US5043515A
Expired / Lapsed
US
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Ethylene oligomerization catalyst and process
Assignee: Shell USA Inc
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Filing: 1989-08-08
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Granted: 1991-08-27
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Expires: 2009-08-08
Abstract
Abstract This invention relates to an oligomerization catalyst comprising a zirconocene and one or more alkyl aluminoxanes wherein the alkyl is selected from methyl, ethyl and mixtures thereof and the ratio of equivalents of methyl to ethyl in the product ranges from about 4 to about 0.25 and wherein the atom ratio of aluminum to zirconium ranges from about 1 to about 100. It further relates to the method for preparing the catalyst and the use of the catalyst in an oligomerization process. The catalyst is particularly suited for the oligomerization of ethylene.
Inventors
- 👤 Lynn H. Slaugh
- 👤 Galeon W. Schoenthal
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 01:31
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/02; B01J31/12; B01J31/14; B01J31/143; B01J31/16; B01J31/22; B01J31/2282; B01J31/2295; C; C07; C07C; C07C2/00; C07C2/02; C07C2/04; C07C2/06; C07C2/08; C07C2/26; C07C2/32; C07C2/34; B01J2231/00; B01J2231/20; B01J2531/00; B01J2531/40; B01J2531/48; C07C2531/00; C07C2531/02; C07C2531/12; C07C2531/14; C07C2531/16; C07C2531/22; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/582; Y10; Y10S; Y10S526/00; Y10S526/943
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
59 words
An olefin oligomerization catalyst comprising the reaction product of a zirconocene and one or more alkyl aluminoxanes wherein alkyl is a mixture of methyl and ethyl groups, wherein the ratio of equivalents of methyl to ethyl ranges from about 4 to about 0.25, and wherein the atom ratio of aluminum to zirconium ranges from about 0.1 to about 100.
Claim 2
Dependent Claim
59 words
An olefin oligomerization catalyst comprising the reaction product of a zirconocene and one or more alkyl aluminoxanes wherein alkyl is a mixture of methyl and ethyl groups, wherein the ratio of equivalents of methyl to ethyl ranges from about 4 to about 0.25, and wherein the atom ratio of aluminum to zirconium ranges from about 0.1 to about 100.
Claim 3
Dependent Claim
19 words
The catalyst of claim 1 wherein the ratio of methyl to ethyl ranges from about 2 to about 0.33.
Claim 4
Dependent Claim
19 words
The catalyst of claim 2 wherein the ratio of methyl to ethyl ranges from about 1 to about 0.5.
Claim 5
Dependent Claim
54 words
The catalyst of any one of claims 1-3 wherein the zirconocene has the general formula (cyclopentadientyl) n ZrY 4-n wherein n is an integer ranging from 1 to 4, Y is selected from the group consisting of hydrogen, a C 1 -C 5 alkyl group, a C 6 -C 20 aryl group and halogen.
Claim 6
Dependent Claim
39 words
The catalyst of claim 4 wherein the zirconocene is selected from bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium dimethyl, bis(methylcyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium methyl chloride, bis(methylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium methyl chloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(n-butyl-cyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium methyl chloride, bis(n-butyl-cyclopentadienyl)zirconium dimethyl.
Claim 7
Dependent Claim
20 words
The catalyst of claim 4 wherein the atom ratio of aluminum to zirconium ranges from about 1 to about 20.
Claim 8
Dependent Claim
20 words
The catalyst of claim 6 wherein the atom ratio of aluminum to zirconium ranges from about 1 to about 10.
Claim 9
Dependent Claim
20 words
The catalyst of claim 7 wherein the atom ratio of aluminum to zirconium ranges from about 1 to about 5.
Claim 10
Dependent Claim
25 words
The catalyst of any one of claims 1-3 wherein the alkyl aluminoxane is prepared by hydrolyzing a mixture of trimethyl aluminum and triethyl aluminum compounds.
Claim 11
Dependent Claim
28 words
The catalyst of any one of claims 1-3 wherein the alkyl aluminoxane is prepared by separately hydrolyzing trimethyl aluminum and triethyl aluminum and mixing the resultant aluminoxanes together.
