US4542185A
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Graft copolymers of alkyl methacrylates--alkyl acrylates onto diene--alkyl acrylate copolymers and their use as impact modifiers
Assignee: NATIONALE ELF AQUITAINE TOUR AQUITAINE Ste
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Filing: 1984-06-22
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Granted: 1985-09-17
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Expires: 2004-06-22
Abstract
Abstract The impact resistance of resin compositions consisting of a thermoplastic polymer, particularly a homopolymer or copolymer of vinyl chloride can be improved by an impact additive of the graft copolymer type. The graft copolymer impact additive consists of a backbone composed of a statistical copolymer of butadiene or isoprene, an alkyl acrylate of a C 2 to C 12 alkyl, and optionally a polyfunctional cross-linking agent, onto which are grafted the chains of a statistical copolymer of an alkyl methacrylate of a C 1 to C 4 alkyl, particularly methyl methacrylate, and an alkyl acrylate of a C 1 to C 8 alkyl, particularly ethyl acrylate. The backbone of the graft copolymer impact additive comprises 0.5-35% by weight butadiene or isoprene, and up to 10 mole % of the cross-linking agent, while the graft chains of the graft copolymer comprise 5 to 50 mole % of the alkyl acrylate of a C 1 to C 8 alkyl, and the weight ratio between the grafted chains and the backbone can range from 10 to 200%. The resin compositions are particularly useful to improve impact strength at low temperatures.
Inventors
- 👤 Gilles Meunier
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 04:19
CPC Classifications
C; C08; C08F; C08F265/00; C08F265/04; C08F265/06; C08L; C08L27/00; C08L27/02; C08L27/04; C08L27/06; C08L51/00; C08L51/04
Claims Analysis
Total Claims: 43
Claim 1
Independent Claim
137 words
A synthetic resin composition having improved impact strength which comprises (a) a thermoplastic polymer (b) from 0.5 to 50 parts by weight per 100 parts by weight of thermoplastic polymer of a graft copolymer impact additive which comprises (i) a backbone consisting essentially of a statistical copolymer of butadiene or isoprene with an alkyl acrylate of C 2 to C 12 alkyl, wherein the butadiene or isoprene represents from about 0.5 to about 35% of the weight of the backbone; (ii) a copolymer grafted onto said backbone, said grafted copolymer consisting essentially of a statistical copolymer of C 1 -C 4 alkyl methacrylate with a C 1 -C 8 alkyl acrylate, said alkyl acrylate comprising a molar proportion of from 5 to 50%, said grafted copolymer representing from 10 to 200% of the weight of the backbone.
Claim 2
Dependent Claim
137 words
A synthetic resin composition having improved impact strength which comprises (a) a thermoplastic polymer (b) from 0.5 to 50 parts by weight per 100 parts by weight of thermoplastic polymer of a graft copolymer impact additive which comprises (i) a backbone consisting essentially of a statistical copolymer of butadiene or isoprene with an alkyl acrylate of C 2 to C 12 alkyl, wherein the butadiene or isoprene represents from about 0.5 to about 35% of the weight of the backbone; (ii) a copolymer grafted onto said backbone, said grafted copolymer consisting essentially of a statistical copolymer of C 1 -C 4 alkyl methacrylate with a C 1 -C 8 alkyl acrylate, said alkyl acrylate comprising a molar proportion of from 5 to 50%, said grafted copolymer representing from 10 to 200% of the weight of the backbone.
Claim 3
Dependent Claim
50 words
A composition according to claim 1 in which the backbone further comprises a polyfunctional cross-linking agent copolymerizable with the diene and alkyl acrylate, said polyfunctional cross-linking agent having at least two unsaturated CH 2 ═C< groups and being present in a molar proportion of from about 0.02% to about 10%.
Claim 4
Dependent Claim
47 words
A resin composition according to claim 2, in which the cross-linking agent is allyl acrylate or methacrylate, alkylene glycol diacrylate or dimethacrylate with 2 to 10 atoms of carbon in the alkylene chain, trimethylolpropane triacrylate or trimethacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl itaconate or divinylbenzene.
