US4218345A
Expired / Lapsed
US
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Olefin polymerization catalyst of chromium and process of preparing it
Assignee: Chemplex Co
•
Filing: 1979-01-15
•
Granted: 1980-08-19
•
Expires: 1999-01-15
Abstract
Abstract A catalyst, a process of preparing the catalyst and a method of making polymers and copolymers of 1-olefins with the catalyst in which the catalyst is prepared by producing finely divided particles of chromium metal by a sublimation process and dispersing the sublimate of chromium particles with an organic liquid and providing a mixture comprising the chromium sublimate particles and a support such as silica. The mixture is then heat activated in an oxidizing atmosphere. In another aspect of the invention the chromium sublimate particles and support particles are further modified by having a titanium compound as a part of the mixture of chromium sublimate particles and support particles.
Inventors
- 👤 Raymond E. Hoff
- 👤 Thomas J. Pullukat
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 06:33
CPC Classifications
B; B01; B01J; B01J23/00; B01J23/16; B01J23/24; B01J23/26; C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 52
Claim 1
Independent Claim
133 words
A dispersion of reactive chromium particles on a support, useful for making an olefin polymerization catalyst by heat activating in an oxidizing gas, prepared by the process of (1) forming a sublimate of chromium metal particles by subliming chromium metal under high vacuum conditions while adding an organic liquid and condensing said chromium and organic liquid on a cold surface that is at a temperature such that the vapor pressure of the organic liquid is 10 -3 torr or less, (2) forming a mixture of said sublimate particles and organic liquid and a finely divided, difficultly reducible support selected from the group consisting of silica, alumina, zirconia, thoria, titania, magnesia and mixtures thereof, (3) heat activating the mixture of (2) in an oxidizing gas atmosphere, and (4) separating the organic liquid by evaporation.
Claim 2
Dependent Claim
133 words
A dispersion of reactive chromium particles on a support, useful for making an olefin polymerization catalyst by heat activating in an oxidizing gas, prepared by the process of (1) forming a sublimate of chromium metal particles by subliming chromium metal under high vacuum conditions while adding an organic liquid and condensing said chromium and organic liquid on a cold surface that is at a temperature such that the vapor pressure of the organic liquid is 10 -3 torr or less, (2) forming a mixture of said sublimate particles and organic liquid and a finely divided, difficultly reducible support selected from the group consisting of silica, alumina, zirconia, thoria, titania, magnesia and mixtures thereof, (3) heat activating the mixture of (2) in an oxidizing gas atmosphere, and (4) separating the organic liquid by evaporation.
Claim 3
Dependent Claim
68 words
The dispersion of claim 1 wherein the sublimate of (1) is formed by vaporizing chromium metal into a chamber under high vacuum conditions by heating the chromium to a temperature such that its equilibrium vapor pressure is between 10 -5 and 10 -2 torr while adding to the chamber an organic liquid and condensing the chromium and organic liquid into a cold surface while maintaining said high vacuum.
Claim 4
Dependent Claim
24 words
The dispersion of claim 2 wherein said chromium sublimate is formed simultaneously with vaporizing and then condensing on said cooled surface said organic liquid.
Claim 5
Dependent Claim
36 words
The dispersion of claim 1 wherein said sublimate of (1) is formed simultaneously with vaporizing and then condensing an organic liquid in the presence of said sublimate to produce chromium sublimate particles dispersed in said liquid.
Claim 6
Dependent Claim
33 words
The dispersion of claim 4 wherein said organic liquid is chilled to a solid on said cooled surface followed by melting the solid to reconstitute the liquid with said chromium particles dispersed therein.
Claim 7
Dependent Claim
30 words
The dispersion of claim 1 wherein said mixture of (2) is formed by adding the chromium particles of (1) to the support while fluidizing with an atmosphere of inert gas.
Claim 8
Dependent Claim
53 words
The dispersion of claim 6 wherein the chromium particles sublimate of (1) is formed by vaporizing bulk chromium metal into a chamber under high vacuum conditions by heating the chromium to a temperature of from 1400° to 1700° C. and condensing the chromium vapor on said solid surface while maintaining said high vacuum.
Claim 9
Dependent Claim
24 words
The dispersion of claim 7 wherein said chromium sublimate is formed simultaneously with vaporizing and then condensing on said cooled surface an organic liquid.
