US3711575A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Three stage emulsion and suspension in process for production of impact resistant thermoplastic resins
Assignee: Resonac Corp
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Filing: 1971-01-28
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Granted: 1973-01-16
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Expires: 1991-01-28
Abstract
Abstract Thermoplastic resins capable of forming molded articles having few flow marks, and a high falling ball impact strength can be produced by polymerizing (I) 1 to 30 percent by weight of tricyclodecenyl acrylate or methacrylate, (II) 50 to 99 percent by weight of at least one alkyl acrylate in which the alkyl group has 1 to 13 carbon atoms and (III) 0 to 20 percent by weight of at least one vinyl compound copolymerizable with said alkyl acrylate (II), in an aqueous emulsion to form a copolymer (A), radical-polymerizing, in the presence of 50 to 90 percent by weight (on solid basis) of the thus obtained aqueous copolymer (A) emulsion, 50 to 10 percent by weight of a monomer mixture (B) comprising 0 to 60 percent by weight of methyl methacrylate, 25 to 80 percent by weight of an aromatic vinyl monomer, 6 to 30 percent by weight of acrylonitrile, and 1 to 10 percent by weight of at least one monomer selected from the group consisting of tricyclodecenyl acrylate, tricyclodecenyl methacrylate, and nonconjugated divinyl compounds, to form a pre-graft-copolymer (C), and subsequently subjecting to graft-copolymerization 10 to 40 percent by weight (on solid basis) of the thus obtained aqueous pre-graft-copolymer (C) emulsion and 90 to 60 percent by weight of a monomer mixture (D) comprising 30 to 60 percent by weight of methyl methacrylate, 60 to 30 percent by we
Inventors
- 👤 K Kakefuda
- 👤 T Ito
- 👤 Y Okano
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 07:33
CPC Classifications
C; C08; C08F; C08F265/00; C08F265/04; C08F285/00
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
274 words
A process for producing an impact resistant, thermoplastic resin having few flow marks, which comprises (1) polymerizing (I) 1 to 30 percent by weight of tricyclodecenyl acrylate or tricyclodecenyl methacrylate, (II) 50 to 99 percent by weight of at least one alkyl acrylate in which the alkyl group has one to 13 carbon atoms and (III) 0 to 20 percent by weight of at least one vinyl compound copolymerizable with said alkyl acrylate (II), in an aqueous emulsion to form a copolymer (A), then (2) radicalpolymerizing, in the presence of 50 to 90 percent by weight, on solid basis, of the resulting aqueous copolymer (A) emulsion, 50 to 10 percent by weight of a monomer mixture (B) comprising 0 to 60% by weight of methyl methacrylate, 25 to 80 percent by weight of an aromatic vinyl monomer, 6 to 30 percent by weight of acrylonitrile and 1 to 10 percent by weight of at least one monomer selected from the group consisting of tricyclodecenyl acrylate, tricyclodecenyl methacrylate and non-conjugated divinyl compounds, to form a pregraft-copolymer (C), (3) subsequently subjecting to graft-copolymerization 10 to 40 percent by weight, on solid basis, of the thus obtained aqueous pregraft-copolymer (C) emulsion and 90 to 60 percent by weight of a monomer mixture (D) comprising 30 to 60 percent by weight of methyl methacrylate, 60 to 30 percent by weight of an aromatic vinyl monomer and 8 to 21% by weight of acrylonitrile, in the presence of a radicalcopolymerization initiator and (4) adding during such graftcopolymerization a partially saponified polyvinyl alcohol in an amount sufficient to convert the emulsion to a suspension in the course of the polymerization.
