CN103819586A - Catalyst system for alkene polymerization reaction - Google Patents
Catalyst system for alkene polymerization reaction Download PDFInfo
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- CN103819586A CN103819586A CN201210465894.2A CN201210465894A CN103819586A CN 103819586 A CN103819586 A CN 103819586A CN 201210465894 A CN201210465894 A CN 201210465894A CN 103819586 A CN103819586 A CN 103819586A
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Abstract
The invention relates to a catalyst system for alkene polymerization reaction. According to the invention, a spherical titanium-containing solid catalyst component using polyol ester compounds and pthalic acid ester compounds as internal electron donors is added with trioxyl benzoate compounds and hydrocarbyl dialkyl alkoxysilane compounds used as external electron donor compounds during the alkene polymerization, thereby further improving the molecular weight of polymers and widening molecular weight distribution of polymers. The widened molecular weight distribution is relatively excellent for subsequent processing application of the polymers. The copolymer obtained by compounding technology can improve the xylene soluble substance in the case that the ethylene content is basically unchanged, which indicates that the content of rubber phase in the copolymer is improved; in addition, the copolymer obtained can improve the toughness of the copolymers in the case that the rigidity is basically unchanged.
Description
Technical field
The present invention relates to a kind of catalyzer for olefinic polyreaction, more particularly, relate to a kind of spherical catalyst component, promotor and three-oxyl benzoic acid ester compounds and composite catalytic systems for polymerization of olefins as external donor compound of alkyl two-oxyl silane compound of comprising.
Technical background
As everyone knows, catalyst system for the equal polymerization of alpha-olefin or copolymerization is generally made up of three parts, and they are: the external donor compound adding when (1) Primary Catalysts (solid catalyst), (2) promotor (being generally aluminum alkyls compounds) and (3) polymerization.
In polymerization process, be that those skilled in the art are in common knowledge by taxis and form that one or more external donor compounds are controlled polymkeric substance.External electron donor, except affecting the taxis of polymkeric substance, has influence on the performance of catalyzer other side to some extent toward contact meeting.Although have multiple compounds perhaps to can be used as external electron donor known, specific catalyzer uses different external donor compounds may produce different polymer performances.Select the suitable external electron donor can be compatible especially with specific catalyzer, that is to say, find a kind of applicable external electron donor can improve significantly the performance of some aspect of polymeric articles, therefore find that one group of external electron donor that can make polymkeric substance have in some aspects outstanding properties for special catalyst is very favorable.
Chinese patent CN02100896.5, CN02100900.7, CN03109781.2, CN03140565.7, CN 200410073623.8, CN200410073621.9 etc. have described and have used 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, the external electron donor alkyl two-oxyl silane that use are current industrial conventional external electron donors, such as Cyclohexylmethyldimethoxysilane (CHMMS) etc.Although Chinese patent CN03109781.2 has also used different external electron donors as a comparison, for example, except using Cyclohexylmethyldimethoxysilane, also used second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane (DCPMS), two (cyclobutylmethyl) dimethoxy silane etc., this catalyst system shows high reactivity, high orientation property and the prepared wide feature of molecular weight distribution.
The inventor is surprised to find that in research work, add during in olefinic polymerization three-oxyl benzoic acid ester compounds and alkyl two-oxyl silane compounds composite as external donor compound at the spherical solid catalyst component using polyol ester compounds and adjacent benzene dicarboxylic acid ester compound as internal electron donor, the molecular weight distribution that can further improve the molecular weight of polymkeric substance and further widen, molecular weight distribution is widened has larger superiority to the following process application of polymkeric substance.
Improve by the above composite multipolymer obtaining xylene soluble part in the situation that ethylene content is substantially constant, also illustrate that in multipolymer, rubber phase content improves; The multipolymer obtaining has in addition improved the toughness of multipolymer in the situation that rigidity is substantially constant.
Summary of the invention
The object of the present invention is to provide a kind of catalyst system for olefinic polyreaction, the polymkeric substance that this catalyst system obtains has higher molecular weight and wider molecular weight distribution.
