US4065612A
Expired / Lapsed
US
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Phenol modified polymerization catalyst and polymerization process
Assignee: Union Carbide Corp
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Filing: 1976-03-30
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Granted: 1977-12-27
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Expires: 1996-03-30
Abstract
Abstract An improved chromate ester catalyst useful for preparing, at relatively low temperatures, ethylene polymers which have a relatively lower molecular weight and which are more stable against oxidation is prepared by treating a silica supported chromate ester first with a phenol compound and then with a strong reducing agent.
Inventors
- 👤 Anthony David Hamer
- 👤 Frederick John Karol
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 19:27
CPC Classifications
C; C08; C08F; C08F10/00; C08F10/02; C08F110/00; C08F110/02
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
120 words
In a process for polymerizing a monomer charge comprising at least a major amount of ethylene by contacting said charge with a catalyst comprising chromate ester deposited on a support comprising silica and treated with strong reducing agent, the improvement which comprises treating said catalyst, prior to said treatment with said reducing agent, with phenol compound, said chromate ester containing one or more groups of the formula CrO.sub.2 Y.sub.2 wherein the Y's are the same or different and are radicals selected from the group consisting of halogen, --O--R--, --O--Ti--OR) 3 , ##STR10## and --O--M--R 3 , and wherein R is a C 1 to C 14 hydrocarbyl group and M is selected from the group consisting of Si and Sn.
Claim 2
Dependent Claim
120 words
In a process for polymerizing a monomer charge comprising at least a major amount of ethylene by contacting said charge with a catalyst comprising chromate ester deposited on a support comprising silica and treated with strong reducing agent, the improvement which comprises treating said catalyst, prior to said treatment with said reducing agent, with phenol compound, said chromate ester containing one or more groups of the formula CrO.sub.2 Y.sub.2 wherein the Y's are the same or different and are radicals selected from the group consisting of halogen, --O--R--, --O--Ti--OR) 3 , ##STR10## and --O--M--R 3 , and wherein R is a C 1 to C 14 hydrocarbyl group and M is selected from the group consisting of Si and Sn.
Claim 3
Dependent Claim
42 words
A process as in claim 1 in which said phenol compound has one of the structures ##STR11## wherein the R's are the same or different and are selected from the group consisting of H, C 1 to C 14 hydrocarbyl and halogen.
Claim 4
Dependent Claim
14 words
A process as in claim 2 in which said chromate ester comprises chromyl chloride.
Claim 5
Dependent Claim
26 words
A process as in claim 3 in which said phenol compound is selected from the group consisting of phenol, p-bromophenol, p-cresol, p-tertiary butyl phenol, and β-naphthol.
Claim 6
Dependent Claim
13 words
A process as in claim 3 in which said phenol compound comprises phenol.
Claim 7
Dependent Claim
15 words
A process as in claim 2 in which said chromate ester comprises silyl chromate ester.
Claim 8
Dependent Claim
16 words
A process as in claim 6 in which said chromate ester comprises bis(triphenyl silyl) chromate ester.
Claim 9
Dependent Claim
26 words
A process as in claim 7 in which said phenol compound is selected from the group consisting of phenol, p-bromophenol, p-cresol, p-tertiary butyl phenol and β-naphthol.
Claim 10
Dependent Claim
13 words
A process as in claim 6 in which said phenol compound comprises phenol.
Claim 11
Dependent Claim
13 words
A process as in claim 6 in which said phenol compound comprises p-bromophenol.
Claim 12
Dependent Claim
13 words
A process as in claim 6 in which said phenol compound comprises p-cresol.
Claim 13
Dependent Claim
15 words
A process as in claim 6 in which said phenol compound comprises p-tertiary butyl phenol.
Claim 14
Dependent Claim
13 words
A process as in claim 6 in which said phenol compound comprises β-naphthol.
Claim 15
Dependent Claim
14 words
A process as in claim 1 in which said monomer charge consists of ethylene.
