US4435518A
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US
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Polymerization catalyst
Assignee: USI CHEMICALS Co Inc
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Filing: 1982-11-24
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Granted: 1984-03-06
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Expires: 2002-11-24
Abstract
Abstract Catalyst compositions which are particularly useful for the preparation of ethylene polymers having a narrow molecular weight distribution are obtained by (1) drying an inorganic oxide having surface hydroxyl groups, e.g., silica, alumina, magnesia, etc., to remove adsorbed water, (2) reacting the surface hydroxyl groups with at least a stoichiometric amount of an organometallic compound having at least one alkyl group attached to a Group III metal, e.g., a trialkylaluminum, (3) reacting the thus-treated inorganic oxide with a vanadium halide, such as (a) VOCl 3 , VOBr 3 , and/or mono-, di-, and/or trihydrocarbyloxy derivatives thereof and/or (b) VCl 4 , VBr 4 , and/or mono-, di-, tri-, and/or tetrahydrocarbyloxy derivatives thereof, and (4) reacting that reaction product with at least about 0.1 mol, per mol of organometallic compound, of an alcohol containing 1 to 18 carbon atoms.
Inventors
- 👤 B. Timothy Pennington
- 👤 Paul V. Roling
- 👤 John T. T. Hsieh
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 03:26
CPC Classifications
C; C08; C08F; C08F10/00; Y; Y10; Y10S; Y10S526/00; Y10S526/901
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
245 words
A catalyst composition consisting essentially of the product obtained by: (1) drying an inorganic oxide having surface hydroxyl groups to form a support that is substantially free of adsorbed water, (2) reacting the surface hydroxyl groups of the support with at least a substantially stoichiometric amount of at least one organometallic compound corresponding to the formula R x MR' y R" z , wherein M is a metal of Group III of the periodic table, R is an alkyl group containing 1 to 12 carbon atoms, R' and R" are independently selected from the group consisting of H, Cl, and alkyl and alkoxy groups containing 1 to 12 carbon atoms, x has a value of 1 to 3, and y and z both represent values of 0 to 2, the sum of which is not greater than 3-x, (3) reacting the thus-treated support with at least about 0.001 mol, per mol of organometallic compound, of at least one vanadium compound corresponding to a formula selected from (RO) n VOX 3-n and (RO) m VX 4-m , in which formulas R represents a C 1 -C 18 monovalent hydrocarbon radical that is free of aliphatic unsaturation, X is Cl or Br, n has a value of 0 to 3, and m has a value of 0 to 4, and (4) reacting the product of step 3 with at least about 0.1 mol, per mol of organometallic compound, of an alcohol containing 1 to 18 carbon atoms.
Claim 2
Dependent Claim
245 words
A catalyst composition consisting essentially of the product obtained by: (1) drying an inorganic oxide having surface hydroxyl groups to form a support that is substantially free of adsorbed water, (2) reacting the surface hydroxyl groups of the support with at least a substantially stoichiometric amount of at least one organometallic compound corresponding to the formula R x MR' y R" z , wherein M is a metal of Group III of the periodic table, R is an alkyl group containing 1 to 12 carbon atoms, R' and R" are independently selected from the group consisting of H, Cl, and alkyl and alkoxy groups containing 1 to 12 carbon atoms, x has a value of 1 to 3, and y and z both represent values of 0 to 2, the sum of which is not greater than 3-x, (3) reacting the thus-treated support with at least about 0.001 mol, per mol of organometallic compound, of at least one vanadium compound corresponding to a formula selected from (RO) n VOX 3-n and (RO) m VX 4-m , in which formulas R represents a C 1 -C 18 monovalent hydrocarbon radical that is free of aliphatic unsaturation, X is Cl or Br, n has a value of 0 to 3, and m has a value of 0 to 4, and (4) reacting the product of step 3 with at least about 0.1 mol, per mol of organometallic compound, of an alcohol containing 1 to 18 carbon atoms.
Claim 3
Dependent Claim
24 words
The composition of claim 1 wherein the support is an inorganic oxide selected from the group consisting of silica, alumina, magnesia, and mixtures thereof.
