CN102286117B - Titanium-containing solid catalyst component and catalyst for polymerization of olefin - Google Patents
Titanium-containing solid catalyst component and catalyst for polymerization of olefin Download PDFInfo
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Abstract
The invention relates to a titanium-containing solid catalyst component and catalyst for polymerization of olefin, and applications of the titanium-containing solid catalyst component and the catalyst in the homopolymerization and copolymerization of the olefin. According to the titanium-containing solid catalyst component, a catalyst synthesized by taking 2,3-disubstituted butanedioic anhydride compound as an internal electron donor is used for the polymerization of the olefin, in particular during the polymerization of the propylene, thus the catalyst has excellent catalytic activity and excellent performances, and the obtain polymers have higher melting index. Before the development of the invention, the 2,3-disubstituted butanedioic anhydride compound disclosed by the invention is never taken as the internal electron donor to be applied to the catalyst for the polymerization of the olefin.
Description
Technical field
The present invention relates to a kind of ingredient of solid catalyst and catalyzer of titaniferous of for olefines polymerization, and its application in olefinic polymerization.
Technical background
As everyone knows, internal electron donor is as one of important composition of a kind of multi-component heterogeneous Ziegler-Natta catalyst, to stereotaxis ability and the active significant effects that produces of catalyzer, in the development course of Ziegler-Natta catalyst, playing the part of important effect.Different internal electron donors have very big difference owing to its chemical constitution and structure is different to the catalyst system Effect on Performance.
In USP4861847, be the solution that solvent makes magnesium chloride with epoxy chloropropane and tributyl phosphate at first, add the precipitation additive phthalic anhydride, use titanium tetrachloride to handle and obtain ingredient of solid catalyst.In this system, use conventional binary aromatic carboxylic acid's ester compound, for example the catalyzer that obtains such as n-butyl phthalate or diisobutyl phthalate be used for polyacrylic synthetic, active high, polymkeric substance degree of isotacticity height.After this, have some patents in this system, to use different internal electron donors again, with improve catalyzer one or more performance.As in CN1298887, use a kind of diether compound to improve the hydrogen response of catalyzer.In CN1542024, a kind of diol-lipid compound is used in described system, resulting catalyzer also has high reactivity.
For thermoplastic olefin polymer, as linear polyethylene, polypropylene and olefin copolymer, the melting index index is the expression of its ability that flows under certain conditions, it is one of index of polymer processing performance, having reflected flowing and processing characteristics of polymkeric substance, is an importance weighing the polymeric articles quality.Polymer processing as extrude or molding etc. in, need carry out modification to initial polymer, increase its flowability, to improve its processibility.Therefore, the initial polymer of high fusion index especially receives an acclaim at polymer processing.Initial polymer described here refers to the polymkeric substance that directly obtains by polyreaction in the polymerization reactor.
The inventor herein finds to use 2 of general formula (I) in research process, the disubstituted Succinic anhydried compounds of 3-is used for olefinic polymerization as the synthetic catalyzer of internal electron donor, especially the polymerization of propylene the time, catalyzer has good catalytic activity, catalyzer has good performance, and the polymkeric substance that obtains has higher high fusion index.Before this, of the present invention 2, the disubstituted Succinic anhydried compounds of 3-also never is used as in the catalyzer that internal electron donor is applied to olefinic polymerization.
Summary of the invention
The ingredient of solid catalyst of a kind of titaniferous for olefinic polymerization of the present invention, it is by forming homogeneous solution in the organic inert solvent system that magnesium halide is dissolved in organic epoxy compounds and organo phosphorous compounds, in the presence of precipitation additive, be Ti (OR with above-mentioned solution and at least a general formula
5)
4-nX
nTitanium compound carry out contact reacts, separate out the ingredient of solid catalyst of titaniferous.In the ingredient of solid catalyst preparation process of titaniferous, add at least a compound shown in the following general formula (I) that is selected from;
R in the general formula (I)
1～R
4Can be identical or inequality, be C
1～C
14The alkyl of straight or branched, C
3～C
10Cycloalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl or aralkyl.The compound mol ratio of the magnesium in the described magnesium halide, the titanium in the titanium compound and general formula (I), Mg: Ti: compound=1～200 of general formula (I): 20～4000: 1; Preferred Mg: Ti: compound=5～100 of general formula (I): 50～2000: 1.
The present invention is dissolved in magnesium halide in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, can prepare magnesium halide solution according to disclosed method among the Chinese patent CN85100997, and disclosed associated viscera is all introduced the present invention as a reference among the CN85100997.