Claim 5
Dependent Claim
49 words
A composition according to claim 2, in which the cross-linking agent is a polyoxyalkylene glycol diacrylate or dimethylacrylate with the formula ##STR2## in which X is hydrogen or methyl, n is a whole number ranging from 2 to 4, and p is whole number ranging from 2 to 20.
Claim 6
Dependent Claim
24 words
A composition according to claim 2 in which the cross-linking agent is present in a molar proportion of from about 0.2% to about 10%.
Claim 7
Dependent Claim
28 words
A composition according to claim 1 in which the polymerized butadiene or isoprene in the backbone comprises from about 1 to about 25% by weight of the backbone.
Claim 8
Dependent Claim
18 words
A composition according to claim 1 in which the alkyl methacrylate of the grafted copolymer is methyl methacrylate.
Claim 9
Dependent Claim
21 words
A composition according to claim 1 in which the alkyl acrylate of the grafted copolymer is C 1 -C 4 alkyl.
Claim 10
Dependent Claim
18 words
A composition according to claim 1 in which the alkyl acrylate of the grafted copolymer is ethyl acrylate.
Claim 11
Dependent Claim
29 words
A composition according to claim 1 in which the alkyl acrylate of the grafted polymer comprises a molar proportion of about 10 to about 30% of the grafted chains.
Claim 12
Dependent Claim
19 words
A composition according to claim 1 in which the thermoplastic polymer comprises a homopolymer or copolymer of vinyl chloride.
Claim 13
Dependent Claim
22 words
A composition according to claim 1 in which the grafted copolymer is from 10% to 60% of the weight of the backbone.
Claim 14
Dependent Claim
165 words
A thermoplastic resin composition having improved low temperature impact strength which comprises (a) a homopolymer or copolymer of vinyl chloride and (b) from 1 to 30 parts by weight per 100 parts by weight of vinyl chloride polymer of a graft copolymer impact additive which comprises (i) a backbone consisting essentially of a statistical polymer containing 1 to 25% by weight of butadiene or isoprene, up to 10 mole % of polyfunctional cross-linking agent containing at least two CH 2 ═C< groups in its molecule, and an alkyl acrylate where the alkyl group is C 1 -C 4 alkyl and (ii) a copolymer grafted onto said backbone, said grafted copolymer consisting essentially of a statistical copolymer of methyl methacrylate and an alkyl acrylate where the alkyl is C 1 -C 4 alkyl, the molar proportion of alkyl acrylate in said grafted copolymer being from about 10 to about 30%, the grafted copolymer being from about 10% to about 60% of the weight of the backbone.
Claim 15
Dependent Claim
165 words
A thermoplastic resin composition having improved low temperature impact strength which comprises (a) a homopolymer or copolymer of vinyl chloride and (b) from 1 to 30 parts by weight per 100 parts by weight of vinyl chloride polymer of a graft copolymer impact additive which comprises (i) a backbone consisting essentially of a statistical polymer containing 1 to 25% by weight of butadiene or isoprene, up to 10 mole % of polyfunctional cross-linking agent containing at least two CH 2 ═C< groups in its molecule, and an alkyl acrylate where the alkyl group is C 1 -C 4 alkyl and (ii) a copolymer grafted onto said backbone, said grafted copolymer consisting essentially of a statistical copolymer of methyl methacrylate and an alkyl acrylate where the alkyl is C 1 -C 4 alkyl, the molar proportion of alkyl acrylate in said grafted copolymer being from about 10 to about 30%, the grafted copolymer being from about 10% to about 60% of the weight of the backbone.
Claim 16
Dependent Claim
31 words
A composition according to claim 13 which contains from about 2 to about 10 parts by weight of graft copolymer impact additive per 100 parts by weight of vinyl chloride polymer.
Claim 17
Dependent Claim
21 words
A composition according to claim 13 in which the backbone contains from 0.05 to 7 mole % of polyfunctional cross-linking agent.
Claim 18
Dependent Claim
47 words
A composition according to claim 15 in which the polyfunctional cross-linking agent comprises allyl acrylate or methacrylate, alkylene glycol diacrylate or dimethacrylate with 2 to 10 atoms of carbon in the alkylene chain, trimethylolpropane triacrylate or trimethacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalates, diallyl itaconate or divinylbenzene.
