US3855189A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Polar compounds improve effectiveness of polyvinyl aromatic compounds
Assignee: Phillips Petroleum Co
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Filing: 1972-02-11
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Granted: 1974-12-17
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Expires: 1992-02-11
Abstract
Abstract Polar compounds, added after polymerization is essentially complete to polymerization systems initiated with lithium based initiators, significantly improve the effectiveness of polyvinyl aromatic compounds in reducing cold flow and improving other polymer properties.
Inventors
- 👤 R Farrar
- 👤 A Rothlisberger
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 11:50
CPC Classifications
C; C08; C08F; C08F297/00; C08F297/02; C08F297/04; C08F297/044; C08C; C08C19/00; C08C19/30; C08C19/42; C08C19/44; C08K; C08K5/00; C08K5/01
Claims Analysis
Total Claims: 13
Claim 1
Independent Claim
128 words
A POLYMERIZATION PROCESS WHICH COMPRISES A. INTRODUCING INTO A POLYMERIZATION ZONE AT LEAST ONE POLYMERIZABLE MONOMER SELECTED FROM THE GROUP CONSISTING OF POLYMERIZABLE CONJUGATED DIENES, POLYMERIZABLE MONOVINYL-SUBSTITUTED AROMATIC COMPOUNDS, AND MIXTURES, UNDER POLYMERIZATION CONDITIONS EMPLOYING AN ORGANOLITHIUM INITIATOR, B. POLYMERIZING SAID POLYMERIZABLE MONOMER WITH SAID ORGANOLITHIUM INITIATOR, THEREBY FORMING POLYMER-LITHIUM MOIETIES, C. TREATING THE RESULTING POLYMERIZATION MIXTURE WITH AT LEAST ONE POLAR COMPOUND IN MINOR AMOUNT EFFECTIVE TO IMPROVIDE COUPLING OF SAID POLYMER-LITHIUM, WHEREIN SAID POLAR ORGANIC COMPOUND IS ETHER, THIOETHER, TERTIARY AMINE, OR TRIAZINE, OR MIXTURE, D. TREATING SAID POLYMERIZATION REACTION SYSTEM WITH AT LEAST ONE POLYVINYL AROMATIC COMPOUND IN MINOR AMOUNT EFFECTIVE TO COUPLE SAID POLYMER-LITHIUM MOIETIES, WHEREIN SAID POLAR COMPOUNDS IS ADDED TO SAID POLYMERIZATION MIXTURE PRIOR TO OR COINCIDENTALLY WITH SAID POLYVINYL AROMATIC COMPOUND.
Claim 2
Dependent Claim
128 words
A POLYMERIZATION PROCESS WHICH COMPRISES A. INTRODUCING INTO A POLYMERIZATION ZONE AT LEAST ONE POLYMERIZABLE MONOMER SELECTED FROM THE GROUP CONSISTING OF POLYMERIZABLE CONJUGATED DIENES, POLYMERIZABLE MONOVINYL-SUBSTITUTED AROMATIC COMPOUNDS, AND MIXTURES, UNDER POLYMERIZATION CONDITIONS EMPLOYING AN ORGANOLITHIUM INITIATOR, B. POLYMERIZING SAID POLYMERIZABLE MONOMER WITH SAID ORGANOLITHIUM INITIATOR, THEREBY FORMING POLYMER-LITHIUM MOIETIES, C. TREATING THE RESULTING POLYMERIZATION MIXTURE WITH AT LEAST ONE POLAR COMPOUND IN MINOR AMOUNT EFFECTIVE TO IMPROVIDE COUPLING OF SAID POLYMER-LITHIUM, WHEREIN SAID POLAR ORGANIC COMPOUND IS ETHER, THIOETHER, TERTIARY AMINE, OR TRIAZINE, OR MIXTURE, D. TREATING SAID POLYMERIZATION REACTION SYSTEM WITH AT LEAST ONE POLYVINYL AROMATIC COMPOUND IN MINOR AMOUNT EFFECTIVE TO COUPLE SAID POLYMER-LITHIUM MOIETIES, WHEREIN SAID POLAR COMPOUNDS IS ADDED TO SAID POLYMERIZATION MIXTURE PRIOR TO OR COINCIDENTALLY WITH SAID POLYVINYL AROMATIC COMPOUND.
