CN104250318A - Olefin polymerization catalyst - Google Patents
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- CN104250318A CN104250318A CN201310268991.7A CN201310268991A CN104250318A CN 104250318 A CN104250318 A CN 104250318A CN 201310268991 A CN201310268991 A CN 201310268991A CN 104250318 A CN104250318 A CN 104250318A
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Abstract
The invention relates to an olefin polymerization catalyst comprising a titanium-containing solid catalyst component using a polyol ester compound as an internal electron donor, an aluminum alkyl component, and an alkenyl trialkyl oxy silane compound and an as an alkyl dialkyl oxy silane compound using as an external electron donor by compounding; by reasonable matching of the internal and external electron donors, the catalyst directional ability and sensitivity to hydrogen regulation are enhanced, and polymerization method is simple. The molecular weight distribution index of a prepared polymer is wider than that of a polymer prepared by using methyl cyclohexyl dimethoxy silane (CHMMS) as an external electron donor, and the olefin polymerization catalyst is conductive to polymer processing.
Description
Technical field
The present invention relates to a kind of catalyzer for olefinic polyreaction, more particularly, relate to and a kind ofly comprise solids containing titanium catalyst component, promotor and alkylene three hydrocarbyloxysilane compound and the composite catalytic systems for polymerization of olefins as external donor compound of alkyl two hydrocarbyloxysilane compound, belong to field of olefin polymerisation.
Background technology
As everyone knows, 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 catalyzer.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 find that one group of external electron donor that polymkeric substance can be made to have fine over-all properties for special catalyst is 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, and mentions methyl benzoate and tetraethoxysilane can be used as Mixed electron donor in patent; Japanese Patent JP19820174495; In JP19920331459, also using tetraethoxysilane as external electron donor, but net effect is all bad.
Chinese patent CN02100896.5, CN02100900.7, CN03109781.2, CN03140565.7, CN200410073623.8, CN200410073621.9 etc. describe and use polyol ester compounds and the composite catalyst component for internal electron donor of adjacent benzene dicarboxylic acid ester compound, when this catalyst component is used for propylene polymerization, external electron donor alkyl two hydrocarbyloxysilane used 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 using Cyclohexylmethyldimethoxysilane, second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane (DCPMS), two (cyclobutylmethyl) dimethoxysilane etc. are also used, but find from disclosed patent, the hydrogen response of this kind of catalyst system is poor.
How to keep with the feature of the polyol ester compounds catalyst system that is internal electron donor, improving orientation property and 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, the granulated ingredient of solid catalyst being internal electron donor using polyol ester compounds in olefinic polymerization time add alkylene three hydrocarbyloxysilane compound and composite orientation property and the hydrogen response improving catalyzer as external donor compound further of alkyl two hydrocarbyloxysilane compound.The molecular weight distributing index of the polymkeric substance obtained is wider as polymkeric substance during external electron donor than using Cyclohexylmethyldimethoxysilane (CHMMS), is conducive to polymer processing.
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.
The present invention is used for the catalyzer of olefinic polyreaction, 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; Described is the diol-lipid compound shown in logical formula I to electric body compound:
R in formula I
1-R
6, R
1-R
2ngroup is identical or different, is hydrogen, halogen, substituted or unsubstituted C
1-C
20the alkyl of straight or branched, C
3-C
20cycloalkyl, C
7-C
20aralkyl, C
7-C
20alkaryl, C
10-C
20fused ring aryl, C
2-C
10alkylene, but R
1and R
2not hydrogen, R
3-R
6and R
1-R
2ngroup optionally comprises one or several heteroatoms as carbon or hydrogen atom or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6and R
1-R
2none or more in group optionally connect into ring; N is the integer of 0-10; Described electron donor compound amount, in every mole of magnesium, is 0.01 ~ 5 mole;
(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, and wherein the aluminium in component (2) and the titanium mol ratio in component (1) are 1 ~ 1000;
(3) compound external donor compound, logical alkylene three hydrocarbyloxysilane shown in formula II and the alkyl shown in logical formula III two hydrocarbyloxysilane;
R in logical formula II
1, R
2, R
3for alkyl, cycloalkyl, aralkyl, alkaryl, fused ring aryl, the alkylene of carbonatoms 1 ~ 20 straight or branched, R
1, R
2, R
3optionally identical or different; R
4for carbonatoms 1 ~ 20 alkylene;
R in its formula of (III)
1, R
2, R
3, R
4for the alkyl or cycloalkyl of carbonatoms 1 ~ 20 straight or branched, R
1, R
2optionally identical or different; R
3, R
4optional identical difference.