Claim 19
Dependent Claim
50 words
A composition according to claim 13 in which the cross-linking agent is a polyoxyalkylene glycol diacrylate or dimethylacrylate with the formula ##STR3## in which X is hydrogen or methyl, n is a whole number ranging from 2 to 4, and p is a whole number ranging from 2 to 20.
Claim 20
Independent Claim
139 words
A method for improving the impact resistance of a thermoplastic resin which comprises incorporating therein from 0.5 to 50% by weight of a graft copolymer impact additive which comprises (i) a backbone consisting essentially of a statistical copolymer containing 0.5 to 35% by weight of butadiene or isoprene, an alkyl acrylate where the alkyl group is C 2 -C 12 alkyl, and up to 10 mole % of a polyfunctional cross-linking agent copolymerizable with the diene and alkyl acrylate and which contains at least two CH 2 ═C< groups, and (ii) a copolymer grafted onto said backbone, said grafted copolymer being 10% to 200% of the weight of the backbone and consisting essentially of a statistical copolymer of a C 1 -C 4 alkyl methacrylate with 5 to 50 mole % of a C 1 -C 8 alkyl acrylate.
Claim 21
Independent Claim
139 words
A method for improving the impact resistance of a thermoplastic resin which comprises incorporating therein from 0.5 to 50% by weight of a graft copolymer impact additive which comprises (i) a backbone consisting essentially of a statistical copolymer containing 0.5 to 35% by weight of butadiene or isoprene, an alkyl acrylate where the alkyl group is C 2 -C 12 alkyl, and up to 10 mole % of a polyfunctional cross-linking agent copolymerizable with the diene and alkyl acrylate and which contains at least two CH 2 ═C< groups, and (ii) a copolymer grafted onto said backbone, said grafted copolymer being 10% to 200% of the weight of the backbone and consisting essentially of a statistical copolymer of a C 1 -C 4 alkyl methacrylate with 5 to 50 mole % of a C 1 -C 8 alkyl acrylate.
Claim 22
Dependent Claim
56 words
A method according to claim 18 in which the backbone contains 0.02 to 10 mole % of a cross-linking agent selected from allyl acrylate or methacrylate, alkylene glycol diacrylate or dimethacrylate with 2 to 10 atoms of carbon in the alkylene chain, trimethylolpropane triacrylate or trimethacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl itaconate or divinylbenzene.
Claim 23
Dependent Claim
58 words
A method according to claim 18 in which the backbone contains 0.02 to 10 mole % of a cross-linking agent selected from polyoxyalkylene glycol diacrylate or dimethylacrylate with the formula ##STR4## in which X is hydrogen or methyl, n is a whole number ranging from 2 to 4, and p is whole number ranging from 2 to 20.
Claim 24
Dependent Claim
21 words
A method according to claim 18 in which the backbone contains from 1 to 25% by weight of butadiene or isoprene.
Claim 25
Dependent Claim
27 words
A method according to claim 21 in which the backbone consisting essentially of a copolymer of butadiene or isoprene with a C 1 -C 4 alkyl acrylate.
Claim 26
Dependent Claim
25 words
A method according to claim 18 in which the grafted copolymer is a copolymer of methyl methacrylate with a C 1 -C 4 alkyl acrylate.
Claim 27
Dependent Claim
24 words
A method according to claim 23 in which the grafted copolymer contains 10 to 30 mole % of C 1 -C 4 alkyl acrylate.
Claim 28
Dependent Claim
13 words
A composition according to claim 24 in which alkyl acrylate is ethyl acrylate.
Claim 29
Dependent Claim
19 words
A method according to claim 18 in which the thermoplastic resin comprises a homopolymer or copolymer of vinyl chloride.
Claim 30
Dependent Claim
28 words
A method according to claim 26 in which the graft copolymer impact modifier is incorporated in an amount of from 1 to 30% by weight of the resin.
Claim 31
Dependent Claim
29 words
A method according to claim 18 which comprises incorporating from about 2 to about 10% by weight of graft copolymer impact modifier into a vinyl chloride homopolymer or copolymer.