Claim 3
Dependent Claim
124 words
The process according to claim 1 wherein said polymerizable conjugated diene contains 4 to 12 carbon atoms per molecule, and said polymerizable monovinyl-substituted aromatic hydrocarbon contains 8 to 20 carbon atoms per molecule, said organolithium initiator is employed in an amount sufficient to provide 0.02 to 2 equivalents of said lithium in said organolithium initiator per 100 parts by weight of monomer charged to the polymerization reaction system, said minor effective amount of said polar compound ranges from 0.001 to 5 parts by weight per 100 parts by weight of said monomer employed in said polymerization process, and said minor effective amount of said polyvinyl aromatic compound ranges from 0.005 to about 4 moles per gram equivalent of lithium used in said organolithium initiator.
Claim 4
Dependent Claim
14 words
The process according to claim 2 wherein said polyvinyl aromatic compound is represented by
Claim 5
Dependent Claim
34 words
The process according to claim 3 wherein said polar compound is added to said polymerization mixture after polymerization of said polymerizable monomer is substantially complete and prior to addition of said polyvinyl aromatic compound.
Claim 6
Dependent Claim
13 words
The process according to claim 4 wherein said polar compound is an ether.
Claim 7
Dependent Claim
22 words
The process according to claim 5 wherein said polymerizable conjugated diene is butadiene, and said polymerizable monovinyl substituted aromatic compound is styrene.
Claim 8
Dependent Claim
11 words
The process according to claim 6 wherein said ether is tetrahydrofuran.
Claim 9
Dependent Claim
13 words
The process according to claim 7 wherein said polyvinyl aromatic compound is divinylbenzene.
Claim 10
Dependent Claim
12 words
The process according to claim 8 wherein said organolithium initiator is n-butyllithium.
Claim 11
Dependent Claim
121 words
A polymerization process which comprises (a) copolymerizing a polymerizable conjugated diene and a polymerizable monovinyl-substituted aromatic compound, under polymerization conditions, in the presence of a randomizing amount of potassium tertiary-amyl oxide, employing an organomonolithium initiator, thereby forming polymer-lithium moieties, b. treating the resulting polymerization mixture from said step (a) with 0.001 to 5 parts by weight of tetrahydrofuran per 100 parts by weight of monomer, said tetrahydrofuran effective to improve coupling of said polymer lithium, c. thereafter treating the resulting polymerization reaction system from said step (b) with 0.05 to 4 moles of divinylbenzene per gram equivalent of lithium, effective to couple said polymer-lithium moieties, wherein said divinylbenzene is added sequentially after said addition of said tetrahydrofuran to said polymerization mixture.
Claim 12
Dependent Claim
121 words
A polymerization process which comprises (a) copolymerizing a polymerizable conjugated diene and a polymerizable monovinyl-substituted aromatic compound, under polymerization conditions, in the presence of a randomizing amount of potassium tertiary-amyl oxide, employing an organomonolithium initiator, thereby forming polymer-lithium moieties, b. treating the resulting polymerization mixture from said step (a) with 0.001 to 5 parts by weight of tetrahydrofuran per 100 parts by weight of monomer, said tetrahydrofuran effective to improve coupling of said polymer lithium, c. thereafter treating the resulting polymerization reaction system from said step (b) with 0.05 to 4 moles of divinylbenzene per gram equivalent of lithium, effective to couple said polymer-lithium moieties, wherein said divinylbenzene is added sequentially after said addition of said tetrahydrofuran to said polymerization mixture.
Claim 13
Dependent Claim
51 words
The process of claim 2 wherein said polar compound iS employed in a range of about 0.05 to 2 parts by weight per 100 parts by weight of monomer; and wherein said polyvinyl aromatic compound is employed in a range of about 0.1 to 2 moles per gram equivalent of lithium.
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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) | 1977-12-16 | 1978-06-17 | 1978-12-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1981-12-16 | 1982-06-17 | 1982-12-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1985-12-16 | 1986-06-17 | 1986-12-17 | $7700.00 | Window Closed / Lapsed |