Patent US5424037A successfully refreshed from Google Patents.
US5334567A
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Cocatalyst for vanadium-containing ethylene polymerization catalyst
Assignee: Equistar Chemicals LP
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Filing: 1993-01-29
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Granted: 1994-08-02
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Expires: 2013-01-29
Abstract
Abstract The present invention is directed to a novel halosilane cocatalyst component which may be used in conjunction with an aluminum-containing cocatalyst to provide enhanced catalytic activity of a vanadium based solid catalyst component in the polymerization of α-olefins. In addition to the enhancement in the catalytic activity obtaining using the present catalyst system, the resultant polymer produced by the present invention exhibits improved physical properties compared with polymers produced by prior art vanadium based catalyst systems. Thus, the catalyst system of the instant invention represents an advance in the art in view of the combination of increased catalytic activity, i.e. yield of polymer produced, and enhanced physical properties of the polyolefin produced. In accordance with the present invention, a catalyst system is provided which comprises a solid catalyst component and a halosilane cocatalyst component. The solid catalyst component of the present invention is the product formed by admixing a solid inorganic oxide, an organometallic compound, a vanadium-containing compound and an organic reagent. In another aspect of the present invention, a process of the polymerization of α-olefins is disclosed. In this process at least one olefin is polymerized under olefin polymerization catalyst utilizing the catalyst system of the present invention, which includes the solid catalyst component of the present invention, and a cocatalyst selected from the group consisting of halosilane compounds and admixtures thereof with aluminum compounds.
Inventors
- 👤 Raghu Menon
- 👤 Albert P. Masino
- 👤 Mark K. Reinking
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 04:10
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/02; B01J31/12; B01J31/14; B01J31/143; B01J31/128; B01J31/16; B01J31/1608; B01J31/1616; B01J31/22; B01J31/2204; B01J31/2208; B01J31/2226; B01J37/00; B01J37/02; B01J37/03; B01J37/031; C; C08; C08F; C08F10/00; B01J2531/00; B01J2531/50; B01J2531/56
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
300 words
An improved catalyst system for polymerizing α-olefins consisting essentially of a silica supported vanadium based solid catalyst component prepared by the steps of: (a) pretreating silica support to remove surface hydroxyl groups; (b) slurrying said pretreated silica with a hydrocarbon solvent; (c) contacting said slurried silica with an organometallic compound having the formula: R.sub.x MR'.sub.y R".sub.z wherein M is a metal of Group IIIA of the Periodic Table of Elements, R is an alkyl group containing 1 to 12 carbon atoms, R' and R" are independently hydrogen, halide, alkyl or alkoxy groups containing from 1 to 12 carbon atoms, x is an integer from 1 to 3, and y and z are 0 or an integer from 1 to 2, the sum of which is not greater than 3-x; (d) contacting said product of step (c) with a vanadium compound having the formula: V(OR).sub.x (O).sub.y (X.sup.2).sub.z wherein X 2 is a halogen, R is a saturated hydrocarbon having from 1 to about 18 carbon atoms, x=0 or an integer from 1 to 5, y=0 or 1, and z=(5-x-2y) or 4 or 3 when x=0, y=0, or mixtures of such vanadium compounds; (e) reacting said product of step (d) with an organic reagent selected from the group consisting of alcohols, ethers, carbonates, amines, and phosphorous compounds; and (f) adding an alkylaluminum first cocatalyst component, and at least one halosilane second cocatalyst component having the formula R f 8 SiX g 3 where X 3 is halogen; R 8 is hydrogen, alkoxy, alkyl, aryl, silyoxy or cycloalkyl; f is 0 or an integer from 1 to 3, and g is an integer from 1 to 4 with the proviso that the sum of f and g is 4, to the silica supported vanadium based solid catalyst component during polymerization of said α-olefin.
Claim 2
Dependent Claim
300 words
An improved catalyst system for polymerizing α-olefins consisting essentially of a silica supported vanadium based solid catalyst component prepared by the steps of: (a) pretreating silica support to remove surface hydroxyl groups; (b) slurrying said pretreated silica with a hydrocarbon solvent; (c) contacting said slurried silica with an organometallic compound having the formula: R.sub.x MR'.sub.y R".sub.z wherein M is a metal of Group IIIA of the Periodic Table of Elements, R is an alkyl group containing 1 to 12 carbon atoms, R' and R" are independently hydrogen, halide, alkyl or alkoxy groups containing from 1 to 12 carbon atoms, x is an integer from 1 to 3, and y and z are 0 or an integer from 1 to 2, the sum of which is not greater than 3-x; (d) contacting said product of step (c) with a vanadium compound having the formula: V(OR).sub.x (O).sub.y (X.sup.2).sub.z wherein X 2 is a halogen, R is a saturated hydrocarbon having from 1 to about 18 carbon atoms, x=0 or an integer from 1 to 5, y=0 or 1, and z=(5-x-2y) or 4 or 3 when x=0, y=0, or mixtures of such vanadium compounds; (e) reacting said product of step (d) with an organic reagent selected from the group consisting of alcohols, ethers, carbonates, amines, and phosphorous compounds; and (f) adding an alkylaluminum first cocatalyst component, and at least one halosilane second cocatalyst component having the formula R f 8 SiX g 3 where X 3 is halogen; R 8 is hydrogen, alkoxy, alkyl, aryl, silyoxy or cycloalkyl; f is 0 or an integer from 1 to 3, and g is an integer from 1 to 4 with the proviso that the sum of f and g is 4, to the silica supported vanadium based solid catalyst component during polymerization of said α-olefin.
