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US4426317A
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Process for making olefin polymerization catalyst
Assignee: USI CHEMICALS Co Inc
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Filing: 1982-11-24
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Granted: 1984-01-17
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Expires: 2002-11-24
Abstract
Abstract Olefin polymerization catalysts of the type prepared by (1) drying an inorganic oxide, such as silica, having surface hydroxyl groups to remove adsorbed water, (2) slurrying the dried inorganic oxide in an inert liquid hydrocarbon, such as a hydrocarbon boiling in the C 4 -C 8 range, (3) reacting the surface hydroxyl groups of the dried inorganic oxide with an organometallic compound, such as a trialkylaluminum, and (4) reacting the thus-treated support with a vanadium compound, such as vanadium oxytrichloride, are made reproducibly uniform at commercial scale by modifying the catalyst syntheses so as to (a) conduct the reactions with agitation in an amount of inert liquid hydrocarbon such as to provide a weight/unit volume solids content of about 10 to 50% and (b) add the vanadium compound to the agitated slurry of treated inorganic oxide particles at a rate such as to ensure substantially uniform coverage of those particles with the vanadium compound as it reacts therewith. In a preferred embodiment of the invention, the organometallic compound is also added to the agitated slurry at a rate such as to ensure substantially uniform coverage of the inorganic oxide particles with the organometallic compound as it reacts with the surface hydroxyl groups.
Inventors
- 👤 Thomas K. Rogers
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 04:31
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
257 words
In a process for preparing an olefin polymerization catalyst composition by: (1) drying an inorganic oxide having surface hydroxyl groups to form a support that is substantially free of adsorbed water, (2) slurry and dried inorganic oxide in an inert liquid hydrocarbon, (3) reacting the surface hydroxyl groups of the dried inorganic oxide with at least about 0.5 mol, per mol of surface hydroxyl groups, 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, and (4) reacting the thus-treated support with at least about 0.001 mol, per mol of organometallic compound, of at least one vanadium compound wherein the vanadium has a valence of at least +3, the improvement which comprises: (A) conducting the reactions with agitation in an amount of inert liquid hydrocarbon such as to provide a weight/unit volume solids content of about 10 to 50% and (B) adding the vanadium compound to the agitated slurry of treated inorganic oxide particles at a rate such as to ensure substantially uniform distribution of the vanadium compound on the particles as it reacts therewith.
Claim 2
Dependent Claim
257 words
In a process for preparing an olefin polymerization catalyst composition by: (1) drying an inorganic oxide having surface hydroxyl groups to form a support that is substantially free of adsorbed water, (2) slurry and dried inorganic oxide in an inert liquid hydrocarbon, (3) reacting the surface hydroxyl groups of the dried inorganic oxide with at least about 0.5 mol, per mol of surface hydroxyl groups, 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, and (4) reacting the thus-treated support with at least about 0.001 mol, per mol of organometallic compound, of at least one vanadium compound wherein the vanadium has a valence of at least +3, the improvement which comprises: (A) conducting the reactions with agitation in an amount of inert liquid hydrocarbon such as to provide a weight/unit volume solids content of about 10 to 50% and (B) adding the vanadium compound to the agitated slurry of treated inorganic oxide particles at a rate such as to ensure substantially uniform distribution of the vanadium compound on the particles as it reacts therewith.
Claim 3
Dependent Claim
28 words
The process of claim 1 wherein the catalyst composition preparation incorporating the improvement is one wherein there is no washing of the composition during or after its preparation.
Claim 4
Dependent Claim
29 words
The process of claim 1 wherein the inorganic oxide is dried in one vessel, and then transferred to another vessel in which the slurrying and reaction steps are conducted.
Claim 5
Dependent Claim
15 words
The process of claim 1 wherein the entire process is conducted in a single vessel.
Claim 6
Dependent Claim
24 words
The process of claim 1 wherein the vanadium compound is added at a rate such as to provide a flow constant of about 0.01-0.1.
Claim 7
Dependent Claim
24 words
The process of claim 5 wherein the vanadium compound is added at a rate such as to provide a flow constant of about 0.025-0.05.
Claim 8
Dependent Claim
32 words
The process of claim 1 wherein the organometallic compound is employed in an amount such as to provide at least about one mol of organometallic compound per mol of surface hydroxyl groups.
Claim 9
Dependent Claim
32 words
The process of claim 1 wherein the organometallic compound is employed in an amount such as to provide less than about one mol of organometallic compound per mol of surface hydroxyl groups.
Claim 10
Dependent Claim
36 words
The process of claim 8 wherein the organometallic compound is also added to the agitated inorganic oxide slurry at a rate such as to ensure its substantially uniform distribution on the particles as it reacts therewith.
Claim 11
Dependent Claim
24 words
The process of claim 1 wherein the support is an inorganic oxide selected from the group consisting of silica, alumina, magnesia, and mixtures thereof.
Claim 12
Dependent Claim
11 words
The process of claim 10 wherein the inorganic oxide is silica.
Claim 13
Dependent Claim
22 words
The process of claim 1 wherein the inert liquid hydrocarbon is a saturated hydrocarbon boiling in the C 4 -C 8 range.
Claim 14
Dependent Claim
12 words
The process of claim 12 wherein the inert liquid hydrocarbon is isobutane.
Claim 15
Dependent Claim
16 words
The process of claim 12 wherein the inert liquid hydrocarbon is a pure or commercial hexane.
Claim 16
Dependent Claim
24 words
The process of claim 3 in which the catalyst is dried in the same vessel in which the slurry and reaction steps are conducted.
Claim 17
Dependent Claim
62 words
The process 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 18
Dependent Claim
12 words
The process of claim 12 wherein the organometallic compound is a trialkylaluminum.
Claim 19
Dependent Claim
10 words
The process of claim 17 wherein the trialkylaluminum is triethylaluminum.
Claim 20
Dependent Claim
10 words
The process of claim 17 wherein the trialkylaluminum is tri-n-hexylaluminum.
Claim 21
Dependent Claim
72 words
The process of claim 1 wherein the vanadium component comprises 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.
Claim 22
Dependent Claim
21 words
The process of claim 20 wherein the vanadium compound is a compound corresponding to the formula (RO) n VOCl 3-n .
Claim 23
Dependent Claim
12 words
The process of claim 21 wherein n has a value of 0.
Claim 24
Dependent Claim
17 words
The process of claim 21 wherein R is alkyl and n has a value of about 1.
Claim 25
Dependent Claim
21 words
The process of claim 20 wherein the vanadium compound is a compound corresponding to the formula (RO) m VCl 4-m .
Claim 26
Dependent Claim
12 words
The process of claim 24 wherein m has a value of 0.
Claim 27
Dependent Claim
29 words
The process of claim 1 wherein the reactants are employed in amounts such as to provide about 5 to 30 mols of organometallic compound per mol of vanadium compound.
Claim 28
Dependent Claim
87 words
The process of claim 26 wherein the inorganic oxide is silica, the inert liquid hydrocarbon is a saturated hydrocarbon boiling in the C 4 -C 8 range, the organometallic compound is a trialkylaluminum, the vanadium compound is VOCl 3 , the amounts of organometallic and vanadium compounds employed are less than those required to react with substantially all of the reactive sites on the particles in the slurry, and the VOCl 3 is added at a rate such as to provide a flow constant of about 0.025-0.05.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-01-16 | 1987-07-18 | 1988-01-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-01-16 | 1991-07-18 | 1992-01-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-01-16 | 1995-07-18 | 1996-01-17 | $7700.00 | Window Closed / Lapsed |