US4122134A
Expired / Lapsed
US
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Method for producing transparent block copolymer resin
Assignee: Sumitomo Chemical Co Ltd
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Filing: 1977-08-23
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Granted: 1978-10-24
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Expires: 1997-08-23
Abstract
Abstract By block-copolymerizing a vinyl aromatic compound and a conjugated diene in a hydrocarbon solvent with an organolithium compound as initiator, there is obtained a block copolymer which comprises in the molecule three blocks of homopolymerized vinyl aromatic compound, randomly copolymerized vinyl aromatic compound and conjugated diene, and homopolymerized diene, respectively. The resulting block copolymer is transparent and excellent in mechanical properties, and is suitable for use in the manufacture of sheeting, film, 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
2026-11-09 13:52
CPC Classifications
C; C08; C08F; C08F297/00; C08F297/02; C08F297/04
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
449 words
In a process for forming a block copolymer having in the molecule at least one plastic block composed of a homopolymer of a vinyl aromatic compound and at least one elastomeric block composed of a vinyl aromatic compound and a conjugated diene 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 as solvent with an organolithium compound as initiator in the presence or absence of 0.01 to 5 mole-% based on total monomer of a Lewis base compound, the improvement whereby a transparent block copolymer is formed, which comprises forming a block copolymer which has a plastic block formed by homopolymerizing 50 to 90% by weight of total vinyl aromatic compound monomer and an elastomeric block composed of (1) a random copolymer segment formed by continuously feeding to the polymerization system a monomer mixture of a vinyl aromatic compound and a conjugated diene in a fixed weight ratio in the range from 0.1 to 3.0, (2) a segment formed by homopolymerizing a conjugated diene, and/or (3) a random copolymer segment formed by feeding a monomer mixture of a vinyl aromatic compound and a conjugated diene in a fixed weight ratio of less than 0.1 continuously to the polymerization system; said segment (1) occupying 50 to 90% by weight of said elastomeric block; said block copolymer having a structure represented by any of the following formulae: S.sub.1 - (S/B).sub.1 - B.sub.1 ( 1) s.sub.1 - b.sub.1 - (s/b).sub.1 ( 2) s.sub.1 - (s/b).sub.1 - b.sub.1 - s.sub.2 ( 3) s.sub.1 - (s/b).sub.1 - b.sub.1 - (s/b).sub.2 - s.sub.2 ( 4) s.sub.1 - b.sub.1 - (s/b).sub.1 - b.sub.2 - s.sub.2 ( 5) s.sub.1 - (s/b).sub.1 - (s/b).sub.2 - b.sub.1 - s.sub.2 ( 6) s.sub.1 - (s/b).sub.1 - b.sub.1 - (s/b).sub.2 - b.sub.2 - (s/b).sub.3 - s.sub.2 ( 7) s.sub.1 - (s/b).sub.1 - s.sub.2 - (s/b).sub.2 - b.sub.1 - s.sub.3 ( 8) s.sub.1 - (s/b).sub.1 - b.sub.1 - s.sub.2 - b.sub.2 - (s/b).sub.2 - s.sub.3 ( 9) s.sub.1 - (s/b).sub.1 - s.sub.2 - b.sub.1 - (s/b).sub.2 ( 10) s.sub.1 - (s/b).sub.1 - s.sub.2 - (s/b).sub.2 - b.sub.1 ( 11) wherein S 1 , S 2 , and S 3 represent homopolymerized vinyl aromatic compound blocks, (S/B) 1 , (S/B) 2 , and (S/B) 3 represent randomly copolymerized vinyl aromatic and conjugated diene segments or segments formed by feeding a vinyl aromatic compound and a conjugated diene in a weight ratio in the range from 0.001 to 0.1; said block copolymer having an average 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
449 words
