US4091053A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Coupled resinous diene copolymer with good integral hinge flex life and high hardness
Assignee: Phillips Petroleum Co
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Filing: 1976-06-24
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Granted: 1978-05-23
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Expires: 1996-06-24
Abstract
Abstract A conjugated diene/monovinyl-substituted aromatic compound resinous copolymer such as a styrene/butadiene block copolymer is produced using two additions of the monovinyl-substituted aromatic component and initiator in a manner such that the product has 71 to 81 wt. percent monovinyl-substituted aromatic component and has a ratio based on the number average molecular weight of monovinyl-substituted aromatic component blocks in first and second polymer chains thus produced prior to coupling within the range of 3 to 7. The final product resulting from coupling such polymers has long integral hinge flex life and high hardness. This is accomplished by using no more than 5 millimoles of initiator per mole of monomer in the second addition.
Inventors
- 👤 Alonzo G. Kitchen
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 19:36
CPC Classifications
C; C08; C08F; C08F297/00; C08F297/02; C08F297/04; C08F297/044; C08G; C08G81/00; C08G81/02; C08G81/021; C08G81/022
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
169 words
A coupled resinous block copolymer of a monovinyl-substituted aromatic compound and a conjugated diene, said copolymer having 71 to 81 weight percent polymerized monovinyl-substituted aromatic compound, wherein chains forming said copolymer prior to coupling comprise a high molecular weight portion and a low molecular weight portion, a ratio of calculated number average molecular weight of polymerized monovinyl-substituted aromatic compound blocks of said high molecular weight portion to polymerized monovinyl-substituted aromatic compound blocks of said low molecular weight portion being in the range of 3 to 7, said copolymer being produced by adding monovinyl-substituted aromatic compound monomer in first and second portions, a weight ratio of said monovinyl-substituted aromatic compound in said first portion to that in said second portion being within the range of 1:1.5 to 2:1, with 2.0 to 2.7 millimoles of initiator per mole of monomer in said first portion being introduced with said first portion and 3 to 5 millimoles of initiator per mole of monomer in said second portion being introduced with said second portion.
Claim 2
Dependent Claim
169 words
A coupled resinous block copolymer of a monovinyl-substituted aromatic compound and a conjugated diene, said copolymer having 71 to 81 weight percent polymerized monovinyl-substituted aromatic compound, wherein chains forming said copolymer prior to coupling comprise a high molecular weight portion and a low molecular weight portion, a ratio of calculated number average molecular weight of polymerized monovinyl-substituted aromatic compound blocks of said high molecular weight portion to polymerized monovinyl-substituted aromatic compound blocks of said low molecular weight portion being in the range of 3 to 7, said copolymer being produced by adding monovinyl-substituted aromatic compound monomer in first and second portions, a weight ratio of said monovinyl-substituted aromatic compound in said first portion to that in said second portion being within the range of 1:1.5 to 2:1, with 2.0 to 2.7 millimoles of initiator per mole of monomer in said first portion being introduced with said first portion and 3 to 5 millimoles of initiator per mole of monomer in said second portion being introduced with said second portion.
Claim 3
Dependent Claim
24 words
A composition according to claim 1 wherein said monovinyl-substituted aromatic compound is styrene and said conjugated diene is 1,4-butadiene, isoprene, or a mixture thereof.
Claim 4
Dependent Claim
56 words
A composition according to claim 2 wherein said ratio of calculated number average molecular weight of said polymerized monovinyl-substituted aromatic compound block of said high molecular weight portion to said calculated number average molecular weight of said polymerized monovinyl-substituted aromatic compound block of said low molecular weight portion is within the range of 3.5 to 4.8.
Claim 5
Dependent Claim
61 words
A composition according to claim 2 wherein the ratio of the calculated number average molecular weight of said polymerized monovinyl-substituted aromatic compound blocks in said high molecular weight portion plus polymerized diene blocks attached thereto to said polymerized monovinyl-substituted aromatic compound blocks of said low molecular weight portion plus polymerized diene attached thereto is within the range of 2 to 4.
Claim 6
Dependent Claim
57 words
A composition according to claim 2 wherein a ratio of said polymerized monovinyl-substituted aromatic compound blocks of said high molecular weight portion plus polymerized diene to said polymerized monovinyl-substituted aromatic compound blocks of said low molecular weight portion plus polymerized diene attached thereto based on number average molecular weight is within the range of 2.5 to 3.3.
Claim 7
Dependent Claim
32 words
A composition according to claim 5 wherein said styrene is present in an amount within the range of 75 to 77 weight percent based on the total weight of styrene plus diene.