A kind of catalyst system for olefinic polyreaction of the present invention, the reaction product that comprises 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 the alkyl that carbonatoms is 1～18, n is 0.1～6;
R in its formula of (II)
wbe 1～20 alkyl, X is Cl, Br or I, the integer that k is 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, replacement 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
2non group, optionally comprise 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 rings that optionally connect in group; N is the integer of 0-10;
Be selected from monobasic or polyhydric aliphatic family 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, the consumption Al/Ti mol ratio of alkylaluminium cpd is 1 ~ 1000;
(3) compound external donor compound, three-oxyl benzoic ethers shown in logical formula IV and the alkyl two-oxyl silane shown in general formula (V);
R in logical formula IV
xfor carbonatoms 1～20 alkyl or cycloalkyl, R
yfor carbonatoms is 1～20 alkyl or cycloalkyl;
R in general formula (V)
1, R
2, R
3, R
4for carbonatoms 1～20 alkyl or cycloalkyl, R
1, R
2optionally identical or different; R
3, R
4optionally identical or different;
The consumption of three described-oxyl benzoic ethers is 0.001～1.0 mole of every mole of aluminum alkyl compound; The consumption of described alkyl dialkoxy silicane is 0.001～1.0 mole of every mole of aluminum alkyl compound; The additional proportion of logical formula IV and general formula (V) compound is 1:100～100:1.
The compound of its formula of (IV) specifically can be selected 3.4.5-tri-methoxybenzoate, 3.4.5-trimethoxybenzoic acid ethyl ester, 3.4.5-trimethoxybenzoic acid propyl ester, 3.4.5-trimethoxybenzoic acid butyl ester, 3.4.5-trimethoxybenzoic acid pentyl ester, 3.4.5-the own ester of trimethoxybenzoic acid, 3.4.5-trimethoxybenzoic acid isopropyl ester, 3.4.5-trimethoxybenzoic acid isobutyl ester, 3.4.5-triethoxy methyl benzoate, 3.4.5-triethoxy ethyl benzoate, 3.4.5-triethoxy propyl benzoate, 3.4.5-triethoxy butyl benzoate, 3.4.5-triethoxy amyl benzoate, 3.4.5-triethoxy hexyl-benzoate, 3.4.5-triethoxy isopropyl benzoate, 3.4.5-triethoxy isobutyl benzoate, 3.4.5-tripropoxy methyl benzoate, 3.4.5-tripropoxy ethyl benzoate, 3.4.5-tripropoxy propyl benzoate, 3.4.5-tripropoxy butyl benzoate, 3.4.5-tripropoxy amyl benzoate, 3.4.5-tripropoxy hexyl-benzoate, 3.4.5-tripropoxy isopropyl benzoate, 3.4.5-tripropoxy isobutyl benzoate, 3.4.5-three butyl phenyl ether methyl-formiates, 3.4.5-three butyl phenyl ether ethyl formates, 3.4.5-three butyl phenyl ether propyl formates, 3.4.5-three butyl phenyl ether butyl formates, 3.4.5-three butyl phenyl ether pentyl formates, 3.4.5-three butyl phenyl ether hexyl formates, 3.4.5-three butyl phenyl ether isopropyl formates, 3.4.5-three butyl phenyl ether tetryl formates etc.General formula is that the consumption of three-oxyl benzoic ethers shown in (IV) is 0.001～1.0 mole of every mole of aluminum alkyl compound, 0.002～0.5 mole of preferred every mole of aluminum alkyl compound.
General formula is three-oxyl benzoic ethers shown in (IV), can adopt conventional synthetic method to be prepared in laboratory, also can, by the way of general chemical product purchasing, 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 identical, also can be different.Specifically can select Cyclohexylmethyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane, dicyclopentyl dimethoxyl silane, methylcyclohexyl diethoxy silane, di-isopropyl diethoxy silane, diisobutyl diethoxy silane, dicyclohexyl diethoxy silane, two cyclopentyl diethoxy silanes, methylcyclohexyl dipropoxy silane, di-isopropyl dipropoxy silane, diisobutyl dipropoxy silane, dicyclohexyl dipropoxy silane, two cyclopentyl dipropoxy silane, methylcyclohexyl dibutoxy silane, di-isopropyl dibutoxy silane, diisobutyl dibutoxy silane, dicyclohexyl dibutoxy silane, two cyclopentyl dibutoxy silane etc.General formula is that the consumption of the alkyl dialkoxy silicane shown in (V) is 0.001～1.0 mole of every mole of aluminum alkyl compound, 0.002～0.5 mole of preferred every mole of aluminum alkyl compound.
