US4954470A
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US
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Chlorinated alcohol-containing catalyst composition for polymerizing alpha-olefins
Assignee: Mobil Oil AS
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Filing: 1988-12-21
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Granted: 1990-09-04
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Expires: 2008-12-21
Abstract
Abstract A supported alpha-olefin polymerization catalyst composition is synthesized by reacting (1) a slurry of a solid catalyst carrier in a non-polar solvent, e.g., hexane, with a dialkyl organomagnesium composition; (2) contacting the slurry of step (1) with a chlorinated alcohol; (3) contacting the slurry of step (2) with at least one transition metal compound; (4) removing the non-polar solvent to obtain a dry-flowing powder; and, (5) activating the powder with an activator. The resulting catalyst composition has high polymerization activity in the polymerization of C2-C10 alpha-olefins and exhibits very good higher (C3-C10) alpha-olefin incorporation properties in the copolymerization of ethylene with the higher alpha-olefins.
Inventors
- 👤 Thomas E. Nowlin
- 👤 Kenneth G. Schurzky
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 19:59
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 52
Claim 1
Independent Claim
135 words
A process for preparing a supported alpha-olefin polymerization catalyst composition which comprises the steps of: (i) contacting a slurry of a solid, porous carrier and a non-polar solvent with at least one organomagnesium composition having the formula R.sub.m MgR.sub.n ' (I) where R and R' are the same or different C 4 -C 12 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg; (ii) contacting the slurry of step (i) with at least one chlorinated alcohol of the formula R"--OH (II) where R" is a C 2 -C 10 chlorinated alkyl group; (iii) contacting the slurry of step (ii) with at least one transition metal compound soluble in the non-polar solvent; and (iv) combining the product of step (iii) with a catalyst activator.
Claim 2
Dependent Claim
135 words
A process for preparing a supported alpha-olefin polymerization catalyst composition which comprises the steps of: (i) contacting a slurry of a solid, porous carrier and a non-polar solvent with at least one organomagnesium composition having the formula R.sub.m MgR.sub.n ' (I) where R and R' are the same or different C 4 -C 12 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg; (ii) contacting the slurry of step (i) with at least one chlorinated alcohol of the formula R"--OH (II) where R" is a C 2 -C 10 chlorinated alkyl group; (iii) contacting the slurry of step (ii) with at least one transition metal compound soluble in the non-polar solvent; and (iv) combining the product of step (iii) with a catalyst activator.
Claim 3
Dependent Claim
16 words
A process of claim 1 wherein R and R' are C 4 -C 10 alkyl groups.
Claim 4
Dependent Claim
16 words
A process of claim 2 wherein R and R' are C 4 -C 8 alkyl groups.
Claim 5
Dependent Claim
20 words
A process of claim 3 wherein R and R' are each butyl groups, m is 1 and n is 1.
Claim 6
Dependent Claim
18 words
A process of claim 4 wherein the non-polar solvent is a hydrocarbon which is liquid at ambient conditions.
Claim 7
Dependent Claim
16 words
A process of claim 5 wherein R" is a C 2 -C 8 chlorinated alkyl group.
Claim 8
Dependent Claim
15 words
A process of claim 6 wherein R" is a chlorinated ethyl, propyl or butyl group.
Claim 9
Dependent Claim
11 words
A process of claim 7 wherein R" is a 2,2,2-trichloroethyl group.
Claim 10
Dependent Claim
17 words
A process of claim 8 wherein the transition metal compound is a compound of titanium or vanadium.
Claim 11
Dependent Claim
13 words
A process of claim 9 wherein the transition metal compound is titanium halide.
Claim 12
Dependent Claim
12 words
A process of claim 10 wherein the titanium halide is titanium tetrahalide.
Claim 13
Dependent Claim
13 words
A process of claim 11 wherein the titanium tetrahalide is TiCl 4 .
Claim 14
Dependent Claim
33 words
A process of claim 12 wherein the amount of the TiCl 4 present in said step (iii) is such that the molar ratio of Mg to Ti is about 1 to about 4.
Claim 15
Dependent Claim
33 words
A process of claim 13 wherein the amount of the TiCl 4 present in said step (iii) is such that the molar ratio of Mg to Ti is about 1.5 to about 3.5.
