US4567234A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Graft copolymers of alkyl methacrylates onto cross-linked butadiene - alkyl acrylate copolymers and their use as impact modifiers
Assignee: Societe National Elf Aquitaine
•
Filing: 1984-06-22
•
Granted: 1986-01-28
•
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 a polyfunctional cross-linking agent, onto which are grafted the chains of a polymer of an alkyl methacrylate of a C 1 to C 4 alkyl, particularly methyl methacrylate. 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 weight ratio of grafted chains to 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 23:26
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: 33
Claim 1
Independent Claim
157 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, and a polyfunctional crosslinking agent copolymerizable with the diene and alkyl acrylate, said polyfunctional cross-linking agent having at least two allyl or vinyl unsaturated [CH 2 ═C] groups and being present in a molar proportion of from about 0.02% to about 10%, and wherein the butadiene or isoprene represents from 0.5 to about 35% of the weight of the backbone, and (ii) a polymer grafted onto said backbone, said grafted polymer consisting essentially of a polymer of a C1-C4 alkyl methacrylate said grafted polymer representing from 10 to 200% of the weight of the backbone.
Claim 2
Dependent Claim
157 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, and a polyfunctional crosslinking agent copolymerizable with the diene and alkyl acrylate, said polyfunctional cross-linking agent having at least two allyl or vinyl unsaturated [CH 2 ═C] groups and being present in a molar proportion of from about 0.02% to about 10%, and wherein the butadiene or isoprene represents from 0.5 to about 35% of the weight of the backbone, and (ii) a polymer grafted onto said backbone, said grafted polymer consisting essentially of a polymer of a C1-C4 alkyl methacrylate said grafted polymer representing from 10 to 200% of the weight of the backbone.
Claim 3
Dependent Claim
57 words
A resin composition according to claim 1, in which the cross-linking agent is selected from the group consisting of one or more of 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, and divinylbenzene.
Claim 4
Dependent Claim
49 words
A composition according to claim 1, in which the crosslinking 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 5
Dependent Claim
24 words
A composition according to claim 1 in which the crosslinking agent is present in a molar proportion of from about 0.2% to about 10%.
Claim 6
Dependent Claim
28 words
A composition according to claim 1 in which the polymerized butadiene or isoprene in the backbone is from about 1 to about 25% by weight of the backbone.
Claim 7
Dependent Claim
18 words
A composition according to claim 1 in which the alkyl methacrylate of the grafted polymer is methyl methacrylate.
Claim 8
Dependent Claim
19 words
A composition according to claim 1 in which the thermoplastic polymer comprises a homopolymer or copolymer of vinyl chloride.
Claim 9
Dependent Claim
22 words
A composition according to claim 1 in which the grafted polymer is from 10% to 60% of the weight of the backbone.
Claim 10
Dependent Claim
139 words
A thermoplastic resin composition according to claim 1, 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 which 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 polymer grafted onto said backbone, said grafted polymer consisting essentially of a polymer of methyl methacrylate, the grafted polymer being from about 10% to about 60% of the weight of the backbone.
Claim 11
Dependent Claim
31 words
A composition according to claim 9 which is from about 2 to about 10 parts by weight of graft copolymer impact additive per 100 parts by weight of vinyl chloride polymer.
Claim 12
Dependent Claim
21 words
A composition according to claim 9 in which the backbone is from 0.05 to 7 mole % of polyfunctional crosslinking agent.
Claim 13
Dependent Claim
48 words
A composition according to claim 11 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, trimethylol propane triacrylate or trimethacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalates, diallyl itaconate or divinylbenzene.
Claim 14
Dependent Claim
50 words
A composition according to claim 9 in which the crosslinking 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 15
Independent Claim
127 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 which 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 from 0.02 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 polymer grafted onto said backbone, said grafted polymer being 10% to 200% of the weight of the backbone and consisting essentially of a polymer of a C 1 -C 4 alkyl methacrylate.
Claim 16
Independent Claim
127 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 which 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 from 0.02 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 polymer grafted onto said backbone, said grafted polymer being 10% to 200% of the weight of the backbone and consisting essentially of a polymer of a C 1 -C 4 alkyl methacrylate.
Claim 17
Dependent Claim
56 words
A method according to claim 14 in which the backbone contains 0.02 to 10 mole % of a cross-linking agent which 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 18
Dependent Claim
58 words
A method according to claim 14 in which the backbone is 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 19
Dependent Claim
21 words
A method according to claim 14 in which the backbone is from 1 to 25% by weight of butadiene or isoprene.
Claim 20
Dependent Claim
25 words
A method according to claim 17 in which the backbone is a copolymer of butadiene or isoprene with a C 1 -C 4 alkyl acrylate.
Claim 21
Dependent Claim
17 words
A composition according to claim 14 in which the grafted polymer is a polymer of methyl methacrylate.
Claim 22
Dependent Claim
19 words
A method according to claim 14 in which the thermoplastic resin comprises a homopolymer or copolymer of vinyl chloride.
Claim 23
Dependent Claim
28 words
A method according to claim 20 in which the graft copolymer impact modifier is incorporated in an amount of from 1 to 30% by weight of the resin.
Claim 24
Dependent Claim
30 words
A method according to claim 14 which comprises incorporating from about 2 to about 10% by weight of the graft copolymer impact modifier into a vinyl chloride homopolymer or copolymer.
Claim 25
Dependent Claim
55 words
A method according to claim 14 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 26
Dependent Claim
120 words
A graft copolymer which consisting essentially of (i) a backbone which 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 from 0.02 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 27
Dependent Claim
120 words
A graft copolymer which consisting essentially of (i) a backbone which 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 from 0.02 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 28
Dependent Claim
58 words
A graft copolymer according to claim 24 in which the backbone is 0.02 to 10 mole % of a cross-linking agent which is a 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 29
Dependent Claim
60 words
A graft copolymer according to claim 24 in which the backbone is 0.02 to 10 mole % of a cross-linking agent which is a 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 30
Dependent Claim
22 words
A graft copolylmer according to claim 24 in which the backbone is from 1 to 25% by weight of butadiene or isoprene.
Claim 31
Dependent Claim
26 words
A graft copolymer according to claim 27 in which the backbone is a copolymer of butadiene or isoprene with a C 1 -C 4 alkyl acrylate.
Claim 32
Dependent Claim
18 words
A graft copolymer according to claim 24 in which the grafted polymer is a polymer of methyl methacrylate.
Claim 33
Dependent Claim
50 words
A graft copolymer according to claim 24 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.
References Cited (Backward Citations)
US3041309A
Cited
US3264373A
Cited
US3655825A
Cited
US3749755A
Cited
US3678133A
Cited
US3842144A
Cited
US3886235A
Cited
US3787522A
Cited
US3959408A
Cited
US4014842A
Cited
US3922321A
Cited
US4078018A
Cited
US3985703A
Cited
US4229549A
Cited
US4173596A
Cited
US4376843A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1989-01-27 | 1989-07-29 | 1990-01-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1993-01-27 | 1993-07-29 | 1994-01-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1997-01-27 | 1997-07-29 | 1998-01-28 | $7700.00 | Window Closed / Lapsed |