General formula is the alkyl two-oxyl silane shown in (V), can adopt conventional synthetic method to be prepared in laboratory, also can, by general chemical product purchasing way, buy on the market.
After logical formula IV and general formula (V) can mix, add, also can add respectively.Both additional proportion 1:100～100:1, preferably 1:20～20:1.
In wherein said component (1), give the compound of electric body compound a preferred formula (VI);
R in formula
1-R
6, R
1-R
2group is as the definition in logical formula III.
In described component (1), give the also compound shown in preferred formula (VII) of electric body compound a;
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-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 9, two (benzoyloxy methyl) fluorenes of 9-etc.
In component of the present invention (1), another electron donor compound b is monobasic or polyhydric aliphatic family carboxylicesters, aromatic carboxylic acid esters or diether compound.For example: 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 esters etc.
Wherein give 1,3-two ethers shown in the 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.Preferably R
vIIand R
vIIIbe selected from C
1-C
41 of alkyl, 3-diether.
Above-mentioned 1 in the present invention, 3-diether compound is disclosed in Chinese patent CN1020448C, CN100348624C and CN1141285A.Its disclosed associated viscera is all introduced 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 1～20 alkyl, X is Cl, Br or I, the integer that k is 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, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, titanous chloride or their mixture, preferably titanium tetrachloride.
Component of the present invention (1) catalyst component can be prepared according to the preparation method of disclosed solid catalyst 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 its disclosed associated viscera is all introduced the present invention as a reference.
The concrete preparation method of magnesium halide alcohol adduct carrier mixes anhydrous magnesium halide and low-carbon alcohol, temperature reaction generates magnesium halide alcohol adduct melt, temperature of reaction is 90～140 ℃, in dispersion medium, after high shear forces, put into cooling inert media, form spherical magnesium halide alcohol polymer particle, after washing, being dried, 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 etc.
The synthetic method of component of the present invention (1) catalyst component is that magnesium halide alcohol adduct obtained above is suspended 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 ℃～0 ℃, preferably-20 ℃～-10 ℃; Then said mixture is heated to 80 ℃～130 ℃, in temperature-rise period, adds electron donor compound a and electron donor compound b.Then add titanium compound and process one or many.Finally, repeatedly wash and obtain ingredient of solid catalyst with inert solvent.
In the preparation process of catalyst component of the present invention, electron donor a and b add in no particular order sequentially.In component of the present invention (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, can select one or more aluminum alkyls to mix and use, preferably triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, Al (n-C
8h
17)
3, AlEt
2cl etc., generally take Al/Ti mol ratio as 1～1000 use abovementioned alkyl aluminum compound.
Component (2) alkylaluminium cpd can contact with component (1) catalyst component separately or as the mixture of two kinds of compositions with component (3) external donor compound.
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 contain (if necessary) polyreaction of the mixture of diolefine on a small quantity.
The polymerization of alkene is carried out according to currently known methods, in liquid monomer or monomer in the liquid phase of the solution in inert solvent, or in gas phase, or operate by the polymerization mix technique in liquid phase.Polymerization temperature is generally 0 ℃～150 ℃, preferably 50 ℃～100 ℃.Polymerization pressure is normal pressure or higher.
Embodiment
Provide following examples to the present invention is described better, 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), get the polymer samples that 2g is dry, be placed in extractor boiling heptane extracting 6 hours, afterwards, residuum is dried to constant weight, and resulting polymers weight (g) is degree of isotacticity with 2 ratio.
