US4054616A
Expired / Lapsed
US
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Process for producing transparent block copolymer resins
Assignee: Sumitomo Chemical Co Ltd
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Filing: 1976-05-10
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Granted: 1977-10-18
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Expires: 1996-05-10
Abstract
Abstract A block copolymer resin having at one or both ends a copolymer block of a vinyl aromatic compound and a conjugated diene is obtained by subjecting a vinyl aromatic compound and a conjugated diene to 2- or 3-stage block copolymerization in a hydrocarbon solvent in the presence of a definite amount of a Lewis base compound using an organolithium compound as an initiator. The block copolymer resin is high in transparency and excellent in mechanical properties, and is successfully usable in the fields of sheets, 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
2026-10-23 21:04
CPC Classifications
C; C08; C08F; C08F297/00; C08F297/02; C08F297/04
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
290 words
A process for producing a transparent block copolymer resin which comprises subjecting 90 to 65 parts by weight of a vinyl aromatic compound monomer and 10 to 35 parts by weight of a conjugated diene monomer to 3-stage block copolymerization in an inert hydrocarbon solvent using an organo-monolithium compound as an initiator, characterized in that at the first stage of polymerization, a mixture of S 1 parts by weight of the vinyl aromatic compound monomer and B 1 parts by weight of the conjugated diene monomer is added and substantially all of the monomer mixture is polymerized; at the second stage of polymerization, S 2 parts by weight of the vinyl aromatic compound monomer is added and the polymerization is continued to polymerize substantially all of the monomers; and at the third stage of polymerization, a mixture of S 3 parts by weight of the vinyl aromatic compound monomer and B 3 parts by weight of the conjugted diene monomer is added and the polymerization is continued to polymerize substantially all of the monomers, wherein the feed weight ratios of the individual monomers are controlled to values within the ranges of: S.sub.1 + S.sub.2 + S.sub.3 = 90 to 65 (parts by weight) B.sub.1 + B.sub.3 = 10 to 35 (parts by weight) S.sub.1 /B.sub.1 = 0.2 to 3.0 S.sub.3 /B.sub.3 = 0.2 to 3.0 S.sub.2 /(S.sub.1 + S.sub.2 + S.sub.3) = 0.35 to 0.90 and the polymerization is effected in the presence of 0.01 to 5 mole % of a Lewis base compound based on the total monomer, to produce a block copolymer resin having an average molecular weight in the range from 0.5 to 1.8 dl/g in terms of intrinsic viscosity as measured in toluene at 30° C.
Claim 2
Dependent Claim
290 words
A process for producing a transparent block copolymer resin which comprises subjecting 90 to 65 parts by weight of a vinyl aromatic compound monomer and 10 to 35 parts by weight of a conjugated diene monomer to 3-stage block copolymerization in an inert hydrocarbon solvent using an organo-monolithium compound as an initiator, characterized in that at the first stage of polymerization, a mixture of S 1 parts by weight of the vinyl aromatic compound monomer and B 1 parts by weight of the conjugated diene monomer is added and substantially all of the monomer mixture is polymerized; at the second stage of polymerization, S 2 parts by weight of the vinyl aromatic compound monomer is added and the polymerization is continued to polymerize substantially all of the monomers; and at the third stage of polymerization, a mixture of S 3 parts by weight of the vinyl aromatic compound monomer and B 3 parts by weight of the conjugted diene monomer is added and the polymerization is continued to polymerize substantially all of the monomers, wherein the feed weight ratios of the individual monomers are controlled to values within the ranges of: S.sub.1 + S.sub.2 + S.sub.3 = 90 to 65 (parts by weight) B.sub.1 + B.sub.3 = 10 to 35 (parts by weight) S.sub.1 /B.sub.1 = 0.2 to 3.0 S.sub.3 /B.sub.3 = 0.2 to 3.0 S.sub.2 /(S.sub.1 + S.sub.2 + S.sub.3) = 0.35 to 0.90 and the polymerization is effected in the presence of 0.01 to 5 mole % of a Lewis base compound based on the total monomer, to produce a block copolymer resin having an average molecular weight in the range from 0.5 to 1.8 dl/g in terms of intrinsic viscosity as measured in toluene at 30° C.
Claim 3
Dependent Claim
231 words
A process for producing a transparent block copolymer resin which comprises subjecting 90 to 65 parts by weight of a vinyl aromatic compound monomer and 10 to 35 parts by weight of a conjugated diene monomer to 2-stage block copolymerization in an inert hydrocarbon solvent using an organo-dilithium compound as an initiator, characterized in that at the first stage of polymerization, S 1 parts by weight of the vinyl aromatic compound monomer is added and substantially all of the monomer is polymerized, and then, at the second stage of polymerization, a mixture of S 2 parts by weight of the vinyl aromatic compound monomer and B parts by weight of the conjugated diene monomer is added and the polymerization is continued to polymerize substantially all of the monomers, wherein the feed weight ratios of the individual monomers are controlled to values within the ranges of: S.sub.1 + S.sub.2 = 90 to 65 (parts by weight) B = 10 to 35 (parts by weight) S.sub.1 /(S.sub.1 + S.sub.2) = 0.35 to 0.90 S.sub.2 /B = 0.2 to 3.0 and the polymerization is effected in the presence of 0.01 to 5 mole % of a Lewis base compound based on the total monomer, to produce a block copolymer having an average molecular weight in the range from 0.5 to 1.8 dl/g in terms of intrinsic viscosity as measured in toluene at 30° C.
