Patent US4277591A successfully refreshed from Google Patents.
US4277591A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for producing random copolymers of conjugated dienes and alpha-methylstyrene type monomers
Assignee: Phillips Petroleum Co
•
Filing: 1979-11-20
•
Granted: 1981-07-07
•
Expires: 1999-11-20
Abstract
Abstract Random copolymers of at least one conjugated diene and at least one alpha-methylstyrene type monomer are produced by solution polymerization in the presence of an organolithium initiator and at least one of selected sodium, potassium, rubidium, and cesium compounds.
Inventors
- 👤 Floyd E. Naylor
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 04:52
CPC Classifications
C; C08; C08F; C08F236/00; C08F236/02; C08F236/04; C08F236/10
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
203 words
A process for producing a random copolymer comprising contacting under solution polymerization conditions in a polymerization zone (1) a mixture of monomers comprising at least one conjugated diene having 4 to 12 carbon atoms per molecule and at least one alpha-methylstyrene type monomer having 9 to 24 carbon atoms and the formula ##STR4## wherein each A is individually selected from the group consisting of hydrogen or alkyl, cycloalkyl, or aryl radicals having 1 to 8 carbon atoms, (2) an organolithium initiator, and (3) an effective amount of at least one alkali metal organic compound selected from those having the formulas: ##STR5## wherein R' is selected from the group consisting of aliphatic, cycloaliphatic, and aromatic radicals, M is an alkali metal selected from the group consisting of sodium, potassium, rubidium, and cesium, R" is selected from the group consisting of aliphatic, cycloaliphatic, and aromatic radicals, Q is selected from the group consisting of ##STR6## radicals wherein R" is as defined before, x is 4 or 5, and y is 1, 2, or 3, R"' is selected from the group consisting of aliphatic, cycloaliphatic, and aromatic radicals, Y is selected from the group consisting of oxygen and sulfur and n is 1, 2, or 3.
Claim 2
Dependent Claim
203 words
A process for producing a random copolymer comprising contacting under solution polymerization conditions in a polymerization zone (1) a mixture of monomers comprising at least one conjugated diene having 4 to 12 carbon atoms per molecule and at least one alpha-methylstyrene type monomer having 9 to 24 carbon atoms and the formula ##STR4## wherein each A is individually selected from the group consisting of hydrogen or alkyl, cycloalkyl, or aryl radicals having 1 to 8 carbon atoms, (2) an organolithium initiator, and (3) an effective amount of at least one alkali metal organic compound selected from those having the formulas: ##STR5## wherein R' is selected from the group consisting of aliphatic, cycloaliphatic, and aromatic radicals, M is an alkali metal selected from the group consisting of sodium, potassium, rubidium, and cesium, R" is selected from the group consisting of aliphatic, cycloaliphatic, and aromatic radicals, Q is selected from the group consisting of ##STR6## radicals wherein R" is as defined before, x is 4 or 5, and y is 1, 2, or 3, R"' is selected from the group consisting of aliphatic, cycloaliphatic, and aromatic radicals, Y is selected from the group consisting of oxygen and sulfur and n is 1, 2, or 3.
Claim 3
Dependent Claim
25 words
A process according to claim 1 wherein said solution polymerization conditions include a temperature in the range of about -80° C. to about 150° C.
Claim 4
Dependent Claim
43 words
A process according to claim 2 wherein each said alkali metal organic compound is selected from those in which each R' contains 1 to 20 carbon atoms, each R" contains 1 to 6 carbon atoms, and R"' contains 4 to 20 carbon atoms.
Claim 5
Dependent Claim
12 words
A process according to claim 3 wherein said conjugated diene is 1,3-butadiene.
Claim 6
Dependent Claim
13 words
A process according to claim 3 wherein said alpha-methylstyrene type monomer is alpha-methylstyrene.
Claim 7
Dependent Claim
13 words
A process according to claim 3 wherein said monomers include 1,3-butadiene and alpha-methylstyrene.
Claim 8
Dependent Claim
24 words
A process according to claim 6 wherein the weight ratio of 1,3-butadiene to alpha-methylstyrene is in the range of about 40:60 to about 95:5.
Claim 9
Dependent Claim
27 words
A process according to claim 7 wherein each said alkali metal organic compound is selected from the group consisting of those having the formula R'(YM) n .
Claim 10
Dependent Claim
10 words
A process according to claim 8 wherein n is 1.
Claim 11
Dependent Claim
17 words
A process according to claim 9 wherein R' is a tertiary alkyl radical and Y is oxygen.
Claim 12
Dependent Claim
21 words
A process according to claim 10 wherein said alkali metal organic compound is selected from alkali metal salts of tert-amyl alcohol.
Claim 13
Dependent Claim
15 words
A process according to claim 1 wherein said alkali metal organic compound is potassium t-amyloxide.
Claim 14
Dependent Claim
35 words
A process according to claim 12 wherein tetrahydrofuran is included in the polymerization mixture in an amount in the range of 0.05 to 10 parts by weight per 100 parts by weight of total monomers.
Claim 15
Dependent Claim
36 words
A process according to claim 13 wherein said organolithium initiator is n-butyllithium and said n-butyllithium is employed in an amount in the range of about 0.11 to about 100 milliequivalents per hundred grams of total monomer.
Claim 16
Dependent Claim
18 words
A process according to claim 14 wherein the molar ratio of potassium to lithium is greater than 1:1.
Claim 17
Dependent Claim
24 words
A process according to claim 14 wherein the molar ratio of potassium to lithium is in the range of about 0.5:1 to about 1.75:1.
Claim 18
Dependent Claim
26 words
A process according to claim 15, and 16 wherein the weight ratio of butadiene to alpha-methylstyrene is in the range of about 40:60 to about 70:30.
Claim 19
Dependent Claim
36 words
A process according to claim 12 wherein said organolithium initiator is n-butyllithium and said n-butyllithium is employed in an amount in the range of about 0.1 to about 100 milliequivalents per hundred grams of total monomer.
Claim 20
Dependent Claim
11 words
A process according to claim 15 wherein said monomers include styrene.
Claim 21
Dependent Claim
26 words
A process according to claim 19 wherein the weight ratios of 1,3-butadiene to alpha-methylstyrene to styrene is in the range of about 50:25:25 to about 80:10:10.
Claim 22
Dependent Claim
35 words
A process according to claim 20 wherein tetrahydrofuran is included in the polymerization mixture in an amount in the range of 0.05 to 10 parts by weight per 100 parts by weight of total monomers.
Claim 23
Dependent Claim
23 words
A process according to claim 21 wherein the molar ratio of potassium to lithium is greater than 1:1 but no greater than 5:1.
Claim 24
Dependent Claim
51 words
A process according to claim 11 wherein the solution polymerization conditions include a temperature in the range of about 0° C. to about 120° C. and the molar ratio of the alkali metal of said alkali metal organic compound to the lithium is in the range of about 0.5/1 to 5/1.
Claim 25
Dependent Claim
28 words
A process according to claim 17 conducted under such conditions that the random copolymer produced has a heterogeneity index in the range of about 2.3 to about 6.2.
Claim 26
Dependent Claim
27 words
A process according to claim 22 conducted under such conditions that the random copolymer produced has a heterogeneity index in the range of about 2.1 to 2.4.
Claim 27
Dependent Claim
26 words
A process according to claim 12 conducted under such conditions that the random copolymer has a heterogeneity index in the range of about 2.3 to 6.2.
References Cited (Backward Citations)
US3294768A
Cited
US3366611A
Cited
US3496154A
Cited
US3825623A
Cited
US3726844A
Cited
US3759919A
Cited
US3734898A
Cited
US3767632A
Cited
US3763126A
Cited
US3992561A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-07-06 | 1985-01-05 | 1985-07-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-07-06 | 1989-01-05 | 1989-07-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-07-06 | 1993-01-05 | 1993-07-07 | $7700.00 | Window Closed / Lapsed |