US4154701A
Expired / Lapsed
US
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Olefin polymerization catalyst
Assignee: BP Corp North America Inc
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Filing: 1978-05-01
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Granted: 1979-05-15
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Expires: 1998-05-01
Abstract
Abstract Olefin polymerization catalyst useful in preparation of polyolefins of broad molecular weight distribution comprising (a) a component prepared by reacting an organoaluminum compound with a mixture comprising a titanium compound, a zirconium compound, and a vanadium compound; and (b) an organoaluminum promoter. The (a) component can be further treated with a deactivating agent. The olefin polymerization performance of the (a) component can be varied depending on the choice of promoter and deactivating agent.
Inventors
- 👤 John L. Melquist
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 00:03
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
268 words
An olefin polymerization catalyst composition useful in the preparation of polyolefins having a broad and controllable molecular weight distribution comprising (a) an active component prepared by reacting a mixture comprising: (1) at least one titanium compound of the formula Ti(OR) m X 4-m wherein R is a hydrocarbon radical, X is halogen, and m runs from 0 to 4; (2) at least one zirconium compound of the formula Zr(OR) m X 4-m , wherein R, X, and m are as described in (1); and (3) at least one vanadium compound having a formula selected from the group consisting of VX n , VOX 2 , and VO(OR) p X 3-p wherein R and X are as described in (1), n is 3 or 4, and p runs from 0 to 3 with at least one organoaluminum compound of the formula AIR q X 3-q , wherein R and X are as defined in (1) and q runs from 1 to 3 and is selected such that said organoaluminum compound contains sufficient halogen to form an active catalyst component; said components being reacted in an amount such that the atomic ratio of titanium to zirconium ranges from about 0.1 to about 10, the atomic ratio of titanium to vanadium ranges from about 0.1 to about 10, and the atomic ratio of aluminum to the sum of the titanium, zirconium, and vanadium ranges from about 0.5 to about 40; and (b) an organoaluminum promoter of the formula AIR q X' 3-q wherein R is as described in (1), q runs from 1 to 3, and X' is hydrogen or halogen.
Claim 2
Dependent Claim
268 words
An olefin polymerization catalyst composition useful in the preparation of polyolefins having a broad and controllable molecular weight distribution comprising (a) an active component prepared by reacting a mixture comprising: (1) at least one titanium compound of the formula Ti(OR) m X 4-m wherein R is a hydrocarbon radical, X is halogen, and m runs from 0 to 4; (2) at least one zirconium compound of the formula Zr(OR) m X 4-m , wherein R, X, and m are as described in (1); and (3) at least one vanadium compound having a formula selected from the group consisting of VX n , VOX 2 , and VO(OR) p X 3-p wherein R and X are as described in (1), n is 3 or 4, and p runs from 0 to 3 with at least one organoaluminum compound of the formula AIR q X 3-q , wherein R and X are as defined in (1) and q runs from 1 to 3 and is selected such that said organoaluminum compound contains sufficient halogen to form an active catalyst component; said components being reacted in an amount such that the atomic ratio of titanium to zirconium ranges from about 0.1 to about 10, the atomic ratio of titanium to vanadium ranges from about 0.1 to about 10, and the atomic ratio of aluminum to the sum of the titanium, zirconium, and vanadium ranges from about 0.5 to about 40; and (b) an organoaluminum promoter of the formula AIR q X' 3-q wherein R is as described in (1), q runs from 1 to 3, and X' is hydrogen or halogen.
Claim 3
Dependent Claim
57 words
The composition of claim 1 wherein the titanium compound is a titanium tetraalkoxide, the zirconium compound is a zirconium tetraalkoxide, the vanadium compound is selected from the group consisting of vanadium trichloride, vanadium tetrachloride, vanadium oxydichloride, vanadium oxytrichloride, and vanadium oxytrialkoxide, the organoaluminum compound is an alkylaluminum dihalide, and the organoaluminum promoter is a lower alkyl trialkylaluminum.