Wherein said magnesium halide is selected from the complex compound, magnesium dihalide molecular formula of the water of magnesium dihalide, magnesium dihalide or alcohol the derivative that one of them or two halogen atoms are replaced by alkyl or halogen-oxyl.Particular compound is as magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.
Wherein said organic epoxy compounds comprises at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.Described organic epoxy compounds concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether or tetrahydrofuran (THF).
Wherein said organo phosphorous compounds is hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete 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 or phosphorous acid benzene methyl.
In order to make magnesium halide dissolve more fully, in this solvent system, optionally add a certain amount of inert diluent.Described inert diluent can adopt hexane, heptane, octane, benzene,toluene,xylene, 1 usually, and 2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound and other help other solvent of magnesium halide dissolving.Inert diluent can use separately, also use capable of being combined.
Described halogenated magnesium compound can be used alone or as a mixture.
Solvent temperature is suitable to be chosen between 10～150 ℃, and wherein ceiling temperature should not surpass the boiling point of solvent for use.
Dissolution time is as the criterion to dissolve fully.
In the process of preparation magnesium halide solution, add the order of each component of solution in no particular order.
Above-mentioned magnesium halide solution is being separated out the solid catalytic ingredient of titaniferous in the presence of the precipitation additive with after the reaction of at least a titanium compound.Wherein said titanium compound is selected from general formula Ti (OR
5)
4-nX
nAt least a in the shown compound, R in the formula
5For carbonatoms is 1～20 alkyl, R
5Preferred C
1～C
14Aliphatic group, X is identical or different, is F, Cl or Br, n is selected from 1～4 integer.Particular compound is as a kind of or its mixture in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, described titanium compound should be completely soluble liquefied compound under application of temperature, in the non-polar solvent, preferred titanium tetrachloride.
The temperature of reaction of described titanium compound and magnesium halide solution is preferably :-40～0 ℃.
In the reaction system temperature-rise period, separate out solid catalyst particle, and can regulate the form of the solid catalyst of titaniferous by the speed of heat-up rate.The ceiling temperature that heats up should be controlled below the boiling point of solvent.
Described general formula (I) electron donor compound can add reaction system in the arbitrary steps in the catalyst component preparation process, is preferably granules of catalyst and forms the back adding.Can obtain the solid catalyst of flowable state through conventional washing, drying and other steps for the granules of catalyst that forms.In order to regulate the content of titanium in the catalyzer, also optionally use fresh titanium compound that granules of catalyst is carried out one or many and handle.
At described general formula (I) 2, in the structure of the disubstituted Succinic anhydried compounds of 3-, preferred group is: R
1～R
2For methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, n-hexyl, cyclopentyl, cyclohexyl, phenmethyl, to methylbenzyl or styroyl; R
3～R
4Be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, phenyl, p-methylphenyl, o-tolyl, a tolyl or phenmethyl.Concrete compound comprises: 2,3-di-isopropyl-Succinic anhydried, 2,3-di-isopropyl Succinic anhydried, 2,3-di-isopropyl Succinic anhydried, 3-methyl-2-sec.-propyl Succinic anhydried, 3-ethyl-2-sec.-propyl Succinic anhydried, 3-propyl group-2-sec.-propyl Succinic anhydried, 3-butyl-2-sec.-propyl Succinic anhydried, 3-phenyl-2-sec.-propyl Succinic anhydried etc.
In above-mentioned general formula (I) compound, particularly preferred group is: R
1～R
4Identical, be methyl, ethyl, n-propyl or sec.-propyl.Particularly preferred compound is 2,3-di-isopropyl-Succinic anhydried.
The compound of described general formula (I) can use separately also and can specifically use as succinate compounds, phthalate compound, diether compound, diol-lipid compound etc. with other electron donor compound.
Wherein said precipitation additive is at least a in organic acid anhydride, organic acid, ether and the ketone compounds, concrete as: diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, propionic acid, butyric acid, acetone, benzophenone, methyl ether, ether, propyl ether etc.
In preparation ingredient of solid catalyst process, wherein in every mole of magnesium halide: organic epoxy compounds: 0.2-10mol, preferred 0.5～4mol; Organo phosphorous compounds: 0.1～3mol, preferred 0.3～1.0mol; Precipitation additive is 0.03～1.0 mole, and titanium compound is 0.5～150 mole, and the compound of general formula (I) is 0.02～0.4 mole.