In a process for forming a block copolymer having in the molecule at least one plastic block composed of a homopolymer of a vinyl aromatic compound and at least one elastomeric block composed of a vinyl aromatic compound and a conjugated diene 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 as solvent with an organolithium compound as initiator in the presence or absence of 0.01 to 5 mole-% based on total monomer of a Lewis base compound, the improvement whereby a transparent block copolymer is formed, which comprises forming a block copolymer which has a plastic block formed by homopolymerizing 50 to 90% by weight of total vinyl aromatic compound monomer and an elastomeric block composed of (1) a random copolymer segment formed by continuously feeding to the polymerization system a monomer mixture of a vinyl aromatic compound and a conjugated diene in a fixed weight ratio in the range from 0.1 to 3.0, (2) a segment formed by homopolymerizing a conjugated diene, and/or (3) a random copolymer segment formed by feeding a monomer mixture of a vinyl aromatic compound and a conjugated diene in a fixed weight ratio of less than 0.1 continuously to the polymerization system; said segment (1) occupying 50 to 90% by weight of said elastomeric block; said block copolymer having a structure represented by any of the following formulae: S.sub.1 - (S/B).sub.1 - B.sub.1 ( 1) s.sub.1 - b.sub.1 - (s/b).sub.1 ( 2) s.sub.1 - (s/b).sub.1 - b.sub.1 - s.sub.2 ( 3) s.sub.1 - (s/b).sub.1 - b.sub.1 - (s/b).sub.2 - s.sub.2 ( 4) s.sub.1 - b.sub.1 - (s/b).sub.1 - b.sub.2 - s.sub.2 ( 5) s.sub.1 - (s/b).sub.1 - (s/b).sub.2 - b.sub.1 - s.sub.2 ( 6) s.sub.1 - (s/b).sub.1 - b.sub.1 - (s/b).sub.2 - b.sub.2 - (s/b).sub.3 - s.sub.2 ( 7) s.sub.1 - (s/b).sub.1 - s.sub.2 - (s/b).sub.2 - b.sub.1 - s.sub.3 ( 8) s.sub.1 - (s/b).sub.1 - b.sub.1 - s.sub.2 - b.sub.2 - (s/b).sub.2 - s.sub.3 ( 9) s.sub.1 - (s/b).sub.1 - s.sub.2 - b.sub.1 - (s/b).sub.2 ( 10) s.sub.1 - (s/b).sub.1 - s.sub.2 - (s/b).sub.2 - b.sub.1 ( 11) wherein S 1 , S 2 , and S 3 represent homopolymerized vinyl aromatic compound blocks, (S/B) 1 , (S/B) 2 , and (S/B) 3 represent randomly copolymerized vinyl aromatic and conjugated diene segments or segments formed by feeding a vinyl aromatic compound and a conjugated diene in a weight ratio in the range from 0.001 to 0.1; said block copolymer having an average 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
26 words
A process according to claim 1, wherein the vinyl aromatic compound is at least one member selected from the group consisting of styrene, α-methylstyrene and vinyltoluene.
Claim 4
Dependent Claim
13 words
A process according to claim 2, wherein the vinyl aromatic compound is styrene.
Claim 5
Dependent Claim
25 words
A process according to claim 1, wherein the conjugated diene is at least one member selected from the group consisting of 1,3-butadiene, isoprene and piperylene.
Claim 6
Dependent Claim
12 words
A process according to claim 4, wherein the conjugated diene is 1,3-butadiene.
Claim 7
Dependent Claim
31 words
A process according to claim 1, wherein the hydrocarbon is at least one member selected from the group consisting of paraffinic, naphthenic and aromatic hydrocarbons having 3 to 20 carbon atoms.
Claim 8
Dependent Claim
27 words
A process according to claim 6, wherein the hydrocarbon is at least one member selected from the group consisting of hexane, heptane, cyclohexane, methylcyclohexane, benzene and toluene.
Claim 9
Dependent Claim
29 words
A process according to claim 1, wherein the hydrocarbon is used in a proportion of 1 to 20 parts by weight per part by weight of the total monomer.
Claim 10
Dependent Claim
30 words
A process according to claim 1, wherein the Lewis base compound is at least one member selected from the group consisting of an ether compound and a tertiary amine compound.
Claim 11
Dependent Claim
28 words
A process according to claim 9, wherein the ether compound is at least one member selected from the group consisting of cyclic ethers, aliphatic monoethers and aliphatic polyethers.
