CN104250319A - Olefin polymerization catalyst system - Google Patents
Olefin polymerization catalyst system Download PDFInfo
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- CN104250319A CN104250319A CN201310269114.1A CN201310269114A CN104250319A CN 104250319 A CN104250319 A CN 104250319A CN 201310269114 A CN201310269114 A CN 201310269114A CN 104250319 A CN104250319 A CN 104250319A
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Abstract
The invention relates to an olefin polymerization catalyst system; a spherical titanium-containing solid catalyst component using a polyol ester compound and a phthalate compound as internal electron donors is added with an alkenyl trialkyl oxy silane compound and an alkyl dialkyl oxy silane compound using as an external electron donor by compounding in olefin polymerization, and under the premise of maintaining the original catalyst wide molecular weight distribution, polymer isotactic index and melt index can be further improved, and meanwhile the relative molecular weight of obtained polymer is greatly increased.
Description
Technical field
The present invention relates to a kind of catalyzer for olefinic polyreaction, more particularly, relate to a kind of by spherical catalyst components, promotor and alkylene three hydrocarbyloxysilane compound and the composite catalytic systems for polymerization of olefins as external donor compound of alkyl two hydrocarbyloxysilane compound.
Background technology
As everyone knows, all be polymerized for alpha-olefin or catalyst system in copolymerization is generally made up of three parts, 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 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, except the taxis affecting polymkeric substance, can have influence on the performance of catalyzer other side to some extent toward contact.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 the performance of some aspect of polymeric articles significantly, therefore find that one group of external electron donor that polymkeric substance can be made to have outstanding properties in some aspects for special catalyst is very favorable.
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 as 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, also used second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane (DCPMS), two (cyclobutylmethyl) dimethoxysilane etc., this catalyst system shows the wide feature of high reactivity, high orientation property and prepared molecular weight distribution.
The present inventor is surprised to find that in research work, using polyol ester compounds and adjacent benzene dicarboxylic acid ester compound as the spherical solid catalyst component of internal electron donor in olefinic polymerization time add alkylene three hydrocarbyloxysilane compound and alkyl two hydrocarbyloxysilane compound is composite as external donor compound, under the prerequisite keeping original catalyzer wide molecular weight distribution, can improve isotactic index and the melting index of polymkeric substance further, the relative molecular weight of the polymkeric substance simultaneously obtained increases much than comparative catalyst.
Summary of the invention
The object of the present invention is to provide a kind of catalyst system for olefinic polyreaction, this catalyst system can improve isotactic index and the melting index of polymkeric substance further, and the relative molecular weight of the polymkeric substance simultaneously obtained increases much than comparative catalyst.
A kind of catalyst system for olefinic polyreaction of the present invention, comprises the reaction product of following component:
(1) a solids containing titanium catalyst component, this catalyst component is at logical formula I MgCl
2.nR
qon magnesium chloride alcohol adduct particle shown in OH, load has logical formula II Ti (OR
w)
4-kx
kshown titanium compound and at least two kinds of electron donor compound as and b;
R in its formula of (I)
qfor carbonatoms is the alkyl of 1 ~ 18, n is 0.1 ~ 6;
R in its formula of (II)
wbe the alkyl of 1 ~ 20, X is Cl, Br or I, and k is the integer of 0 ~ 4;
Be selected from the diol-lipid compound shown in logical formula III wherein to electric body compound a:
R in formula III
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;
Be selected from unitary or polyhydric aliphatic race carboxylicesters, aromatic carboxylic acid esters or diether compound wherein to electric body compound b;
(2) alkylaluminium cpd; Its general formula is AlR " '
3, R " ' be identical or different C
1-8alkyl, wherein one or two alkyl can be replaced by chlorine, and the consumption Al/Ti mol ratio of alkylaluminium cpd is 1 ~ 1000;
(3) compound external donor compound, logical alkyl two hydrocarbyloxysilane shown in alkylene three hydrocarbyloxysilane shown in formula IV and general formula (V);
R in logical formula IV
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 IV, can adopt conventional synthetic method to be prepared in laboratory, also by general chemical product purchasing way, can buy on the market.
R in its formula of (V)
1, R
2, R
3, R
4for carbonatoms 1 ~ 20 alkyl or cycloalkyl, R
1, R
2can be identical, also can be different; R
3, R
4can be the same or different.
