US4089913A
Expired / Lapsed
US
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Process for producing transparent block copolymer resin
Assignee: Sumitomo Chemical Co Ltd
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Filing: 1976-02-27
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Granted: 1978-05-16
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Expires: 1996-02-27
Abstract
Abstract In block-copolymerizing a vinyl aromatic compound and a conjugated diene in a hydrocarbon solvent using an organolithium compound as initiator, a transparent block copolymer resin characterized by having elastomeric random copolymer blocks may be produced by continuously adding a mixture of the vinyl aromatic compound and the conjugated diene. The block copolymer resin thus obtained is transparent, excellent in mechanical characteristics and may be used in the fields of sheetings, films, and various molded articles.
Inventors
- 👤 Tamotsu Miki
- 👤 Shizuo Narisawa
- 👤 Ichiro Ichikawa
- 👤 Hideki Horiike
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 07:49
CPC Classifications
C; C08; C08F; C08F297/00; C08F297/02; C08F297/04
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
221 words
In a process for producing a transparent block copolymer resin by block-copolymerizing 90 to 65 parts by weight of a vinyl aromatic compound monomer and 10 to 35 parts by weight of a conjugated diene monomer in a hydrocarbon solvent using an organolithium compound as initiator in the presence or absence of 0.01 to 5 mole-% based on the total monomer of a Lewis base compound to form a block copolymer in which each polymer molecule has at least one plastic region comprising a homopolymer of the vinyl aromatic compound and at least one elastomeric region comprising a random copolymer of the vinyl aromatic compound and the conjugated diene, the improvement which comprises forming said plastic region by homopolymerizing 50 to 90% by weight of the total vinyl aromatic compound monomer and said random copolymerized elastomeric region by adding continuously to the polymerization system a monomer mixture of a fixed composition, in which the weight ratio of the vinyl aromatic compound monomer to the conjugated diene monomer is 0.1 to 3.0, and under polymerization conditions at such a rate that the fed monomers will polymerize instantly and thus will not accumulate in the polymerization system, the resulting block copolymer having a mean molecular weight of 0.35 to 1.8 dl/g in terms of intrinsic viscosity as measured in toluene at 30° C.
Claim 2
Dependent Claim
221 words
In a process for producing a transparent block copolymer resin by block-copolymerizing 90 to 65 parts by weight of a vinyl aromatic compound monomer and 10 to 35 parts by weight of a conjugated diene monomer in a hydrocarbon solvent using an organolithium compound as initiator in the presence or absence of 0.01 to 5 mole-% based on the total monomer of a Lewis base compound to form a block copolymer in which each polymer molecule has at least one plastic region comprising a homopolymer of the vinyl aromatic compound and at least one elastomeric region comprising a random copolymer of the vinyl aromatic compound and the conjugated diene, the improvement which comprises forming said plastic region by homopolymerizing 50 to 90% by weight of the total vinyl aromatic compound monomer and said random copolymerized elastomeric region by adding continuously to the polymerization system a monomer mixture of a fixed composition, in which the weight ratio of the vinyl aromatic compound monomer to the conjugated diene monomer is 0.1 to 3.0, and under polymerization conditions at such a rate that the fed monomers will polymerize instantly and thus will not accumulate in the polymerization system, the resulting block copolymer having a mean molecular weight of 0.35 to 1.8 dl/g in terms of intrinsic viscosity as measured in toluene at 30° C.
Claim 3
Dependent Claim
27 words
A process according to claim 1, wherein the vinyl aromatic compound monomer is at least one member selected from the group consisting of styrene, α-methylstyrene and vinyltoluene.
Claim 4
Dependent Claim
14 words
A process according to claim 2, wherein the vinyl aromatic compound monomer is styrene.
Claim 5
Dependent Claim
26 words
A process according to claim 1, wherein the conjugated diene monomer is at least one member selected from the group consisting of 1,3-butadiene, isoprene and piperylene.
Claim 6
Dependent Claim
13 words
A process according to claim 4, wherein the conjugated diene monomer is 1,3-butadiene.
Claim 7
Dependent Claim
26 words
A process according to claim 1, wherein the hydrocarbon solvent is at least one member selected from the group consisting of aromatic, aliphatic and alicyclic hydrocarbons.
Claim 8
Dependent Claim
28 words
A process according to claim 6, wherein the hydrocarbon solvent is at least one member selected from the group consisting of hexane, heptane, cyclohexane, methylcyclohexane, benzene and toluene.
Claim 9
Dependent Claim
31 words
A process according to claim 1, wherein the inert hydrocarbon solvent is used in a proportion of 1 to 20 parts by weight per part by weight of the total monomer.
Claim 10
Dependent Claim
20 words
A process according to claim 1, wherein the Lewis base compound is an ether compound or a tertiary amine compound.
Claim 11
Dependent Claim
26 words
A process according to claim 9, wherein the ether compound is one member selected from the group consisting of cyclic ethers, aliphatic monoethers and aliphatic polyethers.