In addition, the present invention also provides a kind of for CH
2=CHR
6The catalyzer of olefinic polyreaction, wherein R
6Be hydrogen or C
1～C
12Alkyl or aryl, preferred C
1～C
6Alkyl, this catalyzer comprise following a), b), c) reaction product of three kinds of components:
A) the above-mentioned solids containing titanium catalyst component that is used for olefinic polymerization of the present invention;
B) alkylaluminium cpd; Its general formula is AlR
7 3, R
7Be C identical or inequality
1～C
8Alkyl, one of them or two alkyl can be replaced by chlorine, can select for use one or more aluminum alkyls mix to use, 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., its consumption are the described alkylaluminium cpds of 50～1000 uses with the Al/Ti mol ratio generally;
C) randomly, a kind of external electron donor compound, for example list or polyfunctional carboxylic acids, carboxylic acid anhydride and carboxylicesters, ketone, ether, alcohol, lactone, and organophosphorus and silicoorganic compound.Preferably have organic silicon compound.Its consumption is 0.005～0.5 mole of every mole of aluminum alkyl compound, 0.02～0.1 mole of preferred every mole of aluminum alkyl compound.
Described external electron donor preferably contains at least one Si-OR
10The general formula of key is R
8 aR
9 bSi (OR
10)
cSilicon compound, wherein a and b are 0,1 or 2 integer, c be 1～3 integer and (a+b+c) and be 4; R
8, R
9And R
10Be C
1-C
18Alkyl, randomly contain heteroatoms.Particularly preferred silicon compound, wherein a is that 1, b is that 1, c is 2, R
8And R
9In have at least one to be to be selected from branched-alkyl, alkenyl, alkylidene group, cycloalkyl or the aromatic yl group with 3～10 carbon atoms, optional heteroatoms and the R of containing
10Be C
1-C
10Alkyl group, particularly methyl.The example of preferred silicon compound has cyclohexyl methyl dimethoxy silane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane and (1,1,1-, three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1,1,1-, three fluoro-2-propyl group)-methyl dimethoxysilane.
In addition, preferred silicon compound also has, and wherein a is that 0, c is 3, R
9Be branched-alkyl or group of naphthene base, optional heteroatoms and the R of containing
10Be methyl.The example of Ren Xuan silicon compound has cyclohexyl trimethoxy silane like this, tert-butyl trimethoxy silane and uncle's hexyl Trimethoxy silane.
Also can select diether compound in addition, 2-sec.-propyl-2-isopentyl-1 wherein, the 3-Propanal dimethyl acetal, two (methoxymethyl) fluorenes of 9,9-are particularly preferred.
Above-mentioned alkylaluminium cpd and optional external electron donor compound can be separately or are carried out contact reacts as two kinds of mixture of ingredients and above-mentioned catalyst component.
Above-mentioned catalyzer is suitable for alkene CH
2=CHR
6, R wherein
6Be the alkyl or aryl of hydrogen or 1～12 carbon, the alkyl of preferred 1～6 carbon and the polyreaction that contains the mixture of (if necessary) a small amount of diolefine.
Catalyst olefinic polymerization provided by the present invention can be adopted the whole bag of tricks of the prior art, and there is no particular limitation.The polymerization of alkene is carried out according to currently known methods, is dissolved in the inert solvent in liquid monomer or monomer, or in gas phase, or by operating in the polymerization mix technology of gas-liquid in mutually.Polymerization temperature is generally 0 ℃～150 ℃, preferred 60 ℃～100 ℃.Polymerization pressure is normal pressure or higher.
It should be noted that, the inventor herein at research process first with a kind of 2 of ad hoc structure that contains, the disubstituted Succinic anhydried compounds of 3-is as the synthetic catalyzer of internal electron donor, and find to use 2, the disubstituted Succinic anhydried compounds of 3-is used for olefinic polymerization as the synthetic catalyzer of internal electron donor, especially the polymerization of propylene the time, the polymkeric substance that obtains has higher high fusion index.
Embodiment
Following Example is used for illustrating the present invention, is not to limit the scope of the invention.
Testing method:
1, melt index: measure according to ASTM D1238-99.
2, polymkeric substance isotactic index: adopt the heptane extraction process to measure (heptane boiling extracting 6 hours): the dry polymer samples of two grams, be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 2 ratio.