Claim 2
Dependent Claim
274 words
A process for producing an impact resistant, thermoplastic resin having few flow marks, which comprises (1) polymerizing (I) 1 to 30 percent by weight of tricyclodecenyl acrylate or tricyclodecenyl methacrylate, (II) 50 to 99 percent by weight of at least one alkyl acrylate in which the alkyl group has one to 13 carbon atoms and (III) 0 to 20 percent by weight of at least one vinyl compound copolymerizable with said alkyl acrylate (II), in an aqueous emulsion to form a copolymer (A), then (2) radicalpolymerizing, in the presence of 50 to 90 percent by weight, on solid basis, of the resulting aqueous copolymer (A) emulsion, 50 to 10 percent by weight of a monomer mixture (B) comprising 0 to 60% by weight of methyl methacrylate, 25 to 80 percent by weight of an aromatic vinyl monomer, 6 to 30 percent by weight of acrylonitrile and 1 to 10 percent by weight of at least one monomer selected from the group consisting of tricyclodecenyl acrylate, tricyclodecenyl methacrylate and non-conjugated divinyl compounds, to form a pregraft-copolymer (C), (3) subsequently subjecting to graft-copolymerization 10 to 40 percent by weight, on solid basis, of the thus obtained aqueous pregraft-copolymer (C) emulsion and 90 to 60 percent by weight of a monomer mixture (D) comprising 30 to 60 percent by weight of methyl methacrylate, 60 to 30 percent by weight of an aromatic vinyl monomer and 8 to 21% by weight of acrylonitrile, in the presence of a radicalcopolymerization initiator and (4) adding during such graftcopolymerization a partially saponified polyvinyl alcohol in an amount sufficient to convert the emulsion to a suspension in the course of the polymerization.
Claim 3
Dependent Claim
36 words
A process according to claim 1, wherein the component (III) is selected from the group consisting of styrene, Alpha -methylstyrene, acrylonitrile, methacrylonitrile, alkyl vinyl ethers, acrylic acid, methacrylic acid, alkyl acrylates, alkyl methacrylates, acrylamide and methacrylamide.
Claim 4
Dependent Claim
27 words
A process according to claim 1, wherein the aromatic vinyl monomer is selected from the group consisting of styrene, Alpha -methylstyrene, Alpha -ethylstyrene, vinyl toluene and chlorostyrene.
Claim 5
Dependent Claim
34 words
A process according to claim 1, wherein the non-conjugated divinyl compound is selected from the group consisting of divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate and triallyl cyanurate.
Claim 6
Dependent Claim
23 words
A process according to claim 1, wherein the copolymer (A) is formed in the presence of a polymerization initiator of the redox type.
Claim 7
Dependent Claim
28 words
A process according to claim 1, wherein the graft-copolymerization of the monomer mixture (D) on the pre-graft-copolymer (C) is effected in the presence of a chain transfer agent.
Claim 8
Dependent Claim
28 words
A process according to claim 6, wherein the amount of the chain transfer agent is 1 percent by weight or less based on the weight of component (D).
Claim 9
Dependent Claim
14 words
A process according to claim 6, wherein the chain transfer agent is tert-dodecyl mercaptan.
Claim 10
Dependent Claim
29 words
A process according to claim 1, wherein the partially saponified polyvinyl alcohol has a polymerization degree of 1,000 to 2,000 and a saponification degree of 80 to 90 percent.
Claim 11
Dependent Claim
13 words
An impact resistant, thermoplastic resin obtained according to the process of claim 1.
Claim 12
Dependent Claim
31 words
A process according to claim 1, wherein said partially saponified polyvinyl alcohol is added when the viscosity of the emulsion during the graft-copolymerization has increased such that smooth agitation becomes difficult.
Claim 13
Dependent Claim
19 words
A process according to claim 11, wherein the polyvinyl alcohol is added when the polymerization conversion exceeds about 60%.
Claim 14
Dependent Claim
23 words
A process according to claim 1, wherein, the tricyclo-Decenyl acrylate or tricyclodecenyl methacrylate have the formula: or wherein R is H or CH3.
Claim 15
Dependent Claim
23 words
A process according to claim 1, wherein, the tricyclodecenyl acrylate is tricyclo( 5.2.1.02,6)dec-3-en-8(or -9)-yl acrylate and the tricyclodecenyl methacrylate is tricyclo(5.2.1.02,6)dec-3-en-8(or -9)-yl methacrylate.
References Cited (Backward Citations)
US3450796A
Cited
US3448173A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1976-01-16 | 1976-07-17 | 1977-01-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1980-01-16 | 1980-07-17 | 1981-01-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1984-01-16 | 1984-07-17 | 1985-01-16 | $7700.00 | Window Closed / Lapsed |