3, molecular weight and distribution tests: polymericular weight and molecular weight distribution PD(PD=Mw/Mn) adopt PL-GPC220 take trichlorobenzene as solvent (the standard specimen: PS of the mensuration at 150 ℃, flow velocity: 1.0ml/min, pillar: 3xPlgel 10um M1xED-B 300x7.5nm).
4, Infrared spectroscopy
The Magna-IR760 type infrared spectrometer that adopts Nicolet instrument company, sample is all prepared test sample with being hot pressed into embrane method, and mold pressing parameter is 170 ℃, 40Mpa.
5, xylene soluble part content measuring
Propene polymer is placed in to 75 ℃ of vacuum drying ovens and toasts after 30min, put into rapidly moisture eliminator and be cooled to room temperature.Get 2g left and right multipolymer weightometer weight, put into 500ml Erlenmeyer flask, add pretreated 200ml dimethylbenzene heating for dissolving, the sample having dissolved is at room temperature put into 25 ℃ of water bath with thermostatic control crystallisation by cooling 60min after cooling 12～14min, with the calculating of after glass funnel filtering for crystallizing thing, solvend heated baking being weighed.
Embodiment 1
Diol ester compound 2, the preparation of 4-pentanediol dibenzoate
The preparation of (1) 2,4-pentanediol
10g 2, the mixture of 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 ℃.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-pentanediol dibenzoates
0.03mol 2, adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in 4-pentanediol, under agitation add 0.075mol Benzoyl chloride, reflux 4h.After cooling, add 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na
2sO
4dry, except desolventizing.Column chromatography or underpressure distillation obtain colourless liquid 2,4-pentanediol 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 dibenzoates
The preparation of (1) 3,5-heptanediol
14.2g 3, the mixture of 5-heptadione and 30ml methyl alcohol at 0-10 ℃, be added drop-wise to 2.5g sodium borohydride,
In the mixing solutions of 0.05g sodium hydroxide and 25ml water.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 carries out completely.m.p.60-65℃。
The preparation of (2) 3,5-heptanediol dibenzoates
0.03mol 3, adds 30ml tetrahydrochysene to bark and mutters and 0.09mol pyridine in 5-heptanediol, under agitation add 0.075mol Benzoyl chloride, reflux 4h.After cooling, add 20m1 saturated aqueous common salt, ethyl acetate extraction, anhydrous Na
2sO
4dry, 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).
4-ethyl-3,5-heptanediol dibenzoate
(1) 4-ethyl-3, the preparation of 5-heptanediol
Preparation method is with preparation 3,5-heptanediol, and just with 4-ethyl-3,5-heptadione replaces 3,5-heptadione.
(2) 4-ethyl-3, the preparation of 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 stirring at the 300ml band of fully replacing through high pure nitrogen, add the titanium tetrachloride of 100ml, be cooled to-20 ℃, add spherical magnesium chloride alcohol adduct (preparation method is referring to Chinese patent CN1330086A), slowly be warming up to stage by stage 110 ℃, in temperature-rise period, add in embodiment 12 of preparation, 4-pentanediol dibenzoate 2.5mmol and dibutyl phthalate 3.9mmol, after 110 ℃ of constant temperature 0.5h, elimination liquid, add titanium tetrachloride and process secondary, then with hexane washing five times, after vacuum-drying, obtain solids containing titanium catalyst component A (Primary Catalysts).