Claim 10
Dependent Claim
35 words
The dispersion of claim 6 wherein said sublimate of (1) is formed simultaneously with vaporizing and then condensing an organic liquid in the presence of said sublimate to produce chromium particles dispersed in said liquid.
Claim 11
Dependent Claim
33 words
The dispersion of claim 9 wherein said organic liquid is chilled to a solid on said cooled surface followed by melting the solid to reconstitute the liquid with said dispersed chromium particles therein.
Claim 12
Dependent Claim
148 words
A dispersion of reactive chromium particles on a support, useful for making an olefin polymerization catalyst by heat activating in an oxidizing gas, prepared by the process of (1) forming a sublimate of chromium metal particles mixed with an organic liquid by subliming chromium metal under high vacuum conditions while adding an organic liquid and condensing said chromium and organic liquid on a cold surface that is at a temperature such that the vapor pressure of the organic liquid is 10 -3 torr or less, (2) forming a mixture of said sublimate particles and organic liquid and a finely divided, difficultly reducible support selected from the group consisting of silica, alumina, zirconia, thoria, titania, magnesia and mixtures thereof, (3) adding a titanium compound to the mixture of (2), (4) heat activating the mixture of (3) in an oxidizing gas atmosphere, and (5) separating the organic liquid by evaporation.
Claim 13
Dependent Claim
148 words
A dispersion of reactive chromium particles on a support, useful for making an olefin polymerization catalyst by heat activating in an oxidizing gas, prepared by the process of (1) forming a sublimate of chromium metal particles mixed with an organic liquid by subliming chromium metal under high vacuum conditions while adding an organic liquid and condensing said chromium and organic liquid on a cold surface that is at a temperature such that the vapor pressure of the organic liquid is 10 -3 torr or less, (2) forming a mixture of said sublimate particles and organic liquid and a finely divided, difficultly reducible support selected from the group consisting of silica, alumina, zirconia, thoria, titania, magnesia and mixtures thereof, (3) adding a titanium compound to the mixture of (2), (4) heat activating the mixture of (3) in an oxidizing gas atmosphere, and (5) separating the organic liquid by evaporation.
Claim 14
Dependent Claim
60 words
The dispersion of claim 11 wherein the sublimate of (1) is formed by vaporizing chromium metal into a chamber under high vacuum conditions by heating the chromium to a temperature of from 1400° to 1700° C. while adding to the chamber an organic liquid and condensing the chromium and organic liquid on a cold surface while maintaining said high vacuum.
Claim 15
Dependent Claim
24 words
The dispersion of claim 11 wherein said chromium sublimate is formed simultaneously with vaporizing and then condensing on said cooled surface an organic liquid.
Claim 16
Dependent Claim
34 words
The dispersion of claim 11 wherein said sublimate of (1) is formed simultaneously with vaporizing and then condensing an organic liquid in the presence of said sublimate to produce chromium dispersed in said liquid.
Claim 17
Dependent Claim
33 words
The dispersion of claim 14 wherein said organic liquid is chilled to a solid on said cooled surface followed by melting the solid to reconstitute the liquid with said chromium particles dispersed therein.
Claim 18
Dependent Claim
33 words
The dispersion of claim 11 wherein said mixture of (2) is formed by adding the chromium particles of (1) to the support while fluidizing with an atmosphere of inert gas such as nitrogen.
Claim 19
Dependent Claim
54 words
The dispersion of claim 16 wherein the chromium particles sublimate of (1) is formed by vaporizing the bulk chromium metal into a chamber under high vacuum conditions by heating the chromium to a temperature of from 1400° to 1700° C. and condensing the chromium vapor on said cold surface while maintaining said high vacuum.
Claim 20
Dependent Claim
24 words
The dispersion of claim 17 wherein said chromium sublimate is formed simultaneously with vaporizing and then condensing on said cooled surface an organic liquid.
Claim 21
Dependent Claim
34 words
The dispersion of claim 16 wherein said sublimate of (1) is formed simultaneously with vaporizing and then condensing an organic liquid in the presence of said sublimate to produce chromium dispersed in said liquid.
Claim 22
Dependent Claim
33 words
The dispersion of claim 19 wherein said organic liquid is chilled to a solid on said cooled surface followed by melting the solid to reconstitute the liquid with said dispersed chromium particles therein.
