propene of 1.0～1.2Kg；In stirring
Quickly interior temperature is risen to 70 DEG C down.At 70 DEG C, polyreaction is after 1 hour, stops stirring, removes unpolymerized propylene monomer,
Collected polymer, is vacuum dried 2 hours, calculated activity of weighing (AC) at 70 DEG C.
Embodiment 3～29
The solid catalyst of preparation in the 2A of embodiment 2, according to the method for propylene polymerization in the 2B of embodiment 2, is pressed respectively
Difference adds the conditions such as hydrogen amount, different external electron donor addition, different polymerization temperatures and carries out polymerization result.Outside adding during polymerization
Electron donor is the hexane solution of alkylene three hydrocarbyloxysilane, and polymerization and test result are shown in Table one, table two.
Comparative example 1～3
The external electron donor of addition, with embodiment 3～29, is simply changed into 1ml cyclohexyl methyl dimethoxy by polymerization
The hexane solution (concentration of CHMMS is 0.1mmol/ml) of silane (CHMMS), polymerization result is shown in Table one, table two.
Comparative example 4～5
The external electron donor of addition, with embodiment 3～29, is simply changed into 1ml dicyclopentyl dimethoxyl silicon by polymerization
The hexane solution (concentration of D is 0.1mmol/ml) of alkane (D), polymerization result is shown in Table one.
Table one
Note: VTMS: vinyltrimethoxy silane
VTES: VTES
ATES: acrylic triethoxysilane
CHMMS: Cyclohexylmethyldimethoxysilane
D: dicyclopentyl dimethoxyl silane
Table two
Claims (13)
1. the catalyst system and catalyzing for olefinic polyreaction, it is characterised in that comprise the product of following component:
(1) a kind of solids containing titanium catalytic component, this catalytic component is at logical formula I MgCl2.nRqMagnesium chloride alcohol shown in OH
Logical formula II Ti (OR it is loaded with on polymer beadsw)4-kXkShown titanium compound and at least two electron donor compound a, b；
R in its formula of (I)qFor the alkyl that carbon number is 1～18, n is 0.1～6；
R in its formula of (II)wFor the alkyl that carbon number is 1～20, X is Cl, Br or I, and k is the integer of 0～4；
Wherein giving electricity body compound a is the diol-lipid compound shown in formula (V):
(V) R in formula1-R6、R1-R2For hydrogen that is identical or that differ, halogen atom, the C of straight or branched1-C20Alkyl, C3-C20Ring
Alkyl, C7-C20Aralkyl or C6-C20Aryl；
Wherein give electricity body compound b selected from unitary or polyhydric aliphatic race carboxylate, aromatic carboxylic acid esters or diether compound；
(2) alkyl aluminum compound；Its formula is AlR " '3, R " ' for identical or different C1-8Alkyl, wherein one or two alkane
Base can be replaced by chlorine, and the consumption Al/Ti mol ratio of alkyl aluminum compound is 1～1000；
(3) external donor compound, by alkylene three hydrocarbyloxysilane shown in logical formula IV,
R in logical formula IV1、R2、R3For the alkyl of carbon number 1～20 straight or branched, cycloalkyl, aralkyl, alkaryl, thick
Cyclophane base, alkylene, R1、R2、R3The most identical or different；R4For carbon number 1～20 alkylene.
Catalyst system and catalyzing for olefinic polyreaction the most according to claim 1, it is characterised in that described component (1)
In to give electricity body compound a be logical compound shown in formula VI；
(VI) R in1-R6For identical or different hydrogen, halogen atom, the C of straight or branched1-C20Alkyl, C3-C20Cycloalkyl, C7-C20
Aralkyl or C6-C20Aryl；R ' is identical or different hydrogen, halogen atom, the C of straight or branched1-C20Alkyl, C3-C20Cycloalkanes
Base, C7-C20Aralkyl or C6-C20Aryl.
Catalyst system and catalyzing for olefinic polyreaction the most according to claim 1, it is characterised in that described component (1)
In give electricity body compound a be 2-isopropyl-2-isopentyl-1,3-propylene glycol dibenzoate, 2,4-PD dibenzoate,
Double (benzoyloxy methyl) fluorenes of 3,5-heptandiol dibenzoate, 4-ethyl-3,5-heptandiol dibenzoate, 9,9-.
Catalyst system and catalyzing for olefinic polyreaction the most according to claim 1, it is characterised in that described component (1)
In give electricity body compound b described in diether compound be 1,3 diether compounds shown in formula (VII),
Wherein RI、RII、RIII、RIV、RVAnd RVIIdentical or different, selected from hydrogen, halogen atom, the C of straight or branched1-C20Alkyl, C3-
C20Cycloalkyl, C7-C20Aralkyl, C6-C20One in aryl, RVIIAnd RVIIIIdentical or different, selected from straight or branched mutually
C1-C20Alkyl, C3-C20Cycloalkyl, C7-C20Aralkyl, C6-C20One in aryl；RI-RVIGroup between can keyed jointing cyclization.
Catalyst system and catalyzing for olefinic polyreaction the most according to claim 4, it is characterised in that described component (1)
In give electricity body compound b in diether compound, RVIIAnd RVIIISelected from C1-C4Alkyl.
Catalyst system and catalyzing for olefinic polyreaction the most according to claim 1, it is characterised in that described component (1)
In preparation process, wherein in terms of every mole of magnesium, electron donor compound a is 0.001～2 mole, and electron donor compound b is
0.01～5 mole.
Catalyst system and catalyzing for olefinic polyreaction the most according to claim 1, it is characterised in that described component (1)
In preparation process, wherein in terms of every mole of magnesium, electron donor compound a is 0.001～1 mole；Electron donor compound b is
0.05～1 mole.
Catalyst system and catalyzing for olefinic polyreaction the most according to claim 1, it is characterised in that described titanium compound
For titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen
A kind of in base titanium, trichlorine one ethanolato-titanium or their mixture.
Catalyst system and catalyzing for olefinic polyreaction the most according to claim 1, it is characterised in that described titanium compound
For titanium tetrachloride.
Catalyst system and catalyzing for olefinic polyreaction the most according to claim 1, it is characterised in that described component (2)
Alkyl aluminum compound is triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, Al (n-C8H17)3、AlEt2In Cl
A kind of or their mixture.
11. catalyst system and catalyzings for olefinic polyreaction according to claim 1, it is characterised in that described component (3)
External donor compound alkylene three hydrocarbyloxysilane is vinyltrimethoxy silane, VTES, second
Thiazolinyl tripropoxy silane, vinyltributoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, alkene
One in propyl group tripropoxy silane, pi-allyl three butoxy silane.
12. the catalyst system and catalyzing for olefinic polyreaction according to claim 1, it is characterised in that described component (3)
In external donor compound, the consumption of alkylene three hydrocarbyloxysilane is every mole aluminium compound 0.001～1.0 moles.
The catalyst system and catalyzing for olefinic polyreaction described in 13. claim 1～12 any one is in olefinic polyreaction
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| CN102040690A (en) * | 2009-10-20 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing polypropylene with low ash content |
| CN102432701A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization |
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| CN102040690A (en) * | 2009-10-20 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing polypropylene with low ash content |
| CN102432701A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization |
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