2B, the equal polymerization of propylene body
In 5 liters of autoclaves; adopt stream of nitrogen gas at 70 ℃, to purge 1 hour; then with gas-phase propene, polymeric kettle is replaced 3 times, under nitrogen protection, 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 2 kinds of external electron donors of 1ml (mix or add respectively), 10ml anhydrous hexane and 8～12mg solids containing titanium catalyst component A (Primary Catalysts).Close autoclave, introduce appropriate hydrogen and the liquid propene of 1.0～1.2Kg; Under agitation fast temperature in Fu is risen to 70 ℃.At 70 ℃, polyreaction, after 1 hour, stops stirring, and removes unpolymerized propylene monomer, collected polymer, vacuum-drying 2 hours at 70 ℃, the calculated activity of weighing (AC).2C, copolymerization of propylene
First carry out the equal polymerization 1h of propylene body according to 2B, then carry out gas-phase copolymerization 1h.Polymerizing condition is as follows:
1, the homopolymerization stage:
AlEt
3：2.5mmol
External electron donor: 0.1mmol
Catalyzer: approximately 8～10mg
H
2：ΔP=1.4NL
Polymerization temperature: 70 ℃
2, copolymerization stage:
Temperature: 75 ℃
Polymerization pressure: 0.8MPa
Copolymerization gas phase composition: third is rare: ethene: hydrogen=1:0.64:0.09 (mol)
Embodiment 3～10
The solid catalyst of preparing in the 2A of embodiment 2, according to the method for propylene polymerization in the 2B of embodiment 2, is carried out to the composite polymerization result obtaining by different hydrogenation amounts, different external electron donor add-on respectively.Polymerization and test result are respectively in table one, table two.
Comparative example 1～3
Polymerization process, with embodiment 2B, just changes the external electron donor adding into the hexane solution (concentration of C-donor is 0.1mmol/ml) of 1ml Cyclohexyl Methyl Dimethoxysilane (C-donor), and polymerization result is in table one, table two.
Embodiment 11～12
The solid catalyst of preparing in the 2A of embodiment 2 is carried out to copolymerization according to the method for propylene polymerization in the 2C of embodiment 2, and polymerization and test result are respectively in table three, table four.
Table one is polymerization result all
Note: ETMB:3.4.5-trimethoxybenzoic acid ethyl ester
MTMB:3.4.5-tri-methoxybenzoate
C-donor: Cyclohexylmethyldimethoxysilane
Table two polymericular weight and distribution results
Table three copolymerization result
Table four multipolymer mechanical experimental results
Claims (12)
1. for a catalyst system for olefinic polyreaction, it is characterized in that the reaction product that comprises 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, b;
R in its formula of (I)
qfor the alkyl that carbonatoms is 1～18, n is 0.1～6;
R in its formula of (II)
wbe 1～20 alkyl, X is Cl, Br or I, the integer that k is 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, replacement 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
2non group, optionally comprise 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 rings that optionally connect in group; N is the integer of 0-10;
Be selected from monobasic or polyhydric aliphatic family 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, can select one or more aluminum alkyls mix use, the consumption Al/Ti mol ratio of alkylaluminium cpd is 1～1000;
(3) compound external donor compound, three-oxyl benzoic ethers shown in logical formula IV and the alkyl two-oxyl silane shown in general formula (V);
R in logical formula IV
xfor carbonatoms 1～20 alkyl or cycloalkyl, R
yfor carbonatoms is 1～20 alkyl or cycloalkyl;
R in general formula (V)
1, R
2, R
3, R
4for carbonatoms 1～20 alkyl or cycloalkyl, R
1, R
2optionally identical or different; R
3, R
4optionally identical or different;
The consumption of three described-oxyl benzoic ethers is 0.001～1.0 mole of every mole of aluminum alkyl compound; The consumption of described alkyl dialkoxy silicane is 0.001～1.0 mole of every mole of aluminum alkyl compound; Additional proportion 1:100～the 100:1 of logical formula IV and general formula (V).
2. the catalyst system for olefinic polyreaction according to claim 1, is characterized in that, the compound external donor compound of component (3), and the consumption of three described-oxyl benzoic ethers is 0.002～0.5 mole of every mole of aluminum alkyl compound; The consumption of described alkyl dialkoxy silicane is 0.002～0.5 mole mole of every mole of aluminum alkyl compound; Additional proportion 1:20～the 20:1 of logical formula IV and general formula (V).
3. the catalyst system for olefinic polyreaction according to claim 1, it is characterized in that, in component (1), 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, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, titanous chloride or their mixture.
4. the catalyst system for olefinic polyreaction according to claim 3, is characterized in that, in component (1), described titanium compound is titanium tetrachloride.