Claim 4
Dependent Claim
231 words
A process for producing a transparent block copolymer resin which comprises subjecting 90 to 65 parts by weight of a vinyl aromatic compound monomer and 10 to 35 parts by weight of a conjugated diene monomer to 2-stage block copolymerization in an inert hydrocarbon solvent using an organo-dilithium compound as an initiator, characterized in that at the first stage of polymerization, S 1 parts by weight of the vinyl aromatic compound monomer is added and substantially all of the monomer is polymerized, and then, at the second stage of polymerization, a mixture of S 2 parts by weight of the vinyl aromatic compound monomer and B parts by weight of the conjugated diene monomer is added and the polymerization is continued to polymerize substantially all of the monomers, wherein the feed weight ratios of the individual monomers are controlled to values within the ranges of: S.sub.1 + S.sub.2 = 90 to 65 (parts by weight) B = 10 to 35 (parts by weight) S.sub.1 /(S.sub.1 + S.sub.2) = 0.35 to 0.90 S.sub.2 /B = 0.2 to 3.0 and the polymerization is effected in the presence of 0.01 to 5 mole % of a Lewis base compound based on the total monomer, to produce a block copolymer having an average molecular weight in the range from 0.5 to 1.8 dl/g in terms of intrinsic viscosity as measured in toluene at 30° C.
Claim 5
Dependent Claim
31 words
A process according to claim 2, wherein the organo-dilithium compound is 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 6
Dependent Claim
22 words
A process according to claim 3, wherein the organo-dilithium compound is one member selected from the group consisting of oligobutadienyl-dilithium and oligoisoprenyl-dilithium.
Claim 7
Dependent Claim
26 words
A process according to claim 2, wherein the organo-dilithium compound is used in a proportion of 0.01 to 1.5 mole % based on the total monomer.
Claim 8
Dependent Claim
25 words
A process according to claim 2 wherein the vinyl aromatic compound monomer is one member selected from the group consisting of styrene, α-methylstyrene and vinyltoluene.
Claim 9
Dependent Claim
25 words
A process according to claim 3 wherein the vinyl aromatic compound monomer is one member selected from the group consisting of styrene, α-methylstyrene and vinyltoluene.
Claim 10
Dependent Claim
24 words
A process according to claim 2 wherein the conjugated diene monomer is one member selected from the group consisting of 1,3-butadiene, isoprene and piperylene.
Claim 11
Dependent Claim
24 words
A process according to claim 3 wherein the conjugated diene monomer is one member selected from the group consisting of 1,3-butadiene, isoprene and piperylene.
Claim 12
Dependent Claim
25 words
A process according to claim 2 wherein the inert hydrocarbon solvent is a paraffinic, naphthenic or aromatic inert hydrocarbon having 3 to 20 carbon atoms.
Claim 13
Dependent Claim
25 words
A process according to claim 3 wherein the inert hydrocarbon solvent is a paraffinic, naphthenic or aromatic inert hydrocarbon having 3 to 20 carbon atoms.
Claim 14
Dependent Claim
31 words
A process according to claim 2 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 15
Dependent Claim
31 words
A process according to claim 3 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 16
Dependent Claim
20 words
A process according to claim 2 wherein the Lewis base compound is an ether compound or a tertiary amine compound.
Claim 17
Dependent Claim
20 words
A process according to claim 3 wherein the Lewis base compound is an ether compound or a tertiary amine compound.
Claim 18
Dependent Claim
27 words
A process according to claim 2 wherein the Lewis base compound is used in a proportion of 0.05 to 2 mole % based on the total monomer.
Claim 19
Dependent Claim
27 words
A process according to claim 3 wherein the Lewis base compound is used in a proportion of 0.05 to 2 mole % based on the total monomer.
Claim 20
Dependent Claim
33 words
A process according to claim 2 wherein the organo-monolithium compound is one member selected from the group consisting of ethyllithium, propyllithium, butyllithium, amyllithium, hexyllithium, 2-ethylhexyllithium, cyclohexyllithium, decyllithium, dodecyllithium, phenyllithium, tolyllithium, xylyllithium and naphthyllithium.
Claim 21
Dependent Claim
26 words
A process according to claim 2 wherein the organo-monolithium compound is used in a proportion of 0.01 to 1.5 mole % based on the total monomer.
Claim 22
Dependent Claim
22 words
A process according to claim 2 wherein the polymerization is effected at a temperature in the range from 20° to 120° C.
Claim 23
Dependent Claim
22 words
A process according to claim 3 wherein the polymerization is effected at a temperature in the range from 20° to 120° C.
Claim 24
Dependent Claim
40 words
A process according to claim 2 wherein, after completion of the polymerization, the polymerization liquid 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 25
Dependent Claim
40 words
A process according to claim 3 wherein, after completion of the polymerization, the polymerization liquid 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 26
Dependent Claim
8 words
Block copolymer resins produced according to claim 2.
Claim 27
Dependent Claim
8 words
Block copolymer resins produces according to claim 3.
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) | 1980-10-17 | 1981-04-18 | 1981-10-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-10-17 | 1985-04-18 | 1985-10-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-10-17 | 1989-04-18 | 1989-10-18 | $7700.00 | Window Closed / Lapsed |