Patent US5093443A successfully refreshed from Google Patents.
US5093443A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Alpha-olefins polymerization with chlorinated alcohol-containing catalyst composition
Assignee: Mobil Oil AS
•
Filing: 1990-06-20
•
Granted: 1992-03-03
•
Expires: 2010-06-20
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 polymirazation 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 01:26
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
211 words
In a process of copolymerizing ethylene with at least one C 3 -C 10 alpha-olefin to produce a copolymer, comprising conducting the polymerization in the presence of a catalyst composition prepared by a process comprising 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 Mg R'.sub.n (I) where R and R' are the same or different C 4 -C 10 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg; (iii) contacting the slurry of step (ii) with at least one transition metal compound soluble in the non-polar solvent; and combining the product of step (iii) with a catalyst activator, the improvement consisting essentially of (ii) contacting the slurry of step (i) with at least one compound of the formula R"--OH (II) where R" is a C 2 -C 12 chlorinated alkyl group; wherein R"--OH is free of chlorine atoms on the alpha carbon atom and has at least one of its hydrogens on a (beta) or higher carbon atom replaced by chlorine; (iv) combining the product of step (iii) with trimethylaluminum or triethyl aluminum, and (v) increasing alpha-olefin incorporation into the copolymer.
Claim 2
Dependent Claim
211 words
In a process of copolymerizing ethylene with at least one C 3 -C 10 alpha-olefin to produce a copolymer, comprising conducting the polymerization in the presence of a catalyst composition prepared by a process comprising 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 Mg R'.sub.n (I) where R and R' are the same or different C 4 -C 10 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg; (iii) contacting the slurry of step (ii) with at least one transition metal compound soluble in the non-polar solvent; and combining the product of step (iii) with a catalyst activator, the improvement consisting essentially of (ii) contacting the slurry of step (i) with at least one compound of the formula R"--OH (II) where R" is a C 2 -C 12 chlorinated alkyl group; wherein R"--OH is free of chlorine atoms on the alpha carbon atom and has at least one of its hydrogens on a (beta) or higher carbon atom replaced by chlorine; (iv) combining the product of step (iii) with trimethylaluminum or triethyl aluminum, and (v) increasing alpha-olefin incorporation into the copolymer.
Claim 3
Dependent Claim
31 words
The process of claim 1, wherein the R"--OH is selected from the group consisting of 2-chloroethanol, 2,2-dichloroethanol, 2,2,2-trichloroethanol, 2-chloro-propanol, 2,2-dichloro-propanol, 2,2,3-trichloro-propanol, 2,2,3,3-tetrachloro-propanol, 2-chloro-n-butanol, 2,3-dichloro-n-butanol, 2,3,4-trichloro-n-butanol, 2,3,4,4-tetrachloro-n-butanol, and 2,2,3,3,4,4-hexachloro-n-butanol and admixtures thereof.
Claim 4
Dependent Claim
16 words
A process of claim 1 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 process of claim 1, 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 24
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 25
Dependent Claim
36 words
A process of claim 23 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 26
Dependent Claim
36 words
A process of claim 24 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 27
Dependent Claim
43 words
A process of claim 1 wherein the C 3 -C 10 alpha-olefin is propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, a mixture of 1-butene and 1-hexene, a mixture of 1-butene and 1-hexene, a mixture of propylene and 1-hexene or a mixture of propylene and 1-butene.
Claim 28
Dependent Claim
16 words
A process of claim 26 wherein the C 3 -C 10 alpha-olefin is 1-butene or 1-hexene.
Claim 29
Dependent Claim
11 words
A process of claim 27 wherein the aluminum trialkyl is trimethylaluminum.
References Cited (Backward Citations)
US4063009A
Cited
US4076698B1
Cited
US4076698A
Cited
US3787384A
Cited
US4148754A
Cited
US4173547A
Cited
US4302566A
Cited
US4378304A
Cited
US4458058A
Cited
US4481301A
Cited
US4727049A
Cited
US4558025A
Cited
US4558024A
Cited
US4579835A
Cited
US4732882A
Cited
US4833111A
Cited
US4849389A
Cited
US4954470A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1995-03-03 | 1995-09-02 | 1996-03-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1999-03-03 | 1999-09-02 | 2000-03-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2003-03-03 | 2003-09-02 | 2004-03-03 | $7700.00 | Window Closed / Lapsed |