CN102040691B - Catalyst component for propylene polymerization and catalyst thereof - Google Patents
Catalyst component for propylene polymerization and catalyst thereof Download PDFInfo
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- CN102040691B CN102040691B CN 200910236109 CN200910236109A CN102040691B CN 102040691 B CN102040691 B CN 102040691B CN 200910236109 CN200910236109 CN 200910236109 CN 200910236109 A CN200910236109 A CN 200910236109A CN 102040691 B CN102040691 B CN 102040691B
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Abstract
The invention relates to a catalyst component for propylene polymerization. The catalyst component for the propylene polymerization contains reaction products of the following components: (1) an allyl-containing amine compound shown as a general formula (I) and (2) a solid component containing titanium, magnesium, chlorine and electron donor compound, wherein in the general formula (I), n is 1, 2 or 3, m is 3-n, and R is methyl or ethyl. The obtained catalyst component is used for the propylene polymerization and has slow polymerization activity attenuation, and meanwhile, the catalyst keeps high isotactic directing property and is suitable for polypropylene production of double (multiple) reactors. (CH2=CH-CH)nNRm(I).
Description
Technical field
The present invention relates to a kind of catalyst component for propylene polymerization and catalyzer thereof.Particularly, the catalyst component and the catalyzer thereof that relate to a kind of titaniferous, magnesium, chlorine, electron donor compound and allyl amine compounds.
Background technology
On the tandem reactor polypropylene production apparatus, the exploitation of the exploitation of the broad molecular weight distribution polypropylene trade mark and the propylene impact copolymers trade mark needs polypropylene catalyst to have slower polymerization activity fade performance, and the productive rate that is conducive between the reactor matches control.
As disclosing a kind of " preparation method of high-performance polypropylene composition " among the Chinese patent CN101058654, adopt double loop reactor asymmetric hydrogenation and the asymmetric method that adds external electron donor to prepare the polypropylene that has than wide molecular weight distribution, the polypropylene of preparation has higher tensile strength and flexural strength.
Disclose a kind of " high melt strength, propylene " in the US Patent No. 7365136, adopted the method for endless tube+gas phase associated plant asymmetric hydrogenation to prepare the polypropylene with high fondant-strength.Productive rate between the double-reactor distributes from 85/15 to 30/70.
Disclose a kind of " second/propylene copolymer that three components form " in the US Patent No. 6300434, adopted the method for three tandem reactors, three step polymerizations (homopolymerization of the first step propylene, second step second/third copolymerization and the 3rd step second/third copolymerization) to synthesize the propylene heterophasic copolymer with high-impact performance.
Above technological method all needs polypropylene catalyst to have long active lifetime, especially slower decay of activity.
A kind of " ingredient of solid catalyst and catalyzer and the process for preparing olefin polymer that are used for olefinic polymerization " disclosed in the European patent EP 1921093, the catalyst component of processing titaniferous, magnesium, chlorine and electron donor compound with the silicoorganic compound of olefine-containing group has prepared a kind of catalyzer, be used for olefinic polymerization and have slower decay of activity, but the vertical structure directional property of the polymkeric substance that obtains is not high, the cost of the silicoorganic compound of olefine-containing group is higher simultaneously, the unfavorable industrial applications of using.
The inventor is unexpected the discovery in the synthetic test of catalyzer, process titaniferous with containing allylic aminated compounds, magnesium, the solid ingredient of chlorine and electron donor compound, particularly process the solid ingredient by magnesium chloride alcohol adduct and titanium compound reaction preparation, the catalyst component that obtains is used for propylene polymerization, has slower polymerization activity decay, catalyzer keeps higher vertical structure directional property simultaneously, be suitable for the polypropylene production of two (many) reactors, and when this catalyst component is used for second the third copolymerization, can obtain the propylene heterophasic copolymer of higher dimethylbenzene solubles content, be conducive to the preparation of high impact resistance polypropylene, compare with the silicoorganic compound of olefine-containing group, contain allylic aminated compounds and have lower cost.
Summary of the invention
The purpose of this invention is to provide a kind of titanium-containing catalyst component for propylene polymerization, it comprises the reaction product of following component:
(1) a kind ofly shown in general formula (I), contains allylic aminated compounds;
(2) a kind of solid ingredient that comprises titanium, magnesium, chlorine and electron donor compound;
(CH
2＝CH-CH)
n N R
m
(I)
In the general formula (I), n is 1,2 or 3; M is 3-n; R is methyl or ethyl.
Mol ratio between the contained titanium of wherein said component (1) and component (2) is 0.6～3: 1, is preferably 1～1.5: 1.
