US4954471A
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Homogeneous or supported vanadium based catalyst for olefin polymerization
Assignee: ExxonMobil Chemical Patents Inc
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Filing: 1988-11-28
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Granted: 1990-09-04
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Expires: 2008-11-28
Abstract
Abstract Disclosed is a homogeneous vanadium catalyst composition prepared by the reaction of an alkylaluminum dihalide with a solid reaction product produced by reacting (A) a silicon alkoxide, (B) a hydrocarbon soluble vanadium compound, and (C) a trialkylaluminum. The solid reaction product may be produced by complexing the (A) silicon alkoxide first with either the (B) vanadium compound or the (C) trialkylaluminum. The intermediate complex (I) of such reaction is then treated with the remaining reagent (either the vanadium compound or the trialkylaluminum as the case may be) whereupon the solid reaction product (II) is formed. The solid reaction product (II) of the silicon alkoxide-vanadium compound/trialkylaluminum reaction is then reacted with (D) an alkylaluminum dihalide to produce a homogeneous hydrocarbon soluble product (III) which is highly active for catalyzing the polymerization of olefins to a polyolefin having a narrow molecular weight distribution. Further, the hydrocarbon soluble product (III) may be used to treat a catalyst support material (E) to produce a heterogeneous supported vanadium-containing catalyst composition (IV) which is highly active for catalyzing the production of polyolefins having a narrow molecular weight distribution.
Inventors
- 👤 Steven A. Best
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 23:50
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/68; C08F10/00
Claims Analysis
Total Claims: 25
Claim 1
Independent Claim
69 words
A method for preparing a hydrocarbon soluble vanadium based catalyst component for the production of polyolefins, comprising the steps of: (i) forming a hydrocarbon insoluble reaction product from a silicon alkoxide, a hydrocarbon soluble vanadium compound and a trialkylaluminum; and (ii) reacting said hydrocarbon insoluble reaction product with an alkylaluminum dihalide to form a hydrocarbon soluble vanadium containing composition which is active for the polymerization of olefins to polyolefins.
Claim 2
Independent Claim
69 words
A method for preparing a hydrocarbon soluble vanadium based catalyst component for the production of polyolefins, comprising the steps of: (i) forming a hydrocarbon insoluble reaction product from a silicon alkoxide, a hydrocarbon soluble vanadium compound and a trialkylaluminum; and (ii) reacting said hydrocarbon insoluble reaction product with an alkylaluminum dihalide to form a hydrocarbon soluble vanadium containing composition which is active for the polymerization of olefins to polyolefins.
Claim 3
Dependent Claim
103 words
The method of claim 1, wherein said silicon alkoxide is of the general formula Si(OR s ) 4-k R s' wherein R s , R s' are C 1-18 hydrocarbon radicals and 0≦k≦3, and said hydrocarbon soluble vanadium compound is selected from the group consisting of the general formulas: ##STR2## wherein: m is 0-3; n is 0,3-4; p is 2-3; q is 0 or 2-3; x and y are 1-2, x≠y; R v is a C 1-18 hydrocarbon radical; R v' is acetylacetonate; X ia --Cl or --Br; and L is a Lewis base capable of forming hydrocarbonsoluble complexes with VX 3 .
Claim 4
Dependent Claim
24 words
The method of claim 2, wherein said trialkyaluminum is of the general formula Al(R) 3 , wherein R is a C 1-18 hydrocarbon radical.
Claim 5
Dependent Claim
29 words
The method of claim 3, wherein said alkylaluminum dihalide is of the formula: Al(R.sup.a)Y.sub.2, wherein R a is a C 1-18 hydrocarbon radical and Y is a halogen atom.
Claim 6
Dependent Claim
37 words
The method of claim 4, wherein said hydrocarbon insoluble reaction product is formed by first reacting said silicon alkoxide with said vanadium compound to form an intermediate product and thereafter reacting said intermediate product with said trialkylaluminum.
Claim 7
Dependent Claim
37 words
The method of claim 4, wherein said hydrocarbon insoluble reaction product is formed by first reacting said silicon alkoxide with said trialkylaluminum to form an intermediate product and thereafter reacting said intermediate product with said vanadium compound.
Claim 8
Independent Claim
14 words
The method of claims 5 or 6, wherein said alkylaluminum dihalide is ethylaluminum dichloride.
Claim 9
Dependent Claim
12 words
The method of claim 7, wherein said silicon alkoxide is silicon tetra-alkoxide.