3, polymericular weight and molecular weight distribution MWD (MWD=Mw/Mn): adopt the gel permeation chromatography method, being solvent with the trichlorobenzene with PL-GPC220 measures (standard specimens down at 150 ℃, polystyrene, flow velocity: 1.0ml/min, pillar: 3xPlgel 10 μ m MIXED-B 300x7.5nm)
Embodiment 1
1, catalyzer is synthetic: in the double glazing reaction flask at 300ML, add the anhydrous MgCl of 5.0 grams successively
2, 120ml toluene, 8.0ml epoxy chloropropane, 10.0ml tributyl phosphate are after dissolving fully under 60 ℃, this solution is cooled to-25 ℃, and Dropwise 5 0ml titanium tetrachloride is kept half an hour under-25 ℃, slowly be warming up to 90 ℃, add 2,3-di-isopropyl Succinic anhydried 5mmol, reaction 1h, titanium tetrachloride with 40ml washs again, use toluene and hexane wash 2 times after the filtration respectively, vacuum-drying obtains solid catalyst.
2, propylene polymerization: in the 5L autoclave, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of CHMMS is 0.1mmol/ml), 10ml anhydrous hexane and the above-mentioned 10mg ingredient of solid catalyst that obtains of 1.25ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce hydrogen 1L (standard volume) and liquid propene 2.3L, be warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
Embodiment 2
Preparation of catalysts is with embodiment 1
In the 5L autoclave, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of CHMMS is 0.1mmol/ml), 10ml anhydrous hexane and the above-mentioned 10mg ingredient of solid catalyst that obtains of 1.25ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce hydrogen 5L (standard volume) and liquid propene 2.3L, be warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
Embodiment 3
1, catalyzer is synthetic: in the double glazing reaction flask at 300ML, add the anhydrous MgCl of 5.0 grams successively
2, 120ml toluene, 8.0ml epoxy chloropropane, 10.0ml tributyl phosphate are after dissolving fully under 60 ℃, this solution is cooled to-25 ℃, and Dropwise 5 0ml titanium tetrachloride is kept half an hour under-25 ℃, slowly be warming up to 90 ℃, add 2,3-di-isopropyl Succinic anhydried 0.25mmol and diisobutyl phthalate 0.25mmol, reaction 1h, titanium tetrachloride with 40ml washs again, use toluene and hexane wash 2 times after the filtration respectively, vacuum-drying obtains solid catalyst.
2, propylene polymerization: in the 5L autoclave, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of CHMMS is 0.1mmol/ml), 10ml anhydrous hexane and the above-mentioned 10mg ingredient of solid catalyst that obtains of 1.25ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce hydrogen 1L (standard volume) and liquid propene 2.3L, be warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
Embodiment 4
Preparation of catalysts is with embodiment 3
In the 5L autoclave, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of CHMMS is 0.1mmol/ml), 10ml anhydrous hexane and the above-mentioned 10mg ingredient of solid catalyst that obtains of 1.25ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce hydrogen 5L (standard volume) and liquid propene 2.3L, be warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
Embodiment 5
1, catalyzer is synthetic: in the double glazing reaction flask at 300ML, add the anhydrous MgCl of 5.0 grams successively
2, 120ml toluene, 8.0ml epoxy chloropropane, 10.0ml tributyl phosphate are after dissolving fully under 60 ℃, this solution is cooled to-25 ℃, and Dropwise 5 0ml titanium tetrachloride is kept half an hour under-25 ℃, slowly be warming up to 90 ℃, add 2,3-di-isopropyl Succinic anhydried 0.25mmol and 9, two (methoxymethyl) fluorenes 0.25mmol of 9-, reaction 1h with the titanium tetrachloride washing of 40ml, uses toluene and hexane wash 2 times respectively again after the filtration, vacuum-drying obtains solid catalyst.
2, propylene polymerization: in the 5L autoclave, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of CHMMS is 0.1mmol/ml), 10ml anhydrous hexane and the above-mentioned 10mg ingredient of solid catalyst that obtains of 1.25ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce hydrogen 1L (standard volume) and liquid propene 2.3L, be warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
Embodiment 6
Preparation of catalysts is with embodiment 5
In the 5L autoclave, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of CHMMS is 0.1mmol/ml), 10ml anhydrous hexane and the above-mentioned 10mg ingredient of solid catalyst that obtains of 1.25ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce hydrogen 5L (standard volume) and liquid propene 2.3L, be warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
Comparative Examples 1
With embodiment 1, just diisobutyl phthalate is replaced 2,3-di-isopropyl Succinic anhydried.