Aminated compounds shown in the general formula (I) is specially triallylamine, diallyl methylamine, allyl dimethyl base amine, diallyl ethylamine, allyl group diethylamide etc.
Component of the present invention (2) forms: titanium: 1.5-3.5wt%; Magnesium: 15-20wt%; Chlorine: 45-55wt%; Electron donor: 7-20wt%.
A kind of titaniferous of component of the present invention (2), magnesium, chlorine and electron donor compound solid component, preferably a kind of such as general formula (II) MgCl
2.p (HOCH
2CH
3) .qH
2Load has the reaction product of titanium compound and electron donor compound on the magnesium chloride alcohol adduct shown in the O, and wherein in general formula (II), p is 2.0～3.5; Q is 0～0.8; The general formula of described titanium compound is Ti (OR
a)
4-mX
m, R in the formula
aC
1～C
14Aliphatic group, X is F, Cl or Br, m is 1～4 integer, specifically can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine three titanium butoxide, dichloro dibutoxy titanium, trichlorine one titanium butoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, the titanous chloride or their mixture, preferred titanium tetrachloride.The preparation method of this magnesium chloride alcohol adduct can be with reference to the disclosed preparation method of Chinese patent ZL93102795.0.
Electron donor compound in the component of the present invention (2) can be the known phthalate compound of the industry, 1, and is at least a in 3-diol-lipid compound and 1, the 3-diether compound.
Phthalate compound specifically can adopt: phthalic ester diethyl ester, phthalic ester diisobutyl ester, phthalic ester di-n-butyl, phthalic ester di-isooctyl, phthalic ester di-n-octyl etc.
1,3-diol-lipid compound specifically can adopt: 1, the 2-propylene glycol dibenzoate, 1,2-propylene glycol two (p-methylbenzoic acid) ester, 1,2-propylene glycol two (p-tert-butyl benzoic acid) ester, 1,2-propylene glycol two (to butylbenzoic acid) ester, the 2-methyl isophthalic acid, the 2-propylene glycol dibenzoate, the 2-methyl isophthalic acid, 2-propylene glycol two (p-methylbenzoic acid) ester, the 2-methyl isophthalic acid, 2-propylene glycol two (p-tert-butyl benzoic acid) ester, the 2-methyl isophthalic acid, 2-propylene glycol two (to butylbenzoic acid) ester, 1, the ammediol dibenzoate, the 2-methyl isophthalic acid, the ammediol dibenzoate, 2-ethyl-1, the ammediol dibenzoate, 2-propyl group-1, the ammediol dibenzoate, 2-butyl-1, the ammediol dibenzoate, 2,2-dimethyl-1, the ammediol dibenzoate, (R)-1-phenyl-1, the ammediol dibenzoate, (S)-1-phenyl-1,3-PD dibenzoate, 1,3-phenylbenzene-1, the ammediol dibenzoate, 1,3-phenylbenzene-2-methyl isophthalic acid, the ammediol dibenzoate, 1,3-phenylbenzene-1, ammediol two n Propanoic acid esters, 1,3-phenylbenzene-2-methyl isophthalic acid, the ammediol dipropionate, 1,3-phenylbenzene-2-methyl isophthalic acid, the ammediol diacetate esters, 1,3-phenylbenzene-2，2-dimethyl-1，3-propanediol dibenzoate etc.
Diether compound specifically can adopt: 2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-butyl-1, the 3-Propanal dimethyl acetal, 2-sec-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-1, the 3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1, the 3-Propanal dimethyl acetal, 2-(2-cyclohexyl ethyl)-1, the 3-Propanal dimethyl acetal, 2-(p-chloro-phenyl-)-1, the 3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1, the 3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-diethyl-1, the 3-Propanal dimethyl acetal, 2,2-dipropyl-1, the 3-Propanal dimethyl acetal, 2,2-di-isopropyl-1, the 3-Propanal dimethyl acetal, 2,2-dibutyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-propyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2, two (the 2-cyclohexyl ethyls)-1 of 2-, the 3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1, the 3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal, 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal, 2,2-phenylbenzene-1, the 3-Propanal dimethyl acetal, 2,2-dibenzyl-1, the 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, the 3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-(1-methyl butyl)-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-benzyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclopentyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclopentyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-the second month in a season-butyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-cyclohexyl methyl-1,3-Propanal dimethyl acetal etc.
Above-mentioned 1 among the present invention, the 3-diether compound is disclosed among Chinese patent CN1020448C, CN100348624C and the CN1141285A.Its disclosed associated viscera is all introduced the present invention as a reference.