R in logical formula II
1, R
2, R
3for carbonatoms 1 ~ 20 alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylene, fused ring aryl, R
1, R
2, R
3can be identical, also can be different; R
4for carbonatoms 1 ~ 20 alkylene.
Particular compound is as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, vinyltributoxysilane, vinyl three cyclopentyloxy silane, vinyl three cyclohexyloxy silane, vinyltriphenoxysilane, propenyl Trimethoxy silane, propenyl triethoxyl silane, propenyl tripropoxy silane, propenyl three butoxy silane, propenyl three cyclopentyloxy silane, propenyl three cyclohexyloxy silane, propenyl 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 group Trimethoxy silane, cinnamyl group triethoxyl silane, 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 butenyl Trimethoxy silane, benzene fourth propenyl triethoxyl silane, 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.
Logical alkylene three hydrocarbyloxysilane shown in formula II, can adopt conventional synthetic method to be prepared in laboratory, also by general chemical product purchasing way, can buy on the market.
Alkyl two hydrocarbyloxysilane in its formula of (III) specifically can select Cyclohexylmethyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane, dicyclopentyl dimethoxyl silane, methylcyclohexyl diethoxy silane, diisopropyldiethoxysilane, diisobutyl diethoxy silane, dicyclohexyl diethoxy silane, bicyclopentyl diethoxy silane, methylcyclohexyl dipropoxy silane, di-isopropyl dipropoxy silane, diisobutyl dipropoxy silane, dicyclohexyl dipropoxy silane, bicyclopentyl dipropoxy silane, methylcyclohexyl dibutoxy silane, di-isopropyl dibutoxy silane, diisobutyl dibutoxy silane, dicyclohexyl dibutoxy silane, bicyclopentyl dibutoxy silane etc., one in preferable methyl cyclohexyl dimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane.
General formula is alkyl two hydrocarbyloxysilane shown in (III), and conventional synthetic method can be adopted to be prepared in laboratory, also by general chemical product purchasing way, can buy on the market.
The consumption of described compound external donor compound alkylene three hydrocarbyloxysilane is every mole aluminum compound 0.001 ~ 1.0 mole; The consumption of described alkyl dialkoxy silicane is every mole aluminum compound 0.001 ~ 1.0 mole; Add after the compound of logical formula II and logical formula III can mix, also can add respectively, the additional proportion of logical formula II and logical formula III compound is 1:100 ~ 100:1.
The compound in electric body compound preferred formula (IV) is given in component of the present invention (1).
(IV) R in formula
1-R
6, R
1-R
2for the C of identical or not identical hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
7-C
20aralkyl or C
6-C
20aryl.
The electric body compound also compound shown in preferred formula (V) is given in described component (1).
(V) R in
1-R
6, R
1-R
2for the C of identical or different hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
7-C
20aralkyl or C
6-C
20aryl; R ' is the C of identical or different hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
7-C
20aralkyl or C
6-C
20aryl.
Particular compound is as 2-sec.-propyl-2-isopentyl-1, ammediol dibenzoate, 2,4-glycol dibenzoate, 3,5-heptanediol dibenzoates, 4-ethyl-3,5-heptanediol dibenzoate, 9,9-two (benzoyloxy methyl) fluorenes etc.
In component (1), the general formula of described titanium compound is: Ti (OR
w)
4-kx
k, wherein R
wbe the alkyl of 1 ~ 20, X is F, Cl, Br or its mixture, and k is the integer of 1 ~ 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.
Component of the present invention (1) solids containing titanium catalyst component can be prepared according to the preparation method of solid catalyst disclosed in Chinese patent CN1436796A, CN1453298A, wherein binary alcohol esters compounds synthesizes according to Chinese patent CN1436766, and associated viscera disclosed in it all introduces the present invention as a reference.
In instant component (1) catalyst component preparation process, wherein in every mole of magnesium, electron donor compound is 0.01 ~ 5 mole, preferably 0.05 ~ 1 mole.
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) compound 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.
Olefinic polymerization 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.
3, molecular chain conformation test: polymericular weight and molecular weight distribution MWD(MWD=Mw/Mn) adopt PL-GPC220 to take trichlorobenzene as the mensuration of solvent at 150 DEG C (standard specimen: PS, flow velocity: 1.0ml/min, pillar: 3xPlgel10um M1xED-B300x7.5nm).
Embodiment 1
The preparation of diol ester compound 2,4-glycol dibenzoate
The preparation of (1) 2,4-pentanediol
The mixture of 10g2,4-diacetylmethane and 30ml methyl alcohol is added drop-wise in the mixing solutions of 2.5g sodium borohydride, 0.1g sodium hydroxide and 25ml water at 0 ~ 10 DEG C.Finish, removal of solvent under reduced pressure, with 40ml ethyl acetate continuous extraction 15h.Except desolventizing, column chromatography, obtains colourless liquid 2,4-pentanediol, yield 90%.