Specifically Cyclohexylmethyldimethoxysilane can be selected, 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 (V), 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 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 logical formula IV and general formula (V) can mix, also can add respectively, the additional proportion of logical formula IV and general formula (V) compound is 1:100 ~ 100:1.
The compound of electric body compound a preferred formula (VI) is given in wherein said component (1);
R in formula
1-R
6, R
1-R
2group is as the definition in logical formula III.
The electric body compound a also compound shown in preferred formula (VII) is given in described component (1);
Wherein R
1-R
6, R
1-R
2group is as the definition in logical formula III, and R ' is the C of identical or not identical hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl or C
7-C
20aralkyl.
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 of the present invention (1), another electron donor compound b is unitary or polyhydric aliphatic race carboxylicesters, aromatic carboxylic acid esters or diether 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.
Wherein give 1,3-two ethers shown in diether compound preferred formula (VIII) described in electric body compound b,
Wherein R
i, R
iI, R
iII, R
iV, R
vand R
vIbe same to each other or different to each other, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl, C
7-C
20one in aralkyl, and R
vIIand R
vIIIcan be identical or different mutually, be selected from the C of straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl, C
7-C
20one in aralkyl; R
i-R
vIgroup between can be keyed to ring.Preferred R
vIIand R
vIIIbe selected from C
1-C
41,3-diether of alkyl.
1,3-diether compound above-mentioned in the present invention is disclosed in Chinese patent CN1020448C, CN100348624C and CN1141285A.Associated viscera disclosed in it all introduces the present invention as a reference.
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 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.
Component of the present invention (1) catalyst component can be prepared according to the preparation method of solid catalyst disclosed in Chinese patent CN93102795.0, MgCl of the present invention
2.nR
qoH alcohol adduct is disclosed in Chinese patent CN1091748, CN1330086A and CN101050245, and associated viscera disclosed in it all introduces the present invention as a reference.
Anhydrous magnesium halide and low-carbon alcohol mix by the concrete preparation method of magnesium halide alcohol adduct carrier, temperature reaction generates magnesium halide alcohol adduct melt, temperature of reaction is 90 ~ 140 DEG C, after high shear forces, the inert media of cooling is put in dispersion medium, form spherical magnesium halide alcohol polymer particle, after washing, drying, obtain ball type carrier.High shear forces can adopt conventional method to obtain, as high-speed mixing method (as CN1330086), spray method (as US6020279) and high-gravity rotating bed (as CN1580136A) and mulser method (CN1463990A) etc.Dispersant system adopts hydro carbons inert solvent, as kerosene, white oil, silicone oil, paraffin oil, Vaseline wet goods.Heat-eliminating medium is selected from pentane, hexane, heptane, sherwood oil, raffinates oil.
The synthetic method of instant component (1) catalyst component is suspended in by magnesium halide alcohol adduct obtained above in the titanium compound of precooling or the mixture of titanium compound and inert solvent, inert solvent is as hexane, heptane, octane, decane, toluene etc., 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, in temperature-rise period, adds electron donor compound a and electron donor compound b.Then titanium compound process one or many is added.Finally, repeatedly wash with inert solvent and obtain ingredient of solid catalyst.
In the preparation process of catalyst component of the present invention, electron donor a and b adds order in no particular order.In instant component (1) catalyst component preparation process, wherein in every mole of magnesium, electron donor compound a is 0.001 ~ 2 mole, preferably 0.001 ~ 1 mole; Electron donor compound b is 0.01 ~ 5 mole, preferably 0.05 ~ 1 mole.
Can jointly use in many ways to electric body compound a and electron donor compound b, the two can use in different step He under different condition, also can add simultaneously.With regard to usage quantity, can add in any proportion to the mol ratio of electric body compound a and electron donor compound b.
Component of the present invention (2) alkylaluminium cpd, its general formula is AlR " '
3, R " ' be 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 can contact with component (1) catalyst component by the mixture separately or as two kinds of compositions with component (3) external donor compound mixture.
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 50 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 GB3682-2000.
2, polymkeric substance isotactic index: adopt heptane extraction process to measure (heptane boiling extracting 6 hours), namely get the polymer samples of 2g drying, 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 0.03mol2,4-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).