Catalyst component of the present invention is concrete preparation method may further comprise the steps:
(1) preparation of solid ingredient
With magnesium chloride alcohol adduct MgCl
2.p (HOCH
2CH
3) .qH
2O is-30 ℃～0 ℃ lower and titanium tetrachloride contact reacts, intensification degree to 100～120 ℃, in temperature-rise period, add described electron donor compound, and 100～120 ℃ of lower reactions 0.5-2 hour, filter solids that liquid obtains with titanium tetrachloride 100-120 ℃ of lower the processing 0.5-2 hour, so process and repeat 1-2 time, the solid that obtains obtains solid ingredient after the drying with hexane washing 4-6 time under vacuum.Ratio between the reactant: the mol ratio of magnesium alcoholate/titanium tetrachloride/electron donor is: 1/5～50/0.1～0.5.
(2) preparation of catalyst component
The solid ingredient that aminated compounds and step (1) are obtained in hexane in-20 ℃～120 ℃ reactions, preferably-20 ℃ to 60 ℃, wherein (mole) ratio between aminated compounds and the solid ingredient (take titanium) as: 3～0.6: 1, preferred 1.5～1: 1, the solid that obtains obtains catalyst component after the drying after washing with hexane under vacuum.
In addition, the invention still further relates to a kind of catalyzer for propylene polymerization, it comprises the reaction product of following a, b, three kinds of components of c:
A, above-mentioned catalyst component;
B, alkylaluminium cpd; Be the known alkylaluminium cpd for propylene polymerization of the industry, comprise 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, Al (CH
2CH
3)
2Cl etc. are generally take the Al/Ti mol ratio as 1～1000 use abovementioned alkyl aluminum compound.
C, randomly, a kind of external donor compound, namely the industry is known for propylene polymerization
External donor compound comprises Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane etc.Its consumption is 0.005～0.5 mole of every mole of aluminum alkyl compound, 0.01～0.25 mole of preferred every mole of aluminum alkyl compound.
Catalyzer of the present invention is applicable to the copolymerization of propylene polymerization and propylene and other alkene, and the polymerization activity decay is slow, and catalyzer keeps higher vertical structure directional property simultaneously.
Embodiment
Following example is used for illustrating the present invention, is not to limit the scope of the invention.
Analyze and testing method
(1) polymer melt flow index (M.I): according to the melt flow index of ASTM D1238-99 standard test polymkeric substance.
(2) polymkeric substance isotactic index (II): adopt the heptane extraction process to measure (heptane boiling extracting 6 hours): with the dry polymer samples of 2 grams, be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is isotactic index with 2 ratio.
(3) polymkeric substance xylene soluble part X.S: according to the content of xylene soluble part in the ASTM D 54922006 standard test polymkeric substance.
Embodiment 1
1) preparation of solid ingredient:
In the glass reaction bottle of 3000ml, add the titanium tetrachloride of 1000ml, be cooled to-20 ℃, add magnesium chloride alcohol adduct (MgCl
2.2.7 (HOCH
2CH
3) 100 grams, be warming up to 120 ℃, in temperature-rise period, add diisobutyl phthalate 15ml, elimination liquid at 120 ℃ of lower washing secondaries, with hexane washing three times, obtains the spherical solid component with titanium tetrachloride 800ml after the vacuum-drying.
2) preparation of catalyst component
In the glass reaction bottle of 300ml, add the hexane of 200ml, be cooled to-20 ℃, add solid ingredient 20g, add triolefin allylamine 2.5ml, be warming up to 50 ℃, 50 ℃ of lower stirrings 30 minutes, filter liquid, then the hexane with 80ml washs three times, and vacuum-drying obtains the 20g catalyst component.
3) propylene polymerization
In the 5L autoclave, add propylene 2.5L, triethyl aluminum 1mmol, CHMMS0.05mmol and 2) catalyst component 10mg, hydrogen 1.5L (standard volume) is warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
In the 5L autoclave, add propylene 2.5L, triethyl aluminum 1mmol, CHMMS0.05mmol and 2) catalyst component 10mg, hydrogen 1.5L (standard volume) is warmed up to 70 ℃, polymerization 2 hours.Test result such as table 1.
Comparative Examples 1
The preparation of catalyst component is with 1 of embodiment 1) preparation of solid ingredient; Polymerization is with embodiment 1 Comparative Examples 2
The preparation of catalyst component is except replacing the triallylamine, with embodiment 1 with diallyl dimethoxy silane; Polymerization is with embodiment 1.
Embodiment 2
The preparation of catalyst component is with embodiment 1.