Claim 32
Dependent Claim
55 words
A method according to claim 18 in which the graft copolymer impact additive has a molten viscosity of between 6 and 40 Nm for the torque of a Brabender rheometer determined using 50 gms of impact additive maintained in said rheometer for 20 minutes at 200° C. with a rotor rotation rate of 40 rpm.
Claim 33
Dependent Claim
115 words
A graft copolymer which comprises: (i) a backbone consisting essentially of a statistical copolymer containing 0.5 to 35% by weight of butadiene or isoprene, an alkyl acrylate where the alkyl group is C 2 -C 12 alkyl, and up to 10 mole % of a polyfunctional cross-linking agent copolymerizable with the diene and alkyl acrylate and which contains at least two CH 2 ═C< groups, and (ii) a copolymer grafted onto said backbone, said grafted copolymer being 10% to 200% of the weight of the backbone and consisting essentially of a statistical copolymer of a C 1 -C 4 alkyl methacrylate with 5 to 50 mole % of a C 1 -C 8 alkyl acrylate.
Claim 34
Dependent Claim
115 words
A graft copolymer which comprises: (i) a backbone consisting essentially of a statistical copolymer containing 0.5 to 35% by weight of butadiene or isoprene, an alkyl acrylate where the alkyl group is C 2 -C 12 alkyl, and up to 10 mole % of a polyfunctional cross-linking agent copolymerizable with the diene and alkyl acrylate and which contains at least two CH 2 ═C< groups, and (ii) a copolymer grafted onto said backbone, said grafted copolymer being 10% to 200% of the weight of the backbone and consisting essentially of a statistical copolymer of a C 1 -C 4 alkyl methacrylate with 5 to 50 mole % of a C 1 -C 8 alkyl acrylate.
Claim 35
Dependent Claim
57 words
A graft copolymer according to claim 30 in which the backbone contains 0.02 to 10 mole % of a cross-linking agent selected from allyl acrylate or methacrylate, alkylene glycol diacrylate or dimethacrylate with 2 to 10 atoms of carbon in the alkylene chain, trimethylolpropane triacrylate or trimethacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl itaconate or divinylbenzene.
Claim 36
Dependent Claim
59 words
A graft copolymer according to claim 30 in which the backbone contains 0.02 to 10 mole % of a cross-linking agent selected from polyoxyalkylene glycol diacrylate or dimethylacrylate with the formula ##STR5## in which X is hydrogen or methyl, n is a whole number ranging from 2 to 4, and p is whole number ranging from 2 to 20.
Claim 37
Dependent Claim
22 words
A graft copolymer according to claim 30 in which the backbone contains from 1 to 25% by weight of butadiene or isoprene.
Claim 38
Dependent Claim
28 words
A graft copolymer according to claim 33 in which the backbone consisting essentially of a copolymer of butadiene or isoprene with a C 1 -C 4 alkyl acrylate.
Claim 39
Dependent Claim
26 words
A graft copolymer according to claim 30 in which the grafted copolymer is a copolymer of methyl methacrylate with a C 1 -C 4 alkyl acrylate.
Claim 40
Dependent Claim
25 words
A graft copolymer according to claim 35 in which the grafted copolymer contains 10 to 30 mole % of C 1 -C 4 alkyl acrylate.
Claim 41
Dependent Claim
14 words
A graft copolymer according to claim 36 in which alkyl acrylate is ethyl acrylate.
Claim 42
Dependent Claim
50 words
A graft copolymer according to claim 30 which has a molten viscosity of between 6 and 40 Nm for the torque of a Brabender rheometer determined using 50 gms of impact additive maintained in said rheometer for 20 minutes at 200° C. with a rotor rotation rate of 40 rpm.
Claim 43
Dependent Claim
23 words
A composition according to claim 1 wherein the graft copolymer further comprises a polyfunctional cross-linking agent copolymerizable with the diene and alkyl acrylate.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-09-16 | 1989-03-18 | 1989-09-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-09-16 | 1993-03-18 | 1993-09-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-09-16 | 1997-03-18 | 1997-09-17 | $7700.00 | Window Closed / Lapsed |