The preparation of diol ester compound 3,5 one heptanediol dibenzoate
The preparation of (1) 3,5-heptanediol
The mixture of 14.2g3,5-heptadione and 30ml methyl alcohol is added drop-wise in the mixing solutions of 2.5g sodium borohydride, 0.05g 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, obtain white solid 3,5-heptanediol, yield 90%.IR spectrogram is at 3400cm
-1there is strong absorption peak at place, and at 1700cm
-1left and right, without absorption peak, proves that reduction reaction is carried out completely.m.p.60-65℃。
The preparation of (2) 3,5-heptanediol dibenzoates
Add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in 0.03mol3,5-heptanediol, under agitation add 0.075mol Benzoyl chloride, reflux 4h.20m1 saturated aqueous common salt is added, extraction into ethyl acetate, anhydrous Na after cooling
2sO
4drying, except desolventizing.Column chromatography obtains colourless viscous liquid 3,5-heptanediol dibenzoate, yield 92%.
1hNMR (TMS, CDCl
3, ppm): δ 0.9 ~ 1.0(6H, m, methyl H), 1.7 ~ 1.8 (4H, m, the methylene radical H of ethyl), 2.0 ~ 2.1 (2H, m, methylene radical H), 5.21 ~ 5.27 (2H, m, the methyne H of ester group), 7.3 ~ 8.1 (10H, m, phenyl ring H).
The preparation of 4-ethyl-3,5-heptanediol dibenzoate
(1) preparation of 4-ethyl-3,5-heptanediol
Preparation method, with preparation 3,5-heptanediol, just replaces 3,5-heptadione with 4-ethyl-3,5-heptadione.
(2) preparation of 4-ethyl-3,5-heptanediol dibenzoate
Preparation method is with preparation 3,5-heptanediol dibenzoate.
1hNMR (TMS, CDCl
3, ppm): δ 7.8(10H, aromatic hydrocarbons), δ 5.3(2H, CH) and, δ 2.0(1H, CH), δ 1.9(2H, CH
2), δ 1.7(4H, CH
2), δ 1.0(9H, CH
3).
Embodiment 2
The preparation of 2A, solids containing titanium catalyst component A
In the glass reaction bottle that the 300ml band of fully replacing through high pure nitrogen stirs, add the titanium tetrachloride of 100ml, be cooled to-20 DEG C, add spherical magnesium chloride alcohol adduct (preparation method is see Chinese patent CN1330086A), slowly be warming up to 110 DEG C stage by stage, 2 of preparation in embodiment 1 are added in temperature-rise period, 4-glycol dibenzoate 2.5mmol and dibutyl phthalate 3.9mmol, after 110 DEG C of constant temperature 0.5h, elimination liquid, add titanium tetrachloride process secondary, then five times are washed with hexane, solids containing titanium catalyst component A (Primary Catalysts) is obtained after vacuum-drying.
2B, bulk propylene are all polymerized
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) (mixing or add respectively) of 1ml2 kind external electron donor, 10ml anhydrous hexane and 8 ~ 12mg solids containing titanium catalyst component A (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 ~ 24
By the solid catalyst prepared in the 2A of embodiment 2 according to the method for propylene polymerization in the 2B of embodiment 2, add hydrogen amount by difference respectively, different external electron donor add-on carries out the composite polymerization result obtained.Polymerization and test result respectively in table one, table two.
Comparative example 1 ~ 3
The external electron donor added, with embodiment 2B, is just changed into the hexane solution (concentration of CHMMS is 0.1mmol/ml) of 1ml Cyclohexyl Methyl Dimethoxysilane (CHMMS) by polymerization process, polymerization result in table one, table two.
Comparative example 4 ~ 5
Polymerization process is with embodiment 2B, and just the external electron donor added is changed into the hexane solution (concentration of D is 0.1mmol/ml) of 1ml dicyclopentyl dimethoxyl silane (D), polymerization result is in table one.