The preparation of (2) 2,4-glycol dibenzoate
Add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in 0.03mo12,4-pentanediol, under agitation add 0.075mol Benzoyl chloride, reflux 4h.20ml saturated aqueous common salt is added, extraction into ethyl acetate, anhydrous Na after cooling
2sO
4drying, except desolventizing.Column chromatography or underpressure distillation obtain colourless liquid 2,4-glycol dibenzoate, yield 95%.
1h NMR(δ, ppm, TMS): 1.3 ~ 1.4 (8H, m, methyl H); 2.0 ~ 2.1 (2H, m, methylene radical H); 5.2 ~ 5.3 (2H, m, the methyne H of ester group); 7.3 ~ 8.0 (10H, m, phenyl ring H).
Embodiment 2
The preparation of 2A, solid catalyst A (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 TiCl
456ml, is slowly warming up to 80 DEG C, in temperature-rise period, separates out solids gradually, adds the diol ester compound 6mmol prepared above, holding temperature 1 hour, after filtration, adds toluene 70ml, and washing secondary, obtains solid sediment.Then toluene 60ml is added, TiCl
440ml, is warmed up to 100 DEG C, processes 2 hours, after venting filtrate, then adds toluene 60ml, TiCl
440ml, is warmed up to 100 DEG C, processes 2 hours, venting filtrate.Add toluene 60ml, boiling state washs three times, then adds hexane 60ml, after boiling state washing secondary, obtains ingredient of solid catalyst.
2B, 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 the composite external electron donor of 1ml, 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 solid catalyst prepared in the 2A of embodiment 2 method according to propylene polymerization in the 2B of embodiment 2, the composite external electron donor adding different ratio during polymerization is respectively the hexane solution of vinyltrimethoxy silane and Cyclohexyl Methyl Dimethoxysilane (or dicyclopentyl dimethoxyl silane), and polymerization and test result are in table one and table two.
Embodiment 10 ~ 17
According to the method for embodiment 3 ~ 9, the composite external electron donor adding different ratio during polymerization is respectively the hexane solution of vinyltriethoxysilane and Cyclohexyl Methyl Dimethoxysilane (or dicyclopentyl dimethoxyl silane), and polymerization and test result are in table one and table two.
Embodiment 18 ~ 24
According to the method for embodiment 3 ~ 9, the composite external electron donor adding different ratio during polymerization is respectively the hexane solution of allyltriethoxysilane and Cyclohexyl Methyl Dimethoxysilane (or dicyclopentyl dimethoxyl silane), and polymerization and test result are in table one and table two.
Comparative example 1 ~ 3
Polymerization process is with embodiment 3 ~ 9, and just the external electron donor added is changed into the hexane solution (concentration of CHMMS is 0.1mmol/ml) of 1ml Cyclohexyl Methyl Dimethoxysilane (CHMMS), polymerization result is in Table table one and table two.
Comparative example 4 ~ 5
Polymerization process is with embodiment 3 ~ 9, and just the external electron donor added is changed into the hexane solution (concentration of D-donor is 0.1mmol/ml) of 1ml dicyclopentyl dimethoxyl silane (D-donor), polymerization result is in table one.
Table one polymerization result
Note: VTMS: vinyltrimethoxy silane
VTES: vinyltriethoxysilane
ATES: allyltriethoxysilane
CHMMS or C: Cyclohexylmethyldimethoxysilane
D or D-donor: dicyclopentyl dimethoxyl silane
As can be seen from table one, use instant component (1), (2) and alkylene three hydrocarbyloxysilane compound and the composite catalyst system as external donor compound of alkyl two hydrocarbyloxysilane compound, after propylene polymerization, under identical hydrogen concentration condition, the polymkeric substance isotactic index obtained and melt index are higher than using Cyclohexylmethyldimethoxysilane (CHMMS) as the isotactic index of polymkeric substance during external electron donor and melt index.
Table two
As can be seen from table two, after using alkylene three hydrocarbyloxysilane compound and the composite catalyst system as external electron donor of alkyl two hydrocarbyloxysilane compound to be used for propylene polymerization, at identical conditions, the molecular weight distributing index of the polymkeric substance obtained is wider as polymkeric substance during external electron donor than using Cyclohexylmethyldimethoxysilane (CHMMS), is conducive to polymer processing.