Claim 3
Dependent Claim
21 words
The catalyst system of claim 1 wherein the halosilane is selected from the group consisting of trimethylchlorosilane, silicon tetrachloride, and trichlorosilane.
Claim 4
Dependent Claim
26 words
The catalyst system of claim 1 wherein the alkylaluminum compound is selected from the group consisting of trialkylaluminum, alkylaluminum halide, alkyl aluminum hydride and mixtures thereof.
Claim 5
Dependent Claim
12 words
The catalyst system of claim 3 wherein the aluminum-containing compound is triethylaluminum.
Claim 6
Dependent Claim
34 words
The catalyst system of claim 1 wherein the aluminum-containing compound and the halosilane compound are added to the solid catalyst in a molar ratio of about 1:1:1 to about 1000:1000:1 based on aluminum:halosilane:solid catalyst.
Claim 7
Dependent Claim
13 words
The catalyst system of claim 1 wherein the organic reagent is an alcohol.
Claim 8
Dependent Claim
16 words
The catalyst system of claim 6 wherein the alcohol contains from 1 to 18 carbon atoms.
Claim 9
Dependent Claim
19 words
The catalyst system of claim 7 wherein the alcohol is a n-alcohol having from 3 to 6 carbon atoms.
Claim 10
Dependent Claim
12 words
The catalyst system of claim 8 wherein the alcohol is 2-methoxy ethanol.
Claim 11
Dependent Claim
147 words
The catalyst system of claim 1 wherein said solid catalyst further comprises: a modifying compound having the structural formula M(R.sup.4).sub.d X.sup.4.sub.3-d wherein M is Al or B, X 3 is a halogen, R 4 is a saturated hydrocarbon having from 2 to about 12 carbon atoms and d is 0 or an integer from 1 to 3 or Mg.sub.e R.sup.5 Y.sub.2-e wherein R 5 is a saturated hydrocarbon having from 1 to about 12 carbon atoms, Y is a halogen or an alkoxy having the formula OR 6 where R 6 is a saturated hydrocarbon having from 2 to about 12 carbon atoms, or a silyl amide having the formula N(SiR 3 7 ) 2 where R 7 is a saturated hydrocarbon having from 2 to about 12 carbon atoms, and e is 0 or an integer from 1 to 2; or mixtures of such modifying compounds.
Claim 12
Dependent Claim
30 words
The catalyst system of claim 1 wherein said organometallic compound is an aluminum-containing compound is an alkylaluminum compound selected from the group consisting of trialkylaluminum, alkylaluminum halide and alkylaluminum hydride.
Claim 13
Dependent Claim
14 words
The catalyst system of claim 11 wherein the aluminum-containing compound is triethylaluminum or triisobutylaluminum.
Claim 14
Dependent Claim
29 words
The catalyst system of claim 1 wherein said vanadium compound is VCl 4 , VCl 3 , VOCl 3 , VO(i-OC 3 H 7 ) 3 or mixtures thereof.
Claim 15
Dependent Claim
24 words
The catalyst system of claim 1 wherein the amount of organometallic compound is from about 0.3 to about 3.0 millimoles per gram of silica.
Claim 16
Dependent Claim
23 words
The catalyst system of claim 1 wherein the amount of vanadium compound is about 0.01 to about 10 millimoles per gram of silica.
Claim 17
Dependent Claim
22 words
The catalyst system of claim 12 wherein the amount of alcohol is about 0.01 to about 10 millimoles per gram of silica.
References Cited (Backward Citations)
US3786032A
Cited
US4004071A
Cited
US4530913A
Cited
US4250287A
Cited
US4611038A
Cited
US4559318A
Cited
US4806433A
Cited
US4831000A
Cited
US4866021A
Cited
US4912074A
Cited
US4972033A
Cited
US5006618A
Cited
US5051388A
Cited
US5104949A
Cited
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