Claim 10
Dependent Claim
192 words
A process for preparing a hydrocarbon soluble vanadium-based catalyst for the production of olefin copolymers, comprising the steps of (i) contacting a silicon alkoxide of the formula Si(OR s ) 4-k R k s' wherein R s , R s' are C 1-18 hydrocarbon radicals, and 0 ≦k≦3 with a vanadium compound selected from the group consisting of the general formulas: ##STR3## wherein: m is 0-3; n is 0,3-4; p is 2-3; q is 0 or 2-3; x and y are 1-2, x≠y; R v is a C 1-18 hydrocarbon radical; R v' is acetylacetonate; X ia --Cl or --Br; and L is a Lewis base capable of forming hydrocarbon-soluble complexes with VX 3 to form an intermediate reaction product (I); (ii) reacting said intermediate reaction product (I) with a trialkyl alminum of the general formula Al(R) 3 , wherein R is a C 1-18 hydrocarbon radical to form a solid reaction product (II); and (iii) adding to said solid reaction product (II) an alkylaluminum dihalide of the formula: Al(R.sup.a)Y.sub.2, wherein R a is a C 1-18 hydrocarbon radical and Y is a halogen atom, to produce a homogeneous catalyst solution (III).
Claim 11
Dependent Claim
192 words
A process for preparing a hydrocarbon soluble vanadium-based catalyst for the production of olefin copolymers, comprising the steps of (i) contacting a silicon alkoxide of the formula Si(OR s ) 4-k R k s' wherein R s , R s' are C 1-18 hydrocarbon radicals, and 0 ≦k≦3 with a vanadium compound selected from the group consisting of the general formulas: ##STR3## wherein: m is 0-3; n is 0,3-4; p is 2-3; q is 0 or 2-3; x and y are 1-2, x≠y; R v is a C 1-18 hydrocarbon radical; R v' is acetylacetonate; X ia --Cl or --Br; and L is a Lewis base capable of forming hydrocarbon-soluble complexes with VX 3 to form an intermediate reaction product (I); (ii) reacting said intermediate reaction product (I) with a trialkyl alminum of the general formula Al(R) 3 , wherein R is a C 1-18 hydrocarbon radical to form a solid reaction product (II); and (iii) adding to said solid reaction product (II) an alkylaluminum dihalide of the formula: Al(R.sup.a)Y.sub.2, wherein R a is a C 1-18 hydrocarbon radical and Y is a halogen atom, to produce a homogeneous catalyst solution (III).
Claim 12
Dependent Claim
54 words
The process of claim 9, wherein the vanadium-based catalyst is prepared in heterogeneous supported form, further including the steps of: (iv) adding to said homogeneous catalyst solution (III) a dry support material to produce a slurry; (v) stirring said slurry for about 30 minutes; and (vi) separating a supported catalyst product from said slurry.
Claim 13
Dependent Claim
191 words
A process for preparing a hydrocarbon soluble vanadium-based catalyst for the production of polyolefin comprising the steps of: (i) contacting a trialkyl aluminum of the general formula Al(R) 3 , wherein R is a C 1-18 hydrocarbon radical, with a silicon alkoxide of the formula Si(OR s ) 4-k R k s' wherein R s , R s' are C 1-18 hydrocarbon radicals, and 0≦k≦3, to form an intermediate reaction product (I); (ii) reacting said intermediate reaction product (I) with a vanadium compound selected from the group consisting of the general formulas: ##STR4## wherein: m is 0-3; n is 0,3-4; p is 2-3; q is 0 or 2-3; x and y are 1-2, x≠y; R v is a C 1-18 hydrocarbon radical; R v' is acetylacetonate; X ia --Cl or --Br; and L is a Lewis base capable of forming hydrocarbon-soluble complexes with VX 3 , to form an intermediate reaction product (II); and (iii) adding to said solid reaction product (II) an alkylaluminum dihalide of the formula: Al(R.sup.a)Y.sub.2, wherein R a is a C 1-18 hydrocarbon radical and Y is a halogen atom, to produce a homogeneous catalyst solution (III).
