Patent US4593009A successfully refreshed from Google Patents.
US4593009A
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US
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Catalyst composition for polymerizing alpha-olefins
Assignee: Mobil Oil AS
•
Filing: 1984-04-04
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Granted: 1986-06-03
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Expires: 2004-04-04
Abstract
Abstract A catalyst composition for polymerizing alpha-olefins is prepared by treating a carrier containing OH groups with an organomagnesium composition and contacting the thus-formed magnesium-containing carrier with a solution of at least one tetravalent vanadium compound. Alternatively, the solution may also contain at least one tetravalent titanium compound in addition to the vanadium compound, thereby producing catalysts containing both, vanadium and titanium. Also disclosed is a process for polymerizing alpha-olefins in the presence of the catalysts of the invention.
Inventors
- 👤 Thomas E. Nowlin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 22:02
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 61
Claim 1
Independent Claim
205 words
A process for preparing a supported catalyst composition for use in alpha-olefin polymerization reactions which comprises the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid, said liquid containing at least one organomagnesium composition having the empirical formula R.sub.n MgR'.sub.(2-n) (I) where R and R' are the same or different and they are C 1 -C 12 hydrocarbyl groups, provided that R' may also be halogen, and n is 0, 1 or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of the OH groups on said carrier; (ii) removing said liquid from step (i) to obtain a magnesium-containing carrier in the form of a dry, free-flowing powder, said dry, free-flowing powder containing a stoichiometric molar excess of the magnesium-containing compounds with respect to the OH groups originally present on said carrier; and (iii) contacting said powder of step (ii) with a solution comprising a liquid medium and at least one tetravalent vanadium compound, said vanadium compound being soluble in said liquid medium, and said magnesium-containing carrier being substantially insoluble in said liquid medium, whereby a compound of vanadium which is insoluble in said liquid medium becomes incorporated onto said carrier.
Claim 2
Dependent Claim
205 words
A process for preparing a supported catalyst composition for use in alpha-olefin polymerization reactions which comprises the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid, said liquid containing at least one organomagnesium composition having the empirical formula R.sub.n MgR'.sub.(2-n) (I) where R and R' are the same or different and they are C 1 -C 12 hydrocarbyl groups, provided that R' may also be halogen, and n is 0, 1 or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of the OH groups on said carrier; (ii) removing said liquid from step (i) to obtain a magnesium-containing carrier in the form of a dry, free-flowing powder, said dry, free-flowing powder containing a stoichiometric molar excess of the magnesium-containing compounds with respect to the OH groups originally present on said carrier; and (iii) contacting said powder of step (ii) with a solution comprising a liquid medium and at least one tetravalent vanadium compound, said vanadium compound being soluble in said liquid medium, and said magnesium-containing carrier being substantially insoluble in said liquid medium, whereby a compound of vanadium which is insoluble in said liquid medium becomes incorporated onto said carrier.
Claim 3
Dependent Claim
29 words
A process of claim 1 wherein the number of moles of said vanadium compound present in said solution of step (iii) is in excess of the stoichiometric amount thereof.
Claim 4
Dependent Claim
33 words
A process of claim 2 wherein the solid, porous carrier, prior to contact thereof with the liquid in step (i), is heated at a temperature of about 100° C. to about 1000° C.
Claim 5
Dependent Claim
23 words
A process of claim 3 wherein the solid, porous carrier is heated at a temperature of about 150° C. to about 850° C.
Claim 6
Dependent Claim
17 words
A process of claim 4 wherein the carrier is heated at a temperature of about 800° C.
Claim 7
Dependent Claim
28 words
A process of claim 5 wherein the heating is continued until the carrier contains about 0.5 to about 5 mmoles of the OH groups per gram of carrier.
Claim 8
Dependent Claim
28 words
A process of claim 6 wherein the heating is continued until the carrier contains about 0.3 to about 0.7 mmoles of the OH groups per gram of carrier.
Claim 9
Dependent Claim
37 words
A process of claim 7 wherein the carrier is silica having a surface hydroxyl group concentration of about 0.5 mmoles/gr, a surface area of 300 m 2 /gram and a pore volume of 1.65 m 3 /gram.