Claim 4
Dependent Claim
32 words
The composition of claim 2 wherein the titanium tetraalkoxide is titanium tetrabutoxide, the zirconium tetraalkoxide is zirconium tetrabutoxide, the alkylaluminum dihalide is ethylaluminum dichloride, and the lower alkyl trialkylaluminum promoter is triethylaluminum.
Claim 5
Dependent Claim
12 words
The composition of claim 3 wherein the vanadium compound is vanadium trichloride.
Claim 6
Dependent Claim
12 words
The composition of claim 3 wherein the vanadium compound is vanadium oxytrichloride.
Claim 7
Dependent Claim
32 words
The composition of claim 2 wherein the titanium tetraalkoxide is titanium tetrabutoxide, the zirconium tetraalkoxide is zirconium tetrabutoxide, the alkylaluminum dihalide is ethylaluminum dichloride, and the lower alkyl trialkylaluminum promoter is triisobutylaluminum.
Claim 8
Dependent Claim
12 words
The composition of claim 6 wherein the vanadium compound is vanadium trichloride.
Claim 9
Dependent Claim
12 words
The composition of claim 6 wherein the vanadium compound is vanadium oxytrichloride.
Claim 10
Dependent Claim
29 words
The composition of claim 1 wherein the (a) component has been treated with a deactivating agent in an amount which is effective to temporarily and reversibly deactivate said component.
Claim 11
Dependent Claim
23 words
The composition of claim 9 wherein the deactivating agent is a material capable of improving the olefin polymerization performance of the catalyst composition.
Claim 12
Dependent Claim
14 words
The composition of claim 10 wherein the deactivating agent is a lower aliphatic alcohol.
Claim 13
Dependent Claim
57 words
The composition of claim 11 wherein the titanium compound is a titanium tetraalkoxide, the zirconium compound is a zirconium tetraalkoxide, the vanadium compound is selected from the group consisting of vanadium trichloride, vanadium tetrachloride, vanadium oxydichloride, vanadium oxytrichloride, and vanadium oxytrialkoxide, the organoaluminum compound is an alkylaluminum dihalide, and the organoaluminum promoter is a lower alkyl trialkylaluminum.
Claim 14
Dependent Claim
32 words
The composition of claim 12 wherein the titanium tetraalkoxide is titanium tetrabutoxide, the zirconium tetraalkoxide is zirconium tetrabutoxide, the alkylaluminum dihalide is ethylaluminum dichloride, and the lower alkyl trialkylaluminum promoter is triethylaluminum.
Claim 15
Dependent Claim
11 words
The composition of claim 13 wherein the deactivating agent is ethanol.
Claim 16
Dependent Claim
12 words
The composition of claim 14 wherein the vanadium compound is vanadium trichloride.
Claim 17
Dependent Claim
12 words
The composition of claim 14 wherein the vanadium compound is vanadium oxytrichloride.
Claim 18
Dependent Claim
32 words
The composition of claim 12 wherein the titanium tetraalkoxide is titanium tetrabutoxide, the zirconium tetraalkoxide is zirconium tetrabutoxide, the alkylaluminum dihalide is ethylaluminum dichloride, and the lower alkyl trialkylaluminum promoter is triisobutylaluminum.
Claim 19
Dependent Claim
11 words
The composition of claim 17 wherein the deactivating agent is ethanol.
Claim 20
Dependent Claim
12 words
The composition of claim 18 wherein the vanadium compound is vanadium trichloride.
Claim 21
Dependent Claim
12 words
The composition of claim 18 wherein the vanadium compound is vanadium oxytrichloride.
Claim 22
Dependent Claim
14 words
The composition of claim 10 wherein the deactivating agent is an anhydrous hydrogen halide.