Claim 12
Dependent Claim
81 words
A process for oligomerizing olefins comprising ethylene which comprises contacting said olefins at a temperature ranging from about 100° to about 130° C. with a catalyst comprising the reaction product of a zirconocene and one or more alkyl aluminoxanes wherein alkyl is a mixture of methyl and ethyl groups, wherein the ratio of equivalents of methyl to ethyl ranges from about 4 to about 0.25, and wherein the atom ratio of aluminum to zirconium ranges from about 0.1 to about 100.
Claim 13
Dependent Claim
81 words
A process for oligomerizing olefins comprising ethylene which comprises contacting said olefins at a temperature ranging from about 100° to about 130° C. with a catalyst comprising the reaction product of a zirconocene and one or more alkyl aluminoxanes wherein alkyl is a mixture of methyl and ethyl groups, wherein the ratio of equivalents of methyl to ethyl ranges from about 4 to about 0.25, and wherein the atom ratio of aluminum to zirconium ranges from about 0.1 to about 100.
Claim 14
Dependent Claim
21 words
The process of claim 11 wherein the catalyst the ratio of methyl to ethyl ranges from about 2 to about 0.33.
Claim 15
Dependent Claim
22 words
The process of claim 12 wherein in the catalyst the ratio of methyl to ethyl ranges from about 1 to about 0.5.
Claim 16
Dependent Claim
16 words
The process of claim 11 wherein the temperature ranges from about 110° to about 125° C.
Claim 17
Dependent Claim
16 words
The process of claim 11 wherein the temperature ranges from about 115° to about 120° C.
Claim 18
Dependent Claim
16 words
The process of claim 12 wherein the temperature ranges from about 110° to about 125° C.
Claim 19
Dependent Claim
16 words
The process of claim 12 wherein the temperature ranges from about 115° to about 120° C.
Claim 20
Dependent Claim
16 words
The process of claim 13 wherein the temperature ranges from about 110° to about 125° C.
Claim 21
Dependent Claim
16 words
The process of claim 13 wherein the temperature ranges from about 115° to about 120° C.
Claim 22
Dependent Claim
25 words
The process of any one of claims 11-19 wherein the olefins being oligomerized additionally comprise one or more C 3 to C 10 alpha olefins.
Claim 23
Dependent Claim
55 words
The process of any one of claims 11-19 wherein in the catalyst the zirconocene has the general formula (cyclopentadienyl)n-ZrY 4-n wherein n is an integer ranging from 1 to 4, Y is selected from the group consisting of hydrogen, a C 1 -C 5 alkyl group, a C 6 -C 20 aryl group and halogen.
Claim 24
Dependent Claim
42 words
The process of claim 21 wherein in the catalyst the zirconocene is selected from bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium methyl chloride, bis(cyclopentadienylzirconium dimethyl, bis(methylcyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium methyl chloride, bis(methylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium methyl chloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(n-butyl-cyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium methyl chloride, bis(n-butylcyclopentadienyl)zirconium dimethyl.
Claim 25
Dependent Claim
23 words
The process of claim 21 wherein in the catalyst the atom ratio of aluminum to zirconium ranges from about 1 to about 20.
Claim 26
Dependent Claim
23 words
The process of claim 23 wherein in the catalyst the atom ratio of aluminum to zirconium ranges from about 1 to about 10.
Claim 27
Dependent Claim
23 words
The process of claim 24 wherein in the catalyst the atom ratio of aluminum to zirconium ranges from about 1 to about 5.
Claim 28
Dependent Claim
28 words
The process of any one of claims 11-19 wherein in the catalyst the alkyl aluminoxane is prepared by hydrolyzing a mixture of trimethyl aluminum and triethyl aluminum compounds.
Claim 29
Dependent Claim
31 words
The process of any one of claims 11-19 wherein in the catalyst the alkyl aluminoxane is prepared by separately hydrolyzing trimethyl aluminum and triethyl aluminum and mixing the resultant aluminoxanes together.
Claim 30
Dependent Claim
25 words
The process of any one of claims 11-19 wherein the olefins being oligomerized additionally comprise one or more C 3 to C 10 alpha olefins.
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