Claim 16
Dependent Claim
13 words
A process of claim 14 wherein the solid, porous carrier contains OH groups.
Claim 17
Dependent Claim
31 words
A process of claim 15 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio of Mg:OH is about 1:1 to about 3:1.
Claim 18
Dependent Claim
31 words
A process of claim 16 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio of Mg:OH is about 1.25:1 to about 3:1.
Claim 19
Dependent Claim
31 words
A process of claim 17 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio of Mg:OH is about 2.3:1 to about 2.6:1.
Claim 20
Dependent Claim
36 words
A process of claim 18 wherein the solid, porous carrier is silica which, prior to contact thereof with the solvent in step (i), is heated at a temperature of about 100° C. to about 1000° C.
Claim 21
Dependent Claim
17 words
A process of claim 19 wherein the silica is heated at a temperature of about 600° C.
Claim 22
Dependent Claim
37 words
A process of claim 20 wherein the silica has, after the heating, surface hydroxyl group concentration of about 0.7 mmoles/gr, a surface area of 300 m 2 /gram and a pore volume of 1.65 m 3 /gram.
Claim 23
Dependent Claim
127 words
A supported alpha-olefin polymerization catalyst composition prepared by: (i) contacting a slurry of a solid, porous carrier and a non-polar solvent with at least one organomagnesium composition having the formula R.sub.m MgR.sub.n ' (I) where R and R' are the same or different C 4 -C 12 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg; (ii) contacting the slurry step (i) with at least one chlorinated compound of the formula R"--OH (II) where R" is a C 2 -C 10 chlorinated alkyl group; (iii) contacting the slurry of step (ii) with at least one transition metal compound soluble in the non-polar solvent; and (iv) combining the product of step (iii) with a catalyst activator.
Claim 24
Dependent Claim
127 words
A supported alpha-olefin polymerization catalyst composition prepared by: (i) contacting a slurry of a solid, porous carrier and a non-polar solvent with at least one organomagnesium composition having the formula R.sub.m MgR.sub.n ' (I) where R and R' are the same or different C 4 -C 12 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg; (ii) contacting the slurry step (i) with at least one chlorinated compound of the formula R"--OH (II) where R" is a C 2 -C 10 chlorinated alkyl group; (iii) contacting the slurry of step (ii) with at least one transition metal compound soluble in the non-polar solvent; and (iv) combining the product of step (iii) with a catalyst activator.
Claim 25
Dependent Claim
17 words
A catalyst composition of claim 22 wherein R and R' are C 4 -C 10 alkyl groups.
Claim 26
Dependent Claim
17 words
A catalyst composition of claim 23 wherein R and R' are C 4 -C 8 alkyl groups.
Claim 27
Dependent Claim
21 words
A catalyst composition of claim 24 wherein R and R' are each butyl groups, m is 1 and n is 1.
Claim 28
Dependent Claim
19 words
A catalyst composition of claim 25 wherein the non-polar solvent is a hydrocarbon which is liquid at ambient conditions.
Claim 29
Dependent Claim
17 words
A catalyst composition of claim 26 wherein R" is a C 2 `C 8 chlorinated alkyl group.
Claim 30
Dependent Claim
16 words
A catalyst composition of claim 27 wherein R" is a chlorinated ethyl, propyl or butyl group.
Claim 31
Dependent Claim
12 words
A catalyst composition of claim 28 wherein R" is a 2,2,2-trichloroethyl group.
Claim 32
Dependent Claim
18 words
A catalyst composition of claim 29 wherein the transition metal compound is a compound of titanium or vanadium.
Claim 33
Dependent Claim
14 words
A catalyst composition of claim 30 wherein the transition metal compound is titanium halide.
Claim 34
Dependent Claim
13 words
A catalyst composition of claim 31 wherein the titanium halide is titanium tetrahalide.
Claim 35
Dependent Claim
14 words
A catalyst composition of claim 32 wherein the titanium tetrahalide is TiCl 4 .
Claim 36
Dependent Claim
34 words
A catalyst composition of claim 33 wherein the amount of the TiCl 4 present in said step (iii) is such that the molar ratio of Mg to Ti is about 1 to about 4.