Claim 4
Dependent Claim
62 words
The composition of claim 1 wherein the organometallic compound is a compound corresponding to the formula RAlR'R", wherein at least one of the R, R', and R" substituents is an alkyl group containing 1 to 12 carbon atoms and the remaining substituents are independently selected from the group consisting of hydrogen and alkyl and alkoxy groups containing 1 to 12 carbon atoms.
Claim 5
Dependent Claim
12 words
The compositions of claim 3 wherein the organometallic compound is a trialkylaluminum.
Claim 6
Dependent Claim
10 words
The composition of claim 4 wherein the trialkylaluminum is triethylaluminum.
Claim 7
Dependent Claim
10 words
The composition of claim 4 wherein the trialkylaluminum is tri-n-hexylaluminum.
Claim 8
Dependent Claim
21 words
The composition of claim 1 wherein the vanadium compound is a compound corresponding to the formula (RO) n VOCl 3-n .
Claim 9
Dependent Claim
17 words
The composition of claim 7 wherein R is alkyl and n has a value of about 1.
Claim 10
Dependent Claim
12 words
The composition of claim 7 wherein n has a value of 0.
Claim 11
Dependent Claim
21 words
The composition of claim 1 wherein the vanadium compound is a compound corresponding to the formula (RO) m VCl 4-m .
Claim 12
Dependent Claim
12 words
The composition of claim 10 wherein m has a value of 0.
Claim 13
Dependent Claim
12 words
The composition of claim 1 wherein the alcohol is a primary alcohol.
Claim 14
Dependent Claim
17 words
The composition of claim 12 wherein the alcohol is an alkanol containing at least 6 carbon atoms.
Claim 15
Dependent Claim
35 words
The composition of claim 1 wherein the amounts of materials employed in its preparation are such as to provide, as starting materials, about 5 to 30 mols of organometallic compound per mol of vanadium compound.
Claim 16
Dependent Claim
25 words
The composition of claim 1 wherein the amount of organometallic compound reacted with the surface hydroxyl groups of the support is the substantially stoichiometric amount.
Claim 17
Dependent Claim
91 words
A process for preparing the catalyst composition of claim 1 which consists essentially of (1) drying the inorganic oxide to remove substantially all adsorbed water, (2) slurrying the dried inorganic oxide in an inert liquid hydrocarbon, (3) adding at least a substantially stoichiometric amount of the organometallic compound to react it with the surface hydroxyl groups of the inorganic oxide, (4) adding the vanadium compound to react it with the treated inorganic oxide, (5) subsequently adding an alcohol containing 1 to 18 carbon atoms, and (6) drying the composition thus formed.
Claim 18
Dependent Claim
34 words
The process of claim 16 wherein the inorganic oxide is dried at about 100° to 1000° C. until substantially all adsorbed water is removed and is then cooled to ambient temperature before being slurried.
Claim 19
Dependent Claim
21 words
The process of claim 17 wherein the inorganic oxide is silica and the drying temperature is about 200° to 600° C.
Claim 20
Dependent Claim
21 words
The process of claim 17 wherein the inorganic oxide is magnesia and the drying temperature is about 200° to 600° C.
Claim 21
Dependent Claim
21 words
The process of claim 17 wherein the inorganic oxide is alumina and the drying temperature is about 500° to 600° C.
Claim 22
Dependent Claim
20 words
The process of claim 16 wherein the organometallic and vanadium compounds are added to the reaction mixture in neat form.
Claim 23
Dependent Claim
30 words
The process of claim 16 wherein at least one of the organometallic and vanadium compounds is added to the reaction mixture in the form of an inert liquid hydrocarbon solution.
References Cited (Backward Citations)
US3457244A
Cited
GB1175593A
Cited
US3535269A
Cited
US3591656A
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GB1489410A
Cited
US4148754A
Cited
US4113933A
Cited
US4330648A
Cited
US4333851A
Cited
US4263171A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-03-06 | 1987-09-05 | 1988-03-06 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-03-06 | 1991-09-05 | 1992-03-06 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-03-06 | 1995-09-05 | 1996-03-06 | $7700.00 | Window Closed / Lapsed |