Claim 12
Dependent Claim
35 words
A process according to claim 10, wherein the ether compound is at least one member selected from the group consisting of tetrahydrofuran, tetrahydropyran, diethyl ether, dibutyl ether, ethylene glycol dimethyl ether and diethyleneglycol diethyl ether.
Claim 13
Dependent Claim
28 words
A process according to claim 9, wherein the tertiary amine compound is at least 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 0.05 to 2 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
28 words
A process according to claim 1, wherein the organolithium compound is at least one member selected from the group consisting of an organomonolithium compound and an organodilithium compound.
Claim 17
Dependent Claim
35 words
A process according to claim 15, wherein the organomonolithium compound is at least one member selected from the group consisting of ethyllithium, propyllithium, butyllithium, amyllithium, hexyllithium, 2-ethylhexyllithium, cyclohexyllithium, decyllithium, dodecyllithium, phenyllithium, tolyllithium, xylyllithium and naphthyllithium.
Claim 18
Dependent Claim
12 words
A process according to claim 16, wherein the organomonolithium compound is butyllithium.
Claim 19
Dependent Claim
33 words
A process according to claim 15, wherein the organodilithium compound is at least one member selected from the group consisting of trimethylenedilithium, tetramethylenedilithium, pentamethylenedilithium, naphthalene-lithium complex, stilbenelithium complex, diphenyl-lithium complex, oligobutadienyldilithium and oligoisoprenyldilithium.
Claim 20
Dependent Claim
24 words
A process according to claim 18, wherein the organodilithium compound is at least one member selected from the group consisting of oligobutadienyldilithium and oligoisoprenyldilithium.
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
44 words
A process according to claim 1, wherein in forming the molecule two or more plastic blocks composed of vinyl aromatic compound homopolymer, the sum of the vinyl aromatic compound used in each plastic block is 50 to 90% by weight of the total monomer.
Claim 23
Dependent Claim
87 words
A process according to claim 1, wherein in forming in the molecule two or more elastomeric blocks composed of a random copolymer of a vinyl aromatic compound and a conjugated diene, the weight ratio between the vinyl aromatic compound and the conjugated diene used in forming each elastomeric block is in the range from 0.1 to 3.0 and the weight ratio between the vinyl aromatic compound and the conjugated diene used in forming all of the elastomeric blocks is also in the range from 0.1 to 3.0.
Claim 24
Dependent Claim
43 words
A process according to claim 22, wherein in forming in the molecule two or more elastomeric blocks by feeding continuously a vinyl aromatic compound and a conjugated diene in a fixed ratio, said fixed ratio is different in each of the elastomeric blocks.
Claim 25
Dependent Claim
33 words
A process according to claim 22, wherein in forming the elastomeric block, the vinyl aromatic compound and the conjugated diene are fed in a fixed ratio continuously or consecutively deemed as substantially continuously.
Claim 26
Dependent Claim
38 words
A process according to claim 24, wherein the monomer mixture is fed at such a rate that the monomers which were fed may polymerize substantially instantly under the polymerization conditions and not remain unpolymerized in the polymerization system.
Claim 27
Dependent Claim
22 words
A process according to claim 1, wherein the conjugated diene homopolymer segment occupies less than 50% by weight of the elastomeric block.
Claim 28
Dependent Claim
53 words
A process according to claim 1, wherein less than 50% by weight of the elastomeric block are occupied by the segment formed by feeding a monomer mixture of a conjugated diene and a vinyl aromatic compound in a fixed weight ratio in the range from 0.001 to 0.1, continuously to the polymerization system.
Claim 29
Dependent Claim
20 words
A process according to claim 1, wherein in forming all blocks, the monomer or the monomer mixture is fed continuously.
Claim 30
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 31
Dependent Claim
40 words
A process according to claim 1, wherein after completion of the polymerization, the polymerization solution 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 32
Dependent Claim
12 words
A block copolymer resin prepared 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) | 1981-10-23 | 1982-04-24 | 1982-10-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-10-23 | 1986-04-24 | 1986-10-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-10-23 | 1990-04-24 | 1990-10-24 | $7700.00 | Window Closed / Lapsed |