Claim 10
Dependent Claim
19 words
A process of claim 8 wherein R is a C 1 -C 4 alkane group and R' is halogen.
Claim 11
Dependent Claim
11 words
A process of claim 9 wherein R' is bromine or chlorine.
Claim 12
Dependent Claim
12 words
A process of claim 10 wherein the organomagnesium composition is ethylmagnesium chloride.
Claim 13
Dependent Claim
13 words
A process of claim 11 wherein the liquid containing ethylmagnesium chloride is tetrahydrofuran.
Claim 14
Dependent Claim
15 words
A process of claim 12 wherein said liquid is removed in step (ii) by evaporation.
Claim 15
Dependent Claim
31 words
A process of claim 13 wherein the molar ratio of the oganomagnesium composition to the number of the moles of OH groups on the carrier is about 1.1 to about 3.5.
Claim 16
Dependent Claim
25 words
A process of claim 14 wherein the molar ratio of the tetravalent vanadium compound to the organomagnesium composition is from about 1 to about 10.
Claim 17
Dependent Claim
25 words
A process of claim 15 wherein the molar ratio of the tetravalent vanadium compound to the organomagnesium composition is from about 3 to about 6.
Claim 18
Dependent Claim
14 words
A process of claim 16 wherein the tetravalent vanadium compound is a vanadium halide.
Claim 19
Dependent Claim
16 words
A process of claim 17 wherein the tetravalent vanadium compound is vanadium tetrachloride or vanadium tetrabromide.
Claim 20
Dependent Claim
13 words
A process of claim 18 wherein the tetravalent vanadium compound is vanadium tetrachloride.
Claim 21
Dependent Claim
25 words
A process of claim 19 wherein the solution used in step (iii) to contact the powder of step (ii) further comprises a tetravalent titanium compound.
Claim 22
Dependent Claim
33 words
A process of claim 20 wherein the molar ratio of the sum of the tetravalent vanadium compound and the tetravalent titanium compound to the organomagnesium composition is from about 1 to about 10.
Claim 23
Dependent Claim
33 words
A process of claim 21 wherein the molar ratio of the sum of the tetravalent vanadium compound and the tetravalent titanium compound to the organomagnesium composition is from about 3 to about 6.
Claim 24
Dependent Claim
14 words
A process of claim 22 wherein the tetravalent titanium compound is a titanium halide.
Claim 25
Dependent Claim
16 words
A process of claim 23 wherein the tetravalent titanium compound is titanium tetrachloride or titanium tetrabromide.
Claim 26
Dependent Claim
13 words
A process of claim 24 wherein the tetravalent titanium compound is titanium tetrachloride.
Claim 27
Dependent Claim
203 words
A catalyst composition for use in alpha-olefin polymerization reactions prepared in a process comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid, said liquid containing at least one organomagnesium composition having the empirical formula R.sub.n MgR'.sub.(2-n) (I) where R and R' are the same or different and they are C 1 -C 12 hydrocarbyl groups, provided that R' may also be halogen, and n is 0, 1 or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of the OH groups on said carrier; (ii) removing said liquid from step (i) to obtain a magnesium-containing carrier in the form of a dry, free-flowing powder, said dry, free-flowing powder containing a stoichiometric molar excess of the magnesium-containing compounds with respect to the OH groups originally present on said carrier; and (iii) contacting said powder of step (ii) with a solution comprising a liquid medium and at least one tetravalent vanadium compound, said vanadium compound being soluble in said liquid medium, and said magnesium-containing carrier being substantially insoluble in said liquid medium, whereby a compound of vanadium which is insoluble in said liquid medium becomes incorporated onto said carrier.
Claim 28
Dependent Claim
203 words
A catalyst composition for use in alpha-olefin polymerization reactions prepared in a process comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid, said liquid containing at least one organomagnesium composition having the empirical formula R.sub.n MgR'.sub.(2-n) (I) where R and R' are the same or different and they are C 1 -C 12 hydrocarbyl groups, provided that R' may also be halogen, and n is 0, 1 or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of the OH groups on said carrier; (ii) removing said liquid from step (i) to obtain a magnesium-containing carrier in the form of a dry, free-flowing powder, said dry, free-flowing powder containing a stoichiometric molar excess of the magnesium-containing compounds with respect to the OH groups originally present on said carrier; and (iii) contacting said powder of step (ii) with a solution comprising a liquid medium and at least one tetravalent vanadium compound, said vanadium compound being soluble in said liquid medium, and said magnesium-containing carrier being substantially insoluble in said liquid medium, whereby a compound of vanadium which is insoluble in said liquid medium becomes incorporated onto said carrier.