Table one
Note: VTMS: vinyltrimethoxy silane
VTES: vinyltriethoxysilane
ATES: propenyl triethoxyl silane
CHMMS or C: Cyclohexylmethyldimethoxysilane
D: dicyclopentyl dimethoxyl silane
Table two
Claims (16)
1. for a catalyst system 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 is at logical formula I MgCl
2.nR
qon magnesium chloride alcohol adduct particle shown in OH, load has logical formula II Ti (OR
w)
4-kx
kshown titanium compound and at least two kinds of electron donor compound as and b;
R in its formula of (I)
qfor carbonatoms is the alkyl of 1 ~ 18, n is 0.1 ~ 6;
R in its formula of (II)
wbe the alkyl of 1 ~ 20, X is Cl, Br or I, and k is the integer of 0 ~ 4;
Be selected from the diol-lipid compound shown in logical formula III wherein to electric body compound a:
R in formula III
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;
Be selected from unitary or polyhydric aliphatic race carboxylicesters, aromatic carboxylic acid esters or diether compound wherein to electric body compound b;
(2) alkylaluminium cpd; Its general formula is AlR " '
3, R " ' be identical or different C
1-8alkyl, wherein one or two alkyl can be replaced by chlorine, and the consumption Al/Ti mol ratio of alkylaluminium cpd is 1 ~ 1000;
(3) compound external donor compound, logical alkyl two hydrocarbyloxysilane shown in alkylene three hydrocarbyloxysilane shown in formula IV and general formula (V);
R in logical formula IV
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 (V)
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 catalyst system for olefinic polyreaction according to claim 1, is characterized in that, is the diol-lipid compound shown in logical formula VI to electric body compound a in described component (1):
(VI) 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 catalyst system for olefinic polyreaction according to claim 1, is characterized in that, is the compound shown in general formula (VII) to electric body compound a in described component (1);
(VII) 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 catalyst system for olefinic polyreaction according to claim 1, it is characterized in that, be 2-sec.-propyl-2-isopentyl-1 to electric body compound a 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 catalyst system for olefinic polyreaction according to claim 1, is characterized in that, in described component (1), electron donor compound b is unitary or polyhydric aliphatic race carboxylicesters, aromatic carboxylic acid esters or diether compound.
6. the catalyst system for olefinic polyreaction according to claim 1, is characterized in that, is 1 shown in general formula (VIII) to the diether compound described in electric body compound b, 3-diether compound in described component (1),
Wherein R
i, R
iI, R
iII, R
iV, R
vand R
vIidentical or different, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
7-C
20aralkyl, C
6-C
20one in aryl, R
vIIand R
vIIIidentical or different mutually, be selected from the C of straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
7-C
20aralkyl, C
6-C
20one in aryl; R
i-R
vIgroup between can be keyed to ring.
7. the catalyst system for olefinic polyreaction according to claim 6, is characterized in that, gives electric body compound b, described R in described component (1)
vIIand R
vIIIbe selected from C
1-C
4alkyl.
8. the catalyst system for olefinic polyreaction according to claim 1, it is characterized in that, in described component (1) preparation process, wherein in every mole of magnesium, electron donor compound a is 0.001 ~ 2 mole, and electron donor compound b is 0.01 ~ 5 mole.
9. the catalyst system for olefinic polyreaction according to claim 1, is characterized in that, in described component (1) preparation process, wherein in every mole of magnesium, electron donor compound a is 0.001 ~ 1 mole; Electron donor compound b is 0.05 ~ 1 mole.
10. the catalyst system 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.
11. catalyst system for olefinic polyreaction according to claim 1, is characterized in that, described titanium compound is titanium tetrachloride.
12. catalyst system 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.
13. 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.
14. 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.
15. catalyst system 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.
The application of the catalyst system for olefinic polyreaction described in 16. claim 1 ~ 15 any one in olefinic polyreaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104610474A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization reaction |
| CN106543310A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalyst system and its application |
| CN107129547A (en) * | 2016-02-29 | 2017-09-05 | 中国石油化工股份有限公司 | Ingredient of solid catalyst, catalyst and application for olefinic polymerization |
| CN114456288A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization reaction, and preparation method and application thereof |
| CN114456289A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization, and preparation method and application thereof |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104610474A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization reaction |
| CN104610474B (en) * | 2013-11-05 | 2017-03-22 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization reaction |
| CN106543310A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalyst system and its application |
| CN106543310B (en) * | 2015-09-23 | 2019-06-28 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalyst system and its application |
| CN107129547A (en) * | 2016-02-29 | 2017-09-05 | 中国石油化工股份有限公司 | Ingredient of solid catalyst, catalyst and application for olefinic polymerization |
| CN114456288A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization reaction, and preparation method and application thereof |
| CN114456289A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization, and preparation method and application thereof |
| CN114456288B (en) * | 2020-10-22 | 2024-02-13 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization reaction, preparation method and application thereof |
| CN114456289B (en) * | 2020-10-22 | 2024-02-13 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization, preparation method and application thereof |
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