Claim 37
Dependent Claim
34 words
A catalyst composition of claim 34 wherein the amount of the TiCl 4 present in said step (iii) is such that the molar ratio of Mg to Ti is about 1.5 to about 3.5.
Claim 38
Dependent Claim
14 words
A catalyst composition of claim 35 wherein the solid, porous carrier contains OH groups.
Claim 39
Dependent Claim
32 words
A catalyst composition of claim 36 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio of Mg:OH is about 1:1 to about 3:1.
Claim 40
Dependent Claim
32 words
A catalyst composition of claim 37 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio of Mg:OH is about 1.25:1 to about 3:1.
Claim 41
Dependent Claim
32 words
A catalyst composition of claim 38 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio of Mg:OH is about 2.3:1 to about 2.6:1.
Claim 42
Dependent Claim
37 words
A catalyst composition of claim 39 wherein the solid, porous carrier is silica which, prior to contact thereof with the solvent in step (i), is heated at a temperature of about 100° C. to about 1000° C.
Claim 43
Dependent Claim
18 words
A catalyst composition of claim 40 wherein the silica is heated at a temperature of about 600° C.
Claim 44
Dependent Claim
38 words
A catalyst composition of claim 41 wherein the silica has, after the heating, surface hydroxyl group concentration of about 0.7 mmoles/gr, a surface area of 300 m 2 /gram and a pore volume of 1.65 m 3 /gram.
Claim 45
Dependent Claim
126 words
A process of claim 1 wherein said step (i) only such an amount of the organomagnesium composition is used which will be deposited onto the carrier; in said step (ii) only such an amount of the compound of the formula (II) is used which is sufficient to convert substantially all of the magnesium alkyl groups on the carrier to magnesium alkoxy or magnesium chloride groups, so that substantially no excess of the formula (II) compound is present in the non-polar solvent after substantially all of the magnesium groups are converted to the magnesium alkoxy or magnesium chloride groups; and in said step (iii) such an amount of the transition metal compound is used which is not greater than that which can be deposited on the carrier.
Claim 46
Dependent Claim
35 words
A process of claim 9 wherein the amount of the transition metal compound present in step (iii) is such that the molar ratio of Mg to the transition metal is about 1 to about 4.
Claim 47
Dependent Claim
36 words
A process of claim 44 wherein the amount of the transition metal compound present in said step (iii) is such that the molar ratio of Mg to the transition metal is about 1.5 to about 3.5.
Claim 48
Dependent Claim
36 words
A process of claim 45 wherein the amount of the transition metal compound present in said step (iii) is such that the molar ratio of Mg to the transition metal is about 1.65 to about 3.0.
Claim 49
Dependent Claim
128 words
A catalyst composition of claim 22 wherein in said step (i) only such an amount of the organomagnesium composition is used which will be deposited onto the carrier; in said step (ii) only such an amount of the compound of the formula (II) is used which is sufficient to convert substantially all of the magnesium alkyl groups on the carrier to magnesium alkoxy or magnesium chloride groups, so that substantially no excess of the formula (II) compound is present in the non-polar solvent after substantially all of the magnesium groups are converted to the magnesium alkoxy or magnesium chloride groups; and in said step (iii) such an amount of the transition metal compound is used which is not greater than that which can be deposited on the carrier.
Claim 50
Dependent Claim
37 words
A catalyst composition of claim 30 wherein the amount of the transition metal compound present in said step (iii) is such that the molar ratio of Mg to the transition metal is about 1 to about 4.
Claim 51
Dependent Claim
37 words
A catalyst composition of claim 48 wherein the amount of the transition metal compound present in said step (iii) is such that the molar ratio of Mg to the transition metal is about 1.5 to about 3.5.
Claim 52
Dependent Claim
37 words
A catalyst composition of claim 48 wherein the amount of the transition metal compound present in said step (iii) is such that the molar ratio of Mg to the transition metal is about 1.65 to about 3.0.
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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) | 1993-09-03 | 1994-03-05 | 1994-09-04 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-09-03 | 1998-03-05 | 1998-09-04 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-09-03 | 2002-03-05 | 2002-09-04 | $7700.00 | Window Closed / Lapsed |