US4035345A
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Thermosetting bis-imide compositions
Assignee: Rhone Poulenc SA
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Filing: 1971-06-23
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Granted: 1977-07-12
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Expires: 1991-06-23
Abstract
Abstract A thermosetting composition is provided which comprises the reaction product of (a) at least one N,N'-bis-imide of an unsaturated dicarboxylic acid, of general formula <IMAGE> (I) in which T represents a divalent organic radical containing a carbon-carbon double bond and Q is a divalent organic radical of 2 to 30 carbon atoms, (b) at least one polyamine of general formula R (NH2)x IN WHICH X IS AN INTEGER AT LEAST EQUAL TO 2, AND R represents an organic radical of valency x, the bis-imide being present in an amount of 0.55 to 25 mols per molar -NH2 group of the polyamine, and (c) at least one monomer other than a bis-imide of formula (I), which contains a carbon-carbon double bond and is heat-polymerizable.
Inventors
- 👤 Maurice Ducloux
- 👤 Pierre Ledru
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 22:38
CPC Classifications
C; C08; C08G; C08G59/00; C08G59/18; C08G59/40; C08G59/4007; C08G59/4014; C08G59/4042; C08F; C08F283/00; C08F283/04; C08G73/00; C08G73/06; C08G73/10; C08G73/12; C08G73/121; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31551; Y10T428/31623
Claims Analysis
Total Claims: 25
Claim 1
Independent Claim
297 words
A thermosetting composition which consists essentially of the reaction product obtained by heating between 50° and 180° C. (a) at least one N,N'-bis-imide of an unsaturated dicarboxylic acid, of general formula: ##STR11## in which T represents a divalent organic radical containing a carbon-carbon double bond derived from an ethylenic dicarboxylic acid anhydride of formula: ##STR12## and Q is a divalent organic radical of 2 to 30 carbon atoms, (b) at least one polyamine of general formula: R (NH.sub.2).sub.x in which x is an integer from 2 to 5, and R represents an organic radical of valency x, the bis-imide being present in an amount from 0.55 to 25 mols per molar -NH 2 group of the polyamine, and (c) 5 to 60% by weight, based on the combined weight of (a) and (b) of at least one monomer possessing at least one vinyl, allyl or acrylic CH 2 ═C< group and polymerisable by heat, selected from the group consisting of a vinyl ester of an acid selected from the group consisting of acetic, propionic, butyric, oxalic, malonic, succinic, adipic, sebacic, acrylic, methacrylic, phenylacrylic, crotonic, maleic, fumaric, citraconic, tetrahydrophthalic, itaconic, acetylene dicarboxylic, benzoic, phenylacetic, ortho-phthalic, terephthalic, isophthalic and trimellitic acid, an allyl ester of an acid selected from the group consisting of acetic, propionic, butyric, oxalic, malonic, succinic, adipic, sebacic, acrylic, methacrylic, phenylacrylic, crotonic, maleic, fumaric, citraconic, tetrahydrophthalic, itaconic, acetylene dicarboxylic, benzoic, phenylacetic, orthophthalic, terephthalic, isophthalic and trimellitic acid, methyl acrylate, methyl methacrylate, styrene, α-methylstyrene, para-chlorostyrene, divinylbenzene, diallylbenzene, vinyl toluene, a vinyl allyl ether, a methallyl ether, a vinyl pryidine, N-vinylpyrrolidone, allyl isocyanurate, allyl cyanurate, a silane containing a group selected from the group consisting of vinyl and allyl, a siloxane containing a group selected from the group consisting of vinyl and allyl, glycidyl acrylate, and glycidyl methacrylate.
Claim 2
Dependent Claim
297 words
A thermosetting composition which consists essentially of the reaction product obtained by heating between 50° and 180° C. (a) at least one N,N'-bis-imide of an unsaturated dicarboxylic acid, of general formula: ##STR11## in which T represents a divalent organic radical containing a carbon-carbon double bond derived from an ethylenic dicarboxylic acid anhydride of formula: ##STR12## and Q is a divalent organic radical of 2 to 30 carbon atoms, (b) at least one polyamine of general formula: R (NH.sub.2).sub.x in which x is an integer from 2 to 5, and R represents an organic radical of valency x, the bis-imide being present in an amount from 0.55 to 25 mols per molar -NH 2 group of the polyamine, and (c) 5 to 60% by weight, based on the combined weight of (a) and (b) of at least one monomer possessing at least one vinyl, allyl or acrylic CH 2 ═C< group and polymerisable by heat, selected from the group consisting of a vinyl ester of an acid selected from the group consisting of acetic, propionic, butyric, oxalic, malonic, succinic, adipic, sebacic, acrylic, methacrylic, phenylacrylic, crotonic, maleic, fumaric, citraconic, tetrahydrophthalic, itaconic, acetylene dicarboxylic, benzoic, phