US4238576A
Expired / Lapsed
US
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Orthoesters as coupling agents for producing novel polymers
Assignee: Phillips Petroleum Co
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Filing: 1979-01-22
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Granted: 1980-12-09
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Expires: 1999-01-22
Abstract
Abstract Orthoesters are used to couple living homopolymers of monovinylarenes, and living copolymers of monovinylarenes and conjugated dienes. Novel coupled polymers are thereby produced.
Inventors
- 👤 William J. Trepka
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 01:14
CPC Classifications
C; C08; C08G; C08G81/00; C08G81/02; C08G81/021; C08G81/022; C08F; C08F8/00
Claims Analysis
Total Claims: 19
Claim 1
Independent Claim
99 words
A method of producing a coupled polymer comprising: (a) forming living polymer molecules in which an alkali metal atom is attached to a terminal monovinylarenyl group in said living polymer molecules, and (b) then adding an orthoester and coupling said living polymer molecules with said orthoester so as to form said coupled polymer, said orthoester having the formula ##STR2## wherein R, R', and R" are the same or different and are individually selected from alkyl groups, and said coupled polymers being prepared from monomers selected from the group consisting of monovinylarenes and a combination of monovinylarenes and conjugated dienes.
Claim 2
Independent Claim
99 words
A method of producing a coupled polymer comprising: (a) forming living polymer molecules in which an alkali metal atom is attached to a terminal monovinylarenyl group in said living polymer molecules, and (b) then adding an orthoester and coupling said living polymer molecules with said orthoester so as to form said coupled polymer, said orthoester having the formula ##STR2## wherein R, R', and R" are the same or different and are individually selected from alkyl groups, and said coupled polymers being prepared from monomers selected from the group consisting of monovinylarenes and a combination of monovinylarenes and conjugated dienes.
Claim 3
Dependent Claim
59 words
A method according to claim 1 wherein said conjugated dienes have 4 to about 12 carbon atoms per monomer unit, wherein said monovinylarenes have 8 to about 20 carbon atoms per monomer unit, wherein said alkali metal is lithium, and wherein R, R', and R" are alkyl groups having from 1 to about 4 carbon atoms per alkyl group.
Claim 4
Dependent Claim
12 words
A method according to claim 2 wherein said orthoester is triethyl orothoformate.
Claim 5
Dependent Claim
38 words
A method according to claim 3 wherein said living polymers are styryllithium-terminated and wherein said triethyl orthoformate is added in an amount within the range from about 0.05 to about 20 moles per mole of lithium in polymer.
Claim 6
Dependent Claim
18 words
A method according to claim 4 wherein said living polymers are living block copolymers of butadiene and styrene.
Claim 7
Dependent Claim
16 words
A method according to claim 4 wherein said living polymers are homopolymers formed from monovinylarene monomers.
Claim 8
Independent Claim
118 words
A method of selectively coupling monovinylarenyllithium-terminated living polymers prepared from monomers selected from the group consisting of conjugated dienes, monovinylarenes, and mixtures thereof, and essentially not coupling conjugated dienyllithium-terminated living polymers prepared from said monomers, said method comprising: (a) charging at least one of said monomers and a polymerization initiator to a polymerization zone and operating said polymerization zone under polymerization conditions so as to form living polymers; and (b) then charging an orthoester to said polymerization zone and operating said polymerization zone under coupling conditions, thereby forming coupled polymers selectively from monovinylarenyllithium-terminated living polymers, said orthoester having the formula ##STR3## wherein R, R', and R" are the same or different and are individually selected from alkyl groups.
Claim 9
Independent Claim
118 words
A method of selectively coupling monovinylarenyllithium-terminated living polymers prepared from monomers selected from the group consisting of conjugated dienes, monovinylarenes, and mixtures thereof, and essentially not coupling conjugated dienyllithium-terminated living polymers prepared from said monomers, said method comprising: (a) charging at least one of said monomers and a polymerization initiator to a polymerization zone and operating said polymerization zone under polymerization conditions so as to form living polymers; and (b) then charging an orthoester to said polymerization zone and operating said polymerization zone under coupling conditions, thereby forming coupled polymers selectively from monovinylarenyllithium-terminated living polymers, said orthoester having the formula ##STR3## wherein R, R', and R" are the same or different and are individually selected from alkyl groups.
Claim 10
Dependent Claim
59 words
A method according to claim 7, wherein said conjugated dienes have 4 to about 12 carbon atoms per monomer unit, wherein said monovinylarenes have 8 to about 20 carbon atoms per monomer unit, wherein said alkali metal is lithium, and wherein R, R', and R" are alkyl groups having from 1 to about 4 carbon atoms per alkyl group.
Claim 11
Dependent Claim
12 words
A method according to claim 8, wherein said orthoester is triethyl orthoformate.
Claim 12
Dependent Claim
43 words
A method according to claim 9, wherein said monovinylarene is styrene, wherein said conjugated diene is butadiene, and wherein said triethyl orthoformate is present in an amount within the range from about 0.05 to about 20 moles per mole of lithium in polymer.
Claim 13
Dependent Claim
93 words
A coupled polymer prepared by the method comprising: (a) forming living polymer molecules in which an alkali metal atom is attached to a terminal monovinylarenyl group in said living polymer molecules, (b) coupling said living polymer molecules with an orthoester so as to form said coupled polymer, said orthoester having the formula ##STR4## wherein R, R', and R" are the same or different and are individually selected from alkyl groups, and said coupled polymers being prepared from monomers selected from the group consisting of monovinylarenes and a combination of monovinylarenes and conjugated dienes.
Claim 14
Dependent Claim
93 words
A coupled polymer prepared by the method comprising: (a) forming living polymer molecules in which an alkali metal atom is attached to a terminal monovinylarenyl group in said living polymer molecules, (b) coupling said living polymer molecules with an orthoester so as to form said coupled polymer, said orthoester having the formula ##STR4## wherein R, R', and R" are the same or different and are individually selected from alkyl groups, and said coupled polymers being prepared from monomers selected from the group consisting of monovinylarenes and a combination of monovinylarenes and conjugated dienes.
Claim 15
Dependent Claim
60 words
A coupled polymer according to claim 11, wherein said conjugated dienes have 4 to about 12 carbon atoms per monomer unit, wherein said monovinylarenes have 8 to about 20 carbon atoms per monomer unit, wherein said alkali metal is lithium, and wherein R, R', and R" are alkyl groups having from 1 to about 4 carbon atoms per alkyl group.
Claim 16
Dependent Claim
13 words
A coupled polymer according to claim 12, wherein said orthoester is triethyl orthoformate.
Claim 17
Dependent Claim
13 words
A coupled polymer according to claim 13, wherein said living polymers are styryllithium-terminated.
Claim 18
Dependent Claim
18 words
A coupled polymer according to claim 14, wherein said living polymers are block copolymers of butadiene and styrene.
Claim 19
Dependent Claim
17 words
A coupled polymer according to claim 14, wherein said living polymers are homopolymers formed from monovinylarene monomers.
References Cited (Backward Citations)
US3281383A
Cited
US3637554A
Cited
US3580895A
Cited
US3594452A
Cited
GB1276320A
Cited
US3551392A
Cited
US3773732A
Cited
US4020258A
Cited
US3803266A
Cited
US3993854A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-12-09 | 1984-06-09 | 1984-12-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-12-09 | 1988-06-09 | 1988-12-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-12-09 | 1992-06-09 | 1992-12-09 | $7700.00 | Window Closed / Lapsed |