Claim 23
Dependent Claim
19 words
The dispersion of claim 1 wherein said chromium is present in an amount to give about 0.1-10 wt.% chromium.
Claim 24
Dependent Claim
27 words
The dispersion of claim 11 wherein said titanium compound is present in an amount to produce about 0.1-8.0 wt.% titanium based on the weight of said support.
Claim 25
Dependent Claim
25 words
The dispersion of claim 1 wherein the mixture of (2) is dried at from about 95°-205° C. for from about 15 minutes to two hours.
Claim 26
Dependent Claim
113 words
The process of preparing an active polymerizing catalyst, comprising: (1) forming a sublimate of chromium metal particles mixed with an organic liquid by subliming chromium metal under high vacuum conditions while adding to the vacuum chamber an organic liquid and condensing said chromium and organic liquid on a cold surface that is at a temperature such that the vapor pressure of the organic liquid is 10 -3 torr or less, (2) forming a mixture of said sublimate particles and a finely divided, difficultly reducible support selected from the group consisting of silica, alumina, zirconia, thoria, titania, magnesia and mixtures thereof, and (3) heat activating the mixture of (2) in an oxidizing gas atmosphere.
Claim 27
Dependent Claim
113 words
The process of preparing an active polymerizing catalyst, comprising: (1) forming a sublimate of chromium metal particles mixed with an organic liquid by subliming chromium metal under high vacuum conditions while adding to the vacuum chamber an organic liquid and condensing said chromium and organic liquid on a cold surface that is at a temperature such that the vapor pressure of the organic liquid is 10 -3 torr or less, (2) forming a mixture of said sublimate particles and a finely divided, difficultly reducible support selected from the group consisting of silica, alumina, zirconia, thoria, titania, magnesia and mixtures thereof, and (3) heat activating the mixture of (2) in an oxidizing gas atmosphere.
Claim 28
Dependent Claim
68 words
The process of claim 24 wherein the sublimate of (1) is formed by vaporizing chromium metal into a chamber under high vacuum conditions by heating the chromium to a temperature such that its equilibrium vapor pressure is between 10 -5 and 10 -2 torr while adding to the chamber an organic liquid and condensing the chromium and organic liquid onto a cold surface while maintaining said high vacuum.
Claim 29
Dependent Claim
24 words
The process of claim 25 wherein said chromium sublimate is formed simultaneously with vaporizing and then condensing on said cooled surface said organic liquid.
Claim 30
Dependent Claim
36 words
The process of claim 24 wherein said sublimate of (1) is formed simultaneously with vaporizing and then condensing an organic liquid in the presence of said sublimate to produce chromium sublimate particles dispersed in said liquid.
Claim 31
Dependent Claim
33 words
The process of claim 27 wherein said organic liquid is chilled to a solid on said cooled surface followed by melting the solid to reconstitute the liquid with said chromium particles dispersed therein.
Claim 32
Dependent Claim
30 words
The process of claim 24 wherein said mixture of (2) is formed by adding the chromium particles of (1) to the support while fluidizing with an atmosphere of inert gas.
Claim 33
Dependent Claim
53 words
The process of claim 29 wherein the chromium particles sublimate of (1) is formed by vaporizing bulk chromium metal into a chamber under high vacuum conditions by heating th chromium to a temperature of from 1400° to 1700° C. and condensing the chromium vapor on said solid surface while maintaining said high vacuum.
Claim 34
Dependent Claim
24 words
The process of claim 30 wherein said chromium sublimate is formed simultaneously with vaporizing and then condensing on said cooled surface an organic liquid.
Claim 35
Dependent Claim
35 words
The process of claim 29 wherein said sublimate of (1) is formed simultaneously with vaporizing and then condensing an organic liquid in the presence of said sublimate to produce chromium particles dispersed in said liquid.
Claim 36
Dependent Claim
33 words
The process of claim 32 wherein said organic liquid is chilled to a solid on said cooled surface followed by melting the solid to reconstitute the liquid with said dispersed chromium particles therein.
Claim 37
Dependent Claim
121 words
The process of preparing an active polymerizing catalyst, comprising: (1) forming a sublimate of chromium metal particles mixed with an organic liquid by subliming chromium metal under high vacuum conditions while adding an organic liquid and condensing said chromium and organic liquid on a cold surface that is at a temperature such that the vapor pressure of the organic liquid is 10 -3 torr or less, (2) forming a mixture of said sublimate particles and organic liquid and a finely divided, difficultly reducible support selected from the group consisting of silica, alumina, zirconia, thoria, titania, magnesia and mixtures thereof, (3) adding a titanium compound to the mixture of (2), and heat activating the mixture of (3) in an oxidizing gas atmosphere.