5. the catalyst system for olefinic polyreaction according to claim 1, is characterized in that, in described component (1), giving electric body compound a is the compound shown in logical formula VI;
R in formula
1-R
6, R
1-R
2group is identical or different, is alkyl, the C of hydrogen, halogen, replacement or unsubstituted C1-C20 straight or branched
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
2on group, optionally comprise 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
2one or more rings that optionally connect in group.
6. the catalyst system for olefinic polyreaction according to claim 1, it is characterized in that, in described component (1), giving electric body compound a is 2-sec.-propyl-2-isopentyl-1, ammediol dibenzoate, 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3, two (benzoyloxy methyl) fluorenes of 5-heptanediol dibenzoate or 9,9-.
7. the catalyst system for olefinic polyreaction according to claim 1, it is characterized in that, in described component (1), giving electric body compound b is ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate or dinoctyl phthalate.
8. the catalyst system for olefinic polyreaction according to claim 1, is characterized in that, it is 1,3-diether compound shown in general formula (VIII) that described component (1) is given the diether compound described in electric body compound b,
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
7-C
20one in alkaryl, R
vIIand R
vIIIidentical or different, be selected from the C of straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
7-C
20aralkyl, C
7-C
20one in alkaryl; R
i-R
vIgroup between be optionally keyed to ring.
9. the 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.
10. the catalyst system for olefinic polyreaction according to claim 1, it is characterized in that, three-oxyl benzoic ethers shown in the logical formula IV of described component (3) are 3.4.5-tri-methoxybenzoate, 3.4.5-trimethoxybenzoic acid ethyl ester, 3.4.5-triethoxy methyl benzoate or 3.4.5-triethoxy ethyl benzoate.
11. catalyst systems for olefinic polyreaction according to claim 1, it is characterized in that, the alkyl two-oxyl silane shown in described component (3) general formula (V) are Cyclohexylmethyldimethoxysilane, diisopropyl dimethoxy silane, methylcyclohexyl diethoxy silane or di-isopropyl diethoxy silane.
The described catalyst body for olefinic polyreaction of one of 12. claims 1 ~ 11 ties up to the application of olefinic polymerization.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482003A (en) * | 2014-10-10 | 2016-04-13 | 中国石油化工股份有限公司 | Carrier for ethylene polymerization catalyst and catalyst of carrier |
| CN105566522A (en) * | 2014-10-10 | 2016-05-11 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization reaction, and catalyst thereof |
| CN105566524A (en) * | 2014-10-10 | 2016-05-11 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization reaction, and catalyst thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743348A (en) * | 2004-09-02 | 2006-03-08 | 中国石油化工股份有限公司 | Catalyst component for olefinic polymerization and its catalyst |
| CN101928359A (en) * | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization |
| WO2011084691A2 (en) * | 2009-12-21 | 2011-07-14 | Basf Corporation | New internal and external donor compounds for olefin polymerization catalysts |
| US20120116031A1 (en) * | 2010-11-10 | 2012-05-10 | Basf Corporation | High Activity Catalyst Component for Olefin Polymerization and Method of Using the Same |
-
2012
- 2012-11-16 CN CN201210465894.2A patent/CN103819586B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743348A (en) * | 2004-09-02 | 2006-03-08 | 中国石油化工股份有限公司 | Catalyst component for olefinic polymerization and its catalyst |
| CN101928359A (en) * | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization |
| WO2011084691A2 (en) * | 2009-12-21 | 2011-07-14 | Basf Corporation | New internal and external donor compounds for olefin polymerization catalysts |
| US20120116031A1 (en) * | 2010-11-10 | 2012-05-10 | Basf Corporation | High Activity Catalyst Component for Olefin Polymerization and Method of Using the Same |
Non-Patent Citations (1)
| Title |
|---|
| 曲广淼等: "外给电子体的研究", 《精细石油化工进展》, vol. 7, no. 11, 25 November 2006 (2006-11-25), pages 36 - 40 * |
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| CN105482003A (en) * | 2014-10-10 | 2016-04-13 | 中国石油化工股份有限公司 | Carrier for ethylene polymerization catalyst and catalyst of carrier |
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