Claim 14
Dependent Claim
191 words
A process for preparing a hydrocarbon soluble vanadium-based catalyst for the production of polyolefin comprising the steps of: (i) contacting a trialkyl aluminum of the general formula Al(R) 3 , wherein R is a C 1-18 hydrocarbon radical, with a silicon alkoxide of the formula Si(OR s ) 4-k R k s' wherein R s , R s' are C 1-18 hydrocarbon radicals, and 0≦k≦3, to form an intermediate reaction product (I); (ii) reacting said intermediate reaction product (I) with a vanadium compound selected from the group consisting of the general formulas: ##STR4## wherein: m is 0-3; n is 0,3-4; p is 2-3; q is 0 or 2-3; x and y are 1-2, x≠y; R v is a C 1-18 hydrocarbon radical; R v' is acetylacetonate; X ia --Cl or --Br; and L is a Lewis base capable of forming hydrocarbon-soluble complexes with VX 3 , to form an intermediate reaction product (II); and (iii) adding to said solid reaction product (II) an alkylaluminum dihalide of the formula: Al(R.sup.a)Y.sub.2, wherein R a is a C 1-18 hydrocarbon radical and Y is a halogen atom, to produce a homogeneous catalyst solution (III).
Claim 15
Dependent Claim
54 words
The process of claim 11, wherein the vanadiumbased catalyst is prepared in heterogeneous supported form, further including the steps of: (iv) adding to said homogeneous catalyst solution (III) a dry support material to produce a slurry; (v) stirring said slurry for about 30 minutes; and (vi) separating a supported catalyst product from said slurry.
Claim 16
Dependent Claim
14 words
The process of claims 9, 10, 11 or 12, wherein said trialkylaluminum is triethylaluminum.
Claim 17
Dependent Claim
16 words
The process of claims 9, 10, 11 or 12, wherein said silicon alkoxide is silicon tetra-alkoxide.
Claim 18
Dependent Claim
16 words
The process of claims 9, 10, 11 or 12, wherein said alkylaluminum dihalide is ethylaluminum dichloride.
Claim 19
Dependent Claim
65 words
A vanadium-based catalyst for the production of polyolefins produced by the process comprising the steps of: (i) forming a hydrocarbon insoluble reaction product from a silicon alkoxide, a hydrocarbon soluble vanadium compound and a trialkylaluminum; and (ii) reacting said hydrocarbon insoluble reaction product with an alkylaluminum dihalide to form a hydrocarbon soluble vanadium containing composition which is active for the polymerization of olefins to polyolefins.
Claim 20
Dependent Claim
65 words
A vanadium-based catalyst for the production of polyolefins produced by the process comprising the steps of: (i) forming a hydrocarbon insoluble reaction product from a silicon alkoxide, a hydrocarbon soluble vanadium compound and a trialkylaluminum; and (ii) reacting said hydrocarbon insoluble reaction product with an alkylaluminum dihalide to form a hydrocarbon soluble vanadium containing composition which is active for the polymerization of olefins to polyolefins.
Claim 21
Dependent Claim
150 words
The vanadium-based catalyst of claim 16, wherein said silicon alkoxide is of the general formula Si(OR s ) 4-k R k s' wherein R 5 , R 5' are C 1-18 hydrocarbon radicals and 0≦k≦3, said hydrocarbon soluble vanadium compound is selected from the group consisting of the general formulas: ##STR5## wherein: m is 0-3; n is 0,3-4; p is 2-3; q is 0 or 2-3; x and y are 1-2, x≠y; R v is a C 1-18 hydrocarbon radical; R v' is acetylacetonate; X ia --Cl or --Br; and L is a Lewis base capable of forming hydrocarbonsoluble complexes with VX 3 ; said trialky-aluminum is of the general formula Al(R) 3 , wherein R is a C 1-18 hydrocarbon radical; and said alkylaluminum dihalide is of the formula: Al(R a )Y 2 , wherein R a is a C 1-18 hydrocarbon radical and Y is a halogen atom.
Claim 22
Dependent Claim
38 words
The vanadium-based catalyst of claim 17, wherein said hydrocarbon insoluble reaction product is formed by first reacting said silicon alkoxide with said vanadium compound to form an intermediate product and thereafter reacting said intermediate product with said trialkylaluminum.
Claim 23
Dependent Claim
38 words
The vanadium-based catalyst of claim 17, wherein said hydrocarbon insoluble reaction product is formed by first reacting said silicon alkoxide with said trialkylaluminum to form an intermediate product and thereafter reacting said intermediate product with said vanadium compound.
Claim 24
Dependent Claim
15 words
The vanadium-based catalyst of claim 18 or 19, wherein said alkylaluminum dihalide is ethylaluminum dichloride.
Claim 25
Dependent Claim
54 words
The vanadium-based catalyst of claim 20 wherein said catalyst is prepared in heterogeneous supported form further including the steps of: (iv) adding to said homogeneous catalyst solution (III) a dry support material to produce a slurry; (v) stirring said slurry for about 30 minutes; and (vi) separating a supported catalyst product from said slurry.
References Cited (Backward Citations)
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