Claim 29
Dependent Claim
30 words
A catalyst composition of claim 26 wherein the number of moles of said vanadium compound present in said solution of step (iii) is in excess of the stoichiometric amount thereof.
Claim 30
Dependent Claim
34 words
A catalyst composition of claim 27 wherein the solid, porous carrier, prior to contact thereof with the liquid in step (i), is heated at a temperature of about 100° C. to about 1000° C.
Claim 31
Dependent Claim
24 words
A catalyst composition of claim 28 wherein the solid, porous carrier is heated at a temperature of about 150° C. to about 850° C.
Claim 32
Dependent Claim
18 words
A catalyst composition of claim 29 wherein the carrier is heated at a temperature of about 800° C.
Claim 33
Dependent Claim
29 words
A catalyst composition of claim 30 wherein the heating is continued until the carrier contains about 0.5 to about 5 mmoles of the OH groups per gram of carrier.
Claim 34
Dependent Claim
28 words
A catalyst composition of claim 31 wherein the heating is continued until the carrier contains about 0.3 to about 0.7 mmoles of OH groups per gram of carrier.
Claim 35
Dependent Claim
38 words
A catalyst composition of claim 32 wherein the carrier is silica having a surface hydroxyl group concentration of about 0.5 mmols/gr, a surface area of 300 m 2 /gram and a pore volume of 1.65 m 3 /gram.
Claim 36
Dependent Claim
20 words
A catalyst composition of claim 33 wherein R is a C 1 -C 4 alkane group and R' is halogen.
Claim 37
Dependent Claim
12 words
A catalyst composition of claim 34 wherein R' is bromine or chlorine.
Claim 38
Dependent Claim
13 words
A catalyst composition of claim 35 wherein the organomagnesium composition is ethylmagnesium chloride.
Claim 39
Dependent Claim
14 words
A catalyst composition of claim 36 wherein the liquid containing ethylmagnesium chloride is tetrahydrofuran.
Claim 40
Dependent Claim
16 words
A catalyst composition of claim 37 wherein said liquid is removed in step (ii) by evaporation.
Claim 41
Dependent Claim
32 words
A catalyst composition of claim 38 wherein the molar ratio of the organomagnesium composition to the number of moles of the OH groups on the carrier is about 1.1 to about 3.5.
Claim 42
Dependent Claim
26 words
A catalyst composition of claim 39 wherein the molar ratio of the tetravalent vanadium compound to the organomagnesium composition is from about 1 to about 10.
Claim 43
Dependent Claim
26 words
A catalyst composition of claim 40 wherein the molar ratio of the tetravalent vanadium compound to the organomagnesium composition is from about 3 to about 6.
Claim 44
Dependent Claim
15 words
A catalyst composition of claim 41 wherein the tetravalent vanadium compound is a vanadium halide.
Claim 45
Dependent Claim
17 words
A catalyst composition of claim 42 wherein the tetravalent vanadium compound is vanadium tetrachloride or vanadium tetrabromide.
Claim 46
Dependent Claim
14 words
A catalyst composition of claim 43 wherein the tetravalent vanadium compound is vanadium tetrachloride.
Claim 47
Dependent Claim
26 words
A catalyst composition of claim 44 wherein the solution used in step (iii) to contact the power of step (ii) further comprises a tetravalent titanium compound.
Claim 48
Dependent Claim
34 words
A catalyst composition of claim 45 wherein the molar ratio of the sum of the tetravalent vanadium compound and the tetravalent titanium compound to the organomagnesium composition is from about 1 to about 10.
Claim 49
Dependent Claim
34 words
A catalyst composition of claim 46 wherein the molar ratio of the sum of the tetravalent vanadium compound and the tetravalent titanium compound to the organomagnesium composition is from about 3 to about 6.