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 (I); Described is the diol-lipid compound shown in logical formula I to electric body compound:
R in formula I
1-R
6, R
1-R
2ngroup is identical or different, is hydrogen, halogen, substituted or unsubstituted C
1-C
20the alkyl of straight or branched, C
3-C
20cycloalkyl, C
7-C
20aralkyl, C
7-C
20alkaryl, C
10-C
20fused ring aryl, C
2-C
10alkylene, but R
1and R
2not hydrogen, R
3-R
6and R
1-R
2ngroup optionally comprises one or several heteroatoms as carbon or hydrogen atom or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6and R
1-R
2none or more in group optionally connect into ring; N is the integer of 0-10; Described electron donor compound amount, in every mole of magnesium, is 0.01 ~ 5 mole;
(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, and wherein the aluminium in component (2) and the titanium mol ratio in component (1) are 1 ~ 1000;
(3) compound external donor compound, logical alkylene three hydrocarbyloxysilane shown in formula II and the alkyl shown in logical formula III two hydrocarbyloxysilane;
（Ⅱ）
R in logical formula II
1, R
2, R
3for alkyl, cycloalkyl, aralkyl, alkaryl, fused ring aryl, the alkylene of carbonatoms 1 ~ 20 straight or branched, R
1, R
2, R
3optionally identical or different; R
4for carbonatoms 1 ~ 20 alkylene;
R in its formula of (III)
1, R
2, R
3, R
4for the alkyl or cycloalkyl of carbonatoms 1 ~ 20 straight or branched, R
1, R
2optionally identical or different; R
3, R
4optional identical difference.
2. the catalyzer for olefinic polyreaction according to claim 1, is characterized in that, is the diol-lipid compound shown in logical formula IV to electric body compound in described component (1):
(IV) R in formula
1-R
6, R
1-R
2for the C of identical or not identical hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
7-C
20aralkyl or C
6-C
20aryl.
3. the catalyzer for olefinic polyreaction according to claim 1, is characterized in that, is the compound shown in general formula (V) to electric body compound in described component (1);
(V) R in
1-R
6, R
1-R
2for the C of identical or different hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
7-C
20aralkyl or C
6-C
20aryl; R ' is the C of identical or different hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
7-C
20aralkyl or C
6-C
20aryl.
4. the catalyzer for olefinic polyreaction according to claim 1, it is characterized in that, be 2-sec.-propyl-2-isopentyl-1 to electric body compound in described component (1), ammediol dibenzoate, 2,4-glycol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 9,9-two (benzoyloxy methyl) fluorenes.
5. the catalyzer for olefinic polyreaction according to claim 1, it is characterized in that, described titanium compound 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 catalyzer 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, is characterized in that, described electron donor compound amount, counts 0.05 ~ 1 mole with every mole of magnesium.
8. the catalyzer for olefinic polyreaction according to claim 1, is characterized in that, described 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.
9. the catalyzer for olefinic polyreaction according to claim 1, is characterized in that, in described component (3) compound external donor compound, the consumption of alkylene three hydrocarbyloxysilane is every mole aluminum compound 0.001 ~ 1.0 mole; The consumption of described alkyl dialkoxy silicane is every mole aluminum compound 0.001 ~ 1.0 mole.
10. the catalyzer for olefinic polyreaction according to claim 1, it is characterized in that, in described component (3) compound 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, it is characterized in that, in described component (3) compound external donor compound, alkyl two hydrocarbyloxysilane is the one in Cyclohexylmethyldimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane.
The application of the catalyzer for olefinic polyreaction described in any one of 12. claims 1 ~ 11 in olefinic polyreaction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019144976A3 (en) * | 2019-04-26 | 2020-03-19 | 营口市向阳催化剂有限责任公司 | Ziegler-natta catalyst having dual-function external electron donor, and application thereof |
| CN114426607A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, application thereof, olefin polymerization method and polymer |
| CN114437263A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Low-VOC low-odor polypropylene resin and preparation method and application thereof |
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| CN102432701A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019144976A3 (en) * | 2019-04-26 | 2020-03-19 | 营口市向阳催化剂有限责任公司 | Ziegler-natta catalyst having dual-function external electron donor, and application thereof |
| CN114426607A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, application thereof, olefin polymerization method and polymer |
| CN114426607B (en) * | 2020-10-15 | 2024-02-13 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, application of catalyst, olefin polymerization method and polymer |
| CN114437263A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Low-VOC low-odor polypropylene resin and preparation method and application thereof |
| CN114437263B (en) * | 2020-10-20 | 2023-12-08 | 中国石油化工股份有限公司 | Low-VOC low-odor polypropylene resin and preparation method and application thereof |
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