Claim 8
Dependent Claim
19 words
A composition according to claim 6 wherein said styrene is present in an amount of about 76 weight percent.
Claim 9
Dependent Claim
27 words
A composition according to claim 7 wherein said composition has a shore D hardness of at least 73 and a flex life of at least 650 cycles.
Claim 10
Dependent Claim
17 words
A composition according to claim 2 wherein said copolymer has a styrene content of about 76 percent.
Claim 11
Independent Claim
242 words
A method for preparing a polymer comprising (a) introducing a first portion of monovinyl-substituted aromatic compound monomer into a reaction zone; (b) introducing a first portion of an initiator into said reaction zone and polymerizing said first portion of said monovinyl-substituted aromatic compound; (c) thereafter introducing a second portion of a monovinyl-substituted aromatic compound into said reaction zone, a weight ratio of said monovinyl-substituted aromatic compound in said first portion to monovinyl-substituted aromatic compound in said second portion being within the range of 1:1.5 to 2:1; (d) introducing a second portion of said initiator into said reaction zone and polymerizing said second portion of said monovinyl-substituted aromatic compound, said first portion of initiator being introduced in an amount within the range of 2.0 to 2.7 millimoles per mole of said monomer in said first portion, and said second portion of initiator being introduced in an amount within the range of 3 to 5 millimoles per mole of said monomer in said second portion, (e) introducing at least one conjugated diene into said reaction zone and polymerizing said at least one conjugated diene; and (f) introducing a polyfunctional coupling agent into said reaction zone to form said polymer having a ratio of calculated number average molecular weight of polymerized monovinyl-substituted aromatic compound blocks from polymerizing said first portion of said monovinyl-substituted aromatic compound to that formed by polymerizing said second portion of said monovinyl-substituted aromatic compound within the range of 3 to 7.
Claim 12
Independent Claim
242 words
A method for preparing a polymer comprising (a) introducing a first portion of monovinyl-substituted aromatic compound monomer into a reaction zone; (b) introducing a first portion of an initiator into said reaction zone and polymerizing said first portion of said monovinyl-substituted aromatic compound; (c) thereafter introducing a second portion of a monovinyl-substituted aromatic compound into said reaction zone, a weight ratio of said monovinyl-substituted aromatic compound in said first portion to monovinyl-substituted aromatic compound in said second portion being within the range of 1:1.5 to 2:1; (d) introducing a second portion of said initiator into said reaction zone and polymerizing said second portion of said monovinyl-substituted aromatic compound, said first portion of initiator being introduced in an amount within the range of 2.0 to 2.7 millimoles per mole of said monomer in said first portion, and said second portion of initiator being introduced in an amount within the range of 3 to 5 millimoles per mole of said monomer in said second portion, (e) introducing at least one conjugated diene into said reaction zone and polymerizing said at least one conjugated diene; and (f) introducing a polyfunctional coupling agent into said reaction zone to form said polymer having a ratio of calculated number average molecular weight of polymerized monovinyl-substituted aromatic compound blocks from polymerizing said first portion of said monovinyl-substituted aromatic compound to that formed by polymerizing said second portion of said monovinyl-substituted aromatic compound within the range of 3 to 7.
Claim 13
Dependent Claim
25 words
A method according to claim 10 wherein said monovinyl-substituted aromatic compound is styrene and said conjugated diene is selected from 1,3-butadiene, isoprene, and mixtures thereof.
Claim 14
Dependent Claim
28 words
A method according to claim 11 wherein said wt ratio of monovinyl-substituted aromatic compound in said first and second portions is within the range of 1:1 to 1.9:1.
Claim 15
Dependent Claim
39 words
A method according to claim 12 wherein said styrene is present in an amount within the range of 75 to 77 weight percent based on the total weight of styrene and conjugated diene and wherein said diene is 1,3-butadiene.
Claim 16
Dependent Claim
50 words
A method according to claim 13 wherein said first portion of initiator is introduced in an amount within the range of 2.14 to 2.57 millimoles per mole of monomer and said second portion is introduced in an amount within the range of 3.66 to 4.93 millimoles per mole of monomer.
Claim 17
Dependent Claim
27 words
A method according to claim 14 wherein said coupling agent is epoxidized soybean oil containing about 4 epoxy groups per formula weight and said initiator is n-butyllithium.
References Cited (Backward Citations)
US3639517A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-05-22 | 1981-11-21 | 1982-05-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-05-22 | 1985-11-21 | 1986-05-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-05-22 | 1989-11-21 | 1990-05-23 | $7700.00 | Window Closed / Lapsed |