Claim 12
Dependent Claim
34 words
A process according to claim 10, wherein the ether compound is one member selected from the group consisting of tetrahydrofuran, tetrahydropyran, diethyl ether, dibutyl ether, ethylene glycol dimethyl ether and diethylene glycol diethyl ether.
Claim 13
Dependent Claim
26 words
A process according to claim 9, wherein the tertiary amine compound is one member selected from the group consisting of triethylamine, tripropylamine, tributylamine, N,N'-dimethylaniline and pyridine.
Claim 14
Dependent Claim
26 words
A process according to claim 1, wherein the Lewis base compound is used in a proportion of 0.01 to 5 mole-% based on the total monomer.
Claim 15
Dependent Claim
14 words
A process according to claim 1, wherein the Lewis base compound is not used.
Claim 16
Dependent Claim
18 words
A process according to claim 1, wherein the organolithium compound is an organomonolithium compound or an organodilithium compound.
Claim 17
Dependent Claim
35 words
A process according to claim 15, wherein the organo-monolithium compound is at least one member selected from the group consisting of ethyllithium, propyllithium, butyllithium, amyllithium, hexyllithium, 2-ethylhexyllithium, cyclohexyllithium, decyllithium, dodecyllithium, phenyllithium, tolyllithium, xylyllitium and naphthyllithium.
Claim 18
Dependent Claim
12 words
A process according to claim 16, wherein the organo-monolithium compound is butyllithium.
Claim 19
Dependent Claim
33 words
A process according to claim 15, wherein the organo-dilithium compound is at least one member selected from the group consisting of trimethylene-dilithium, tetramethylene-dilithium, pentamethylene-dilithium, naphthalene-lithium complex, stilbene-lithium complex, diphenyl-lithium complex, oligobutadienyl-dilithium and oligoisoprenyl-dilithium.
Claim 20
Dependent Claim
22 words
A process according to claim 18, wherein the organo-dilithium compound is one member selected from the group consisting of oligobutadienyl-dilithium and oligoisoprenyl-dilithium.
Claim 21
Dependent Claim
25 words
A process according to claim 1, wherein the organolithium compound is used in a proportion of 0.002 to 5 mole-% based on the total monomer.
Claim 22
Dependent Claim
48 words
A process accoeding to claim 1, wherein in forming two or more plastic regions composed of homopolymers of a vinyl aromatic compound, sum of the vinyl aromatic compound used in forming each plastic region is 50 to 90% by weight based on the total vinyl aromatic compound monomer.
Claim 23
Dependent Claim
81 words
A process according to claim 1, wherein in forming two or more elastomeric regions composed of random copolymers of a vinyl aromatic compound and a conjugated diene, the weight ratio of the vinyl aromatic compound to the conjugated diene used in forming each elastomeric region is in the range from 0.1 to 3.0 and the weight ratio of the vinyl aromatic compound to the conjugated diene used in forming all elastomeric regions is also in the range from 0.1 to 3.0.
Claim 24
Dependent Claim
41 words
A process according to claim 22, wherein in forming two or more elastomeric regions by continuous addition of the vinyl aromatic compound and the conjugated diene in a fixed ratio, said ratio is different among the elastomeric regions from one another.
Claim 25
Dependent Claim
169 words
A process according to claim 1, wherein the structure of the block copolymer to be formed is selected from the group consisting of (1) S 1 - (S/B) 1 , (2) s 1 - (s/b) 1 - s 1 , (3) s 1 - (s/b) 1 - s 2 , (4) s 1 - (s/b) 1 - (s/b) 2 - s 2 , (5) s 1 - (s/b) 1 - s 2 - (s/b) 2 , (6) s 1 - (s/b) 1 - (s/b) 2 - s 3 , and (7) S 1 - (S/B) 1 - (S/B) 2 - (S/B) 1 - S 1 , where S 1 , S 2 , and S 3 represent homopolymer regions of a vinyl aromatic compound and (S/B) 1 and (S/B) 2 represent random copolymer regions, formed by adding continuously to the polymerization system a monomer mixture of a fixed composition, in which the weight ratio of the vinyl aromatic compound monomer to the conjugated diene monomer is 0.1 to 3.0.
Claim 26
Dependent Claim
22 words
A process according to claim 1, wherein the polymerization is effected at a temperature in the range from 20° to 120° C.
Claim 27
Dependent Claim
40 words
A process according to claim 1, wherein, after completion of the polymerization, the polymerization mixture is contacted with excess of a lower alcohol, or directly heated to dryness, or mixed with steam, thereby removing the solvent to recover the polymer.
Claim 28
Dependent Claim
12 words
A block copolymer resin produced by the process according to claim 1.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-05-15 | 1981-11-14 | 1982-05-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-05-15 | 1985-11-14 | 1986-05-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-05-15 | 1989-11-14 | 1990-05-16 | $7700.00 | Window Closed / Lapsed |