Claim 16
Dependent Claim
20 words
A process as in claim 1 in which said monomer charge comprises ethylene and at least one other alpha olefin.
Claim 17
Dependent Claim
15 words
A process as in claim 15 in which said monomer charge comprises ethylene and propylene.
Claim 18
Dependent Claim
51 words
A process as in claim 1 in which said catalyst is prepared from, in parts by weight, per 100 parts by weight of said support, of 0.001 to 10 parts of said chromate ester, 0.001 to 5 parts of said phenol compound, and 0.01 to 20 parts of said reducing agent.
Claim 19
Dependent Claim
88 words
An ethylene polymerization catalyst which comprises chromate ester deposited on a support comprising silica and sequentially treated with phenol compound and strong reducing agent, said chromate ester containing one or more groups of the formula CrO.sub.2 Y.sub.2 wherein the Y's are the same or different and are radicals selected from the group consisting of halogen, --O--R, --O--Ti--OR) 3 , ##STR12## and --O--M--R) 3 , and wherein R is a C 1 to C 14 hydrocarbyl grop and M is selected from the group consisting of Si and Sn.
Claim 20
Dependent Claim
88 words
An ethylene polymerization catalyst which comprises chromate ester deposited on a support comprising silica and sequentially treated with phenol compound and strong reducing agent, said chromate ester containing one or more groups of the formula CrO.sub.2 Y.sub.2 wherein the Y's are the same or different and are radicals selected from the group consisting of halogen, --O--R, --O--Ti--OR) 3 , ##STR12## and --O--M--R) 3 , and wherein R is a C 1 to C 14 hydrocarbyl grop and M is selected from the group consisting of Si and Sn.
Claim 21
Dependent Claim
42 words
A catalyst as in claim 18 in which said phenol compound has one of the structures ##STR13## wherein the R's are the same or different and are selected from the group consisting of H, C 1 to C 14 hydrocarbyl and halogen.
Claim 22
Dependent Claim
14 words
A catalyst as in claim 19 in which said chromate ester comprises chromyl chloride.
Claim 23
Dependent Claim
26 words
A catalyst as in claim 20 in which said phenol compound is selected from the group consisting of phenol, p-bromophenol, p-cresol, p-tertiary butyl phenol and β-naphthol.
Claim 24
Dependent Claim
13 words
A catalyst as in claim 20 in which said phenol compound comprises phenol.
Claim 25
Dependent Claim
15 words
A catalyst as in claim 19 in which said chromate ester comprises silyl chromate ester.
Claim 26
Dependent Claim
14 words
A catalyst as in claim 23 in which said chromate ester comprises bis(triphenyl silyl)chromate.
Claim 27
Dependent Claim
26 words
A catalyst as in claim 24 in which said phenol compound is selected from the group consisting of phenol, p-bromophenol, p-cresol, p-tertiary butyl phenol and β-naphthol.
Claim 28
Dependent Claim
13 words
A catalyst as in claim 23 in which said phenol compound comprises phenol.
Claim 29
Dependent Claim
13 words
A catalyst as in claim 23 in which said phenol compound comprises p-bromophenol.
Claim 30
Dependent Claim
13 words
A catalyst as in claim 23 in which said phenol compound comprises p-cresol.
Claim 31
Dependent Claim
15 words
A catalyst as in claim 23 in which said phenol compound comprises p-tertiary butyl phenol.
Claim 32
Dependent Claim
13 words
A catalyst as in claim 23 in which said phenol compound comprises β-naphthol.
Claim 33
Dependent Claim
54 words
A catalyst as in claim 18 which is prepared from, in parts by weight, per 100 parts by weight of said support, of 0.001 to 10 parts by weight of said chromate ester, 0.001 to 5 parts by weight of said phenol compound, and 0.01 to 20 parts by weight of said reducing agent.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-12-26 | 1981-06-27 | 1981-12-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-12-26 | 1985-06-27 | 1985-12-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-12-26 | 1989-06-27 | 1989-12-27 | $7700.00 | Window Closed / Lapsed |