The propylene/ethylene copolymerization
In the 5L autoclave, add propylene 2.5L, triethyl aluminum 1mmol, CHMMS0.05mmol and .1) catalyst component 10mg, hydrogen 4.5L (standard volume) is warmed up to 70 ℃, polymerization 1.5 hours, open blow-off valve and bleed off unreacted propylene, pass into continuously the gas mixture (propylene/ethylene/hydrogen mol ratio: 1: 1: 0.1) of propylene, ethene and the hydrogen of 1.0MPa pressure, at 75 ℃ of lower polymerase 10 .5 hours.Test result such as table 2.
Comparative Examples 3
The preparation of catalyst component is with 1 of embodiment 1) preparation of solid ingredient.
The propylene/ethylene copolymerization is with embodiment 2, test result such as table 2.
Comparative Examples 4
The preparation of catalyst component is with Comparative Examples 2.
The propylene/ethylene copolymerization is with embodiment 2, test result such as table 2.
Table 1 propylene homopolymerization result
Active (2hr)/active (1hr) value is larger, and then decay of activity is slower, and comparative example 1 and Comparative Examples 1 can be found out, process the catalyst component that obtains with aminated compounds and are used for propylene polymerization, have slower decay of activity.
Comparative example 1 and Comparative Examples 2 can be found out, process the catalyst component that obtains with aminated compounds and be used for propylene polymerization, not only have slower decay of activity, and catalyzer has higher vertical structure directional property, the polymkeric substance that obtains has higher isotactic index.
The copolymerization of table 2 propylene/ethylene
| Embodiment | Polymkeric substance X.S |
| Embodiment 2 | 11.9 |
| Comparative Examples 3 | 8.1 |
| Comparative Examples 4 | 10.6 |
From the results shown in Table 2, catalyzer of the present invention is used for the copolymerization of propylene/ethylene, can obtain the propylene heterophasic copolymer of higher dimethylbenzene solubles content, is conducive to the preparation of high impact resistance polypropylene.
Claims (5)
1. catalyst component that is used for propylene polymerization, it comprises the reaction product of following component:
(1) a kind of as leading to the allylic aminated compounds that contains shown in the formula I;
(2) a kind of solid ingredient that comprises titanium, magnesium, chlorine and electron donor compound;
(CH
2＝CH-CH)
nNR
m
（Ⅰ）
In the logical formula I, n is 1,2 or 3; M is 3-n; R is methyl or ethyl;
Described component (2) is at a kind of as logical formula II MgCl
2.p (HOCH
2CH
3) .qH
2Load has the reaction product of titanium compound and electron donor compound on the magnesium chloride alcohol adduct shown in the O, and wherein in logical formula II, p is 2.0-3.5; Q is 0-0.8; The general formula of described titanium compound is Ti (OR
a)
4-mX
m, R in the formula
aC
1～C
14Aliphatic group, X is F, Cl or Br, m is 1～4 integer;
Mol ratio between the contained titanium of wherein said component (1) and component (2) is 0.6～3:1.
2. the catalyst component for propylene polymerization according to claim 1, the mol ratio between the contained titanium of wherein said component (1) and component (2) is 1～1.5:1.
3. the catalyst component for propylene polymerization according to claim 1, wherein said electron donor compound is phthalate compound, 1, at least a in 3-diol-lipid compound and 1, the 3-diether compound.
4. the catalyst component for propylene polymerization according to claim 1, wherein said component (2) form: titanium: 1.5-3.5wt%; Magnesium: 15-20wt%; Chlorine: 45-55wt%; Electron donor compound: 7-20wt%.
5. catalyzer that is used for propylene polymerization, it comprises the reaction product of following component:
The described catalyst component of one of a, claim 1-4;
B, alkylaluminium cpd;
C, randomly, the external electron donor component.
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|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058654A (en) * | 2006-04-20 | 2007-10-24 | 中国石油化工股份有限公司 | Method of preparing high-performance polypropylene composition |
| EP1921093A1 (en) * | 2005-08-31 | 2008-05-14 | Toho Catalyst Co., Ltd. | Solid catalyst component for olefin polymerization, catalyst and method for producing olefin polymer by using same |
| CN101434665A (en) * | 2008-12-25 | 2009-05-20 | 南开大学 | Supported catalyst for olefinic polymerization, and preparation and use thereof |
-
2009
- 2009-10-20 CN CN 200910236109 patent/CN102040691B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1921093A1 (en) * | 2005-08-31 | 2008-05-14 | Toho Catalyst Co., Ltd. | Solid catalyst component for olefin polymerization, catalyst and method for producing olefin polymer by using same |
| CN101058654A (en) * | 2006-04-20 | 2007-10-24 | 中国石油化工股份有限公司 | Method of preparing high-performance polypropylene composition |
| CN101434665A (en) * | 2008-12-25 | 2009-05-20 | 南开大学 | Supported catalyst for olefinic polymerization, and preparation and use thereof |
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