Claim 50
Dependent Claim
15 words
A catalyst composition of claim 47 wherein the tetravalent titanium compound is a titanium halide.
Claim 51
Dependent Claim
17 words
A catalyst composition of claim 48 wherein the tetravalent titanium compound is titanium tetrachloride or titanium tetrabromide.
Claim 52
Dependent Claim
14 words
A catalyst composition of claim 49 wherein the tetravalent titanium compound is titanium tetrachloride.
Claim 53
Dependent Claim
196 words
A catalyst composition for use in alpha-olefin polymerization reactions prepared in a process comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid, said liquid containing at least one organomagnesium composition having the empirical formula R.sub.n MgR'.sub.(2-n) (I) where R and R' are the same or different and they are C 1 -C 12 hydrocarbyl groups, provided that R' may also be halogen, and n is 0, 1 or 2; (ii) removing said liquid from step (i) to obtain a magnesium-containing carrier in the form of a dry, free-flowing powder, said dry, free-flowing powder containing a stoichiometric molar excess of the magnesium-containing compounds with respect to the OH groups originally present on said carrier; and (iii) contacting said powder of step (ii) with a solution comprising a liquid medium and at least one tetravalent vanadium compound, the number of moles of said vanadium compound being in excess of the stoichiometric amount thereof, said vanadium compound being soluble in said liquid medium, and said magnesium-containing carrier being substantially insoluble in said liquid medium, whereby a compound of vanadium which is insoluble in said liquid medium becomes incorporated onto said carrier.
Claim 54
Dependent Claim
196 words
A catalyst composition for use in alpha-olefin polymerization reactions prepared in a process comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid, said liquid containing at least one organomagnesium composition having the empirical formula R.sub.n MgR'.sub.(2-n) (I) where R and R' are the same or different and they are C 1 -C 12 hydrocarbyl groups, provided that R' may also be halogen, and n is 0, 1 or 2; (ii) removing said liquid from step (i) to obtain a magnesium-containing carrier in the form of a dry, free-flowing powder, said dry, free-flowing powder containing a stoichiometric molar excess of the magnesium-containing compounds with respect to the OH groups originally present on said carrier; and (iii) contacting said powder of step (ii) with a solution comprising a liquid medium and at least one tetravalent vanadium compound, the number of moles of said vanadium compound being in excess of the stoichiometric amount thereof, said vanadium compound being soluble in said liquid medium, and said magnesium-containing carrier being substantially insoluble in said liquid medium, whereby a compound of vanadium which is insoluble in said liquid medium becomes incorporated onto said carrier.
Claim 55
Dependent Claim
38 words
A catalyst composition of claim 51 wherein the number of moles of said organomagnesium composition contained in said liquid used in step (i) is in excess of the number of moles of the OH groups on said carrier.
Claim 56
Dependent Claim
31 words
A process of claim 20 wherein the molar ratio of vanadium to titanium in the solution used in step (iii) to contact the powder of step (ii) is 0.01 to 99.
Claim 57
Dependent Claim
31 words
A process of claim 53 wherein the molar ratio of vanadium to titanium in the solution used in step (iii) to contact the powder of step (ii) is 0.1 to 10.
Claim 58
Dependent Claim
31 words
A process of claim 54 wherein the molar ratio of vanadium to titanium in the solution used in step (iii) to contact the powder of step (ii) is 0.2 to 5.0.
Claim 59
Dependent Claim
32 words
A catalyst composition of claim 45 wherein the molar ratio of vanadium to titanium in the solution used in step (iii) to contact the powder of step (ii) is 0.01 to 99.
Claim 60
Dependent Claim
32 words
A catalyst composition of claim 56 wherein the molar ratio of vanadium to titanium in the solution used in step (iii) to contact the powder of step (ii) is 0.1 to 10.
Claim 61
Dependent Claim
32 words
A catalyst composition of claim 57 wherein the molar ratio of vanadium to titanium in the solution used in step (iii) to contact the powder of step (ii) is 0.2 to 5.0.
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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) | 1989-06-02 | 1989-12-02 | 1990-06-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1993-06-02 | 1993-12-02 | 1994-06-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1997-06-02 | 1997-12-02 | 1998-06-03 | $7700.00 | Window Closed / Lapsed |