The performance of table 1 catalyzer
| Embodiment | Polymerization activity (kgPP/gcat) | Polymkeric substance I.I (%) | Polymkeric substance MI (g/10min) | Molecular weight distribution |
| Embodiment 1 | 15.3 | 87.1 | 64.0 | 7.1 |
| Embodiment 2 | 23.0 | 83.8 | 93.6 | 6.8 |
| Embodiment 3 | 30.6 | 92.2 | 58.7 | 6.0 |
| Embodiment 4 | 30.3 | 89.7 | 60.2 | 5.4 |
| Embodiment 5 | 61.5 | 97.3 | 16.5 | 16.5 |
| Embodiment 6 | 40.8 | 97.8 | 40.3 | 40.3 |
| Comparative Examples 1 | 19.3 | 97.9 | 27.6 | 5.6 |
Claims (8)
1. ingredient of solid catalyst that is used for the titaniferous of olefinic polymerization, it is by forming homogeneous solution in the organic inert solvent system that magnesium halide is dissolved in organic epoxy compounds and organo phosphorous compounds, is Ti (OR with above-mentioned solution and at least a general formula
5)
4-nX
nTitanium compound carry out contact reacts, separate out the ingredient of solid catalyst of titaniferous, R in the formula
5Be C
1～C
14Aliphatic group, X is identical or different, is F, Cl or Br, n is selected from 1～4 integer; It is characterized in that, in the ingredient of solid catalyst preparation process of titaniferous, add at least a compound shown in the following general formula (I) that is selected from;
（I）
In the general formula (I), R
1～R
4Can be identical or different, represent C
1～C
10Straight or branched alkyl, C
3～C
10Cycloalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl; The compound mol ratio of the magnesium in the described magnesium halide, the titanium in the titanium compound and general formula (I), Mg:Ti: the compound=1～200:20～4000:1 of general formula (I).
2. the ingredient of solid catalyst of titaniferous according to claim 1 is characterized in that, in the described general formula (I), and R
1～R
4Identical or different, be C
1～C
4The alkyl of straight or branched.
3. the ingredient of solid catalyst of titaniferous according to claim 1 is characterized in that, in the described general formula (I), and R
1～R
4Identical or different, be methyl, ethyl, n-propyl or sec.-propyl.
4. the ingredient of solid catalyst of titaniferous according to claim 1, it is characterized in that, the compound of described general formula (I) is selected from following compounds: 2,3-di-isopropyl Succinic anhydried, 3-methyl-2-sec.-propyl Succinic anhydried, 3-ethyl-2-sec.-propyl Succinic anhydried, 3-propyl group-2-sec.-propyl Succinic anhydried, 3-butyl-2-sec.-propyl Succinic anhydried or 3-phenyl-2-sec.-propyl Succinic anhydried.
5. the ingredient of solid catalyst of titaniferous according to claim 1 is characterized in that, the compound of described general formula (I) uses separately or randomly uses with other known internal electron donor compound.
6. the ingredient of solid catalyst of titaniferous according to claim 5 is characterized in that, described other known internal electron donor compound is succinate compounds, phthalate compound, diether compound or diol-lipid compound.
7. one kind is used for CH
2=CHR
6The catalyzer of olefinic polyreaction, wherein R
6Be hydrogen or C
1～C
6Alkyl, this catalyzer comprises the reaction product of following component:
1) the described solids containing titanium catalyst component of one of claim 1～6;
2) alkylaluminium cpd;
3) randomly, external electron donor component;
Wherein the alkylaluminium cpd general formula is AlR
7 3, R
7Be C identical or inequality
1～C
8Alkyl, one of them or two alkyl can be replaced by chlorine, are 50～1000 to use the abovementioned alkyl aluminum compounds with the Al/Ti mol ratio;
Wherein the external electron donor component is general formula R
8 aR
9 bSi(OR
10)
cSilicon compound, wherein a and b are respectively 0,1 or 2 integer, c be 1～3 integer and (a+b+c) and be 4; R
8, R
9And R
10Be C
1～C
18Alkyl, randomly contain heteroatoms, its consumption is that every mole of aluminum alkyl compound is counted 0.005～0.5 mole.
8. according to claim 7 for CH
2=CHR
6The catalyzer of olefinic polyreaction, the wherein R in the external electron donor component general formula
8, R
9And R
10Identical or different, be C
1～C
4The alkyl of straight or branched, C
5～C
6Cycloalkyl; Its consumption is counted 0.02～0.1 mole with every mole of aluminum alkyl compound.
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| CN102286117A (en) | 2011-12-21 |
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