Claim 23
Dependent Claim
57 words
The composition of claim 21 wherein the titanium compound is a titanium tetraalkoxide, the zirconium compound is a zirconium tetraalkoxide, the vanadium compound is selected from the group consisting of vanadium trichloride, vanadium tetrachloride, vanadium oxydichloride, vanadium oxytrichloride, and vanadium oxytrialkoxide, the organoaluminum compound is a alkylaluminum dihalide, and the organoaluminum promoter is a lower alkyl trialkylaluminum.
Claim 24
Dependent Claim
32 words
The composition of claim 22 wherein the titanium tetraalkoxide is titanium tetrabutoxide, the zirconium tetraalkoxide is zirconium tetrabutoxide, the alkylaluminum dihalide is ethylaluminum dichloride, and the lower alkyl trialkylaluminum promoter is triethylaluminum.
Claim 25
Dependent Claim
12 words
The composition of claim 23 wherein the hydrogen halide is hydrochloric acid.
Claim 26
Dependent Claim
12 words
The composition of claim 24 wherein the vanadium compound is vanadium trichloride.
Claim 27
Dependent Claim
12 words
The composition of claim 24 wherein the vanadium compound is vanadium oxytrichloride.
Claim 28
Dependent Claim
32 words
The composition of claim 21 wherein the titanium tetraalkoxide is titanium tetrabutoxide, the zirconium tetraalkoxide is zirconium tetrabutoxide, the alkylaluminum dihalide is ethylaluminum dichloride, and the lower alkyl trialkylaluminum promoter is triisobutylaluminum.
Claim 29
Dependent Claim
12 words
The composition of claim 27 wherein the hydrogen halide is hydrochloric acid.
Claim 30
Dependent Claim
12 words
The composition of claim 28 wherein the vanadium compound is vanadium trichloride.
Claim 31
Dependent Claim
12 words
The composition of claim 28 wherein the vanadium compound is vanadium oxytrichloride.
Claim 32
Dependent Claim
108 words
An olefin polymerization catalyst composition useful in the preparation of polyolefins having a broad and controllable molecular weight distribution comprising (a) an active component prepared by reacting ethylaluminum dichloride with a mixture comprising titanium tetrabutoxide, zirconium tetrabutoxide, and vanadium trichloride or vanadium oxytrichloride, wherein the atomic ratio of titanium to zirconium ranges from about 0.2 to about 2, the atomic ratio of titanium to vanadium ranges from about 0.2 to about 2, and the atomic ratio of aluminum to the sum of the titanium, zirconium, and vanadium ranges from about 2 to about 20; and (b) an organoaluminum promoter selected from the group consisting of triethylaluminum and triisobutylaluminum.
Claim 33
Dependent Claim
108 words
An olefin polymerization catalyst composition useful in the preparation of polyolefins having a broad and controllable molecular weight distribution comprising (a) an active component prepared by reacting ethylaluminum dichloride with a mixture comprising titanium tetrabutoxide, zirconium tetrabutoxide, and vanadium trichloride or vanadium oxytrichloride, wherein the atomic ratio of titanium to zirconium ranges from about 0.2 to about 2, the atomic ratio of titanium to vanadium ranges from about 0.2 to about 2, and the atomic ratio of aluminum to the sum of the titanium, zirconium, and vanadium ranges from about 2 to about 20; and (b) an organoaluminum promoter selected from the group consisting of triethylaluminum and triisobutylaluminum.
Claim 34
Dependent Claim
35 words
The composition of claim 31 wherein the (a) component has been treated with an effective amount, ranging up to about 10 mols per mol of metal-alkyl groups contained in (a), of a lower aliphatic alcohol.
Claim 35
Dependent Claim
33 words
The composition of claim 31 wherein the (a) component has been treated with an effective amount, ranging up to about 10 mols per mol of metal-alkyl contained in (a), of anhydrous hydrogen halide.
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) | 1982-05-14 | 1982-11-13 | 1983-05-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-05-14 | 1986-11-13 | 1987-05-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-05-14 | 1990-11-13 | 1991-05-15 | $7700.00 | Window Closed / Lapsed |