Claim 38
Dependent Claim
121 words
The process of preparing an active polymerizing catalyst, comprising: (1) forming a sublimate of chromium metal particles mixed with an organic liquid by subliming chromium metal under high vacuum conditions while adding an organic liquid and condensing said chromium and organic liquid on a cold surface that is at a temperature such that the vapor pressure of the organic liquid is 10 -3 torr or less, (2) forming a mixture of said sublimate particles and organic liquid and a finely divided, difficultly reducible support selected from the group consisting of silica, alumina, zirconia, thoria, titania, magnesia and mixtures thereof, (3) adding a titanium compound to the mixture of (2), and heat activating the mixture of (3) in an oxidizing gas atmosphere.
Claim 39
Dependent Claim
60 words
The process of claim 34 wherein the sublimate of (1) is formed by vaporizing chromium metal into a chamber under high vacuum conditions by heating the chromium to a temperature of from 1400° to 1700° C. while adding to the chamber an organic liquid and condensing the chromium and organic liquid on a cold surface while maintaining said high vacuum.
Claim 40
Dependent Claim
24 words
The process of claim 34 wherein said chromium sublimate is formed simultaneously with vaporizing and then condensing on said cooled surface an organic liquid.
Claim 41
Dependent Claim
34 words
The process of claim 34 wherein said sublimate of (1) is formed simultaneously with vaporizing and then condensing an organic liquid in the presence of said sublimate to produce chromium dispersed in said liquid.
Claim 42
Dependent Claim
33 words
The process of claim 37 wherein said organic liquid is chilled to a solid on said cooled surface followed by melting the solid to reconstitute the liquid with said chromium particles dispersed therein.
Claim 43
Dependent Claim
33 words
The process of claim 34 wherein said mixture of (2) is formed by adding the chromium particles of (1) to the support while fluidizing with an atmosphere of inert gas such as nitrogen.
Claim 44
Dependent Claim
54 words
The process of claim 39 wherein the chromium particles sublimate of (1) is formed by vaporizing the bulk chromium metal into a chamber under high vacuum conditions by heating the chromium to a temperature of from 1400° to 1700° C. and condensing the chromium vapor on said cold surface while maintaining said high vacuum.
Claim 45
Dependent Claim
24 words
The process of claim 40 wherein said chromium sublimate is formed simultaneously with vaporizing and then condensing on said cooled surface an organic liquid.
Claim 46
Dependent Claim
34 words
The process of claim 39 wherein said sublimate of (1) is formed simultaneously with vaporizing and then condensing an organic liquid in the presence of said sublimate to produce chromium dispersed in said liquid.
Claim 47
Dependent Claim
33 words
The process of claim 42 wherein said organic liquid is chilled to a solid on said cooled surface followed by melting the solid to reconstitute the liquid with said dispersed chromium particles therein.
Claim 48
Dependent Claim
19 words
The process of claim 24 wherein said chromium is present in an amount to give about 0.1-10 wt.% chromium.
Claim 49
Dependent Claim
27 words
The process of claim 34 wherein said titanium compound is present in an amount to produce about 0.1-8.0 wt.% titanium based on the weight of said support.
Claim 50
Dependent Claim
10 words
The process of claim 24 wherein said gas comprises air.
Claim 51
Dependent Claim
25 words
The process of claim 24 wherein the mixture of (2) is dried at from about 95°-205° C. for from about 15 minutes to two hours.
Claim 52
Dependent Claim
68 words
The process of claim 34 wherein the sublimate of (1) is formed by vaporizing chromium metal into a chamber under high vacuum conditions by heating the chromium to a temperature such that its equilibrium vapor pressure is between 10 -5 and 10 -2 torr while adding to the chamber an organic liquid and condensing the chromium and organic liquid on a cold surface while maintaining said high vacuum.
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) | 1983-08-19 | 1984-02-18 | 1984-08-19 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-08-19 | 1988-02-18 | 1988-08-19 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-08-19 | 1992-02-18 | 1992-08-19 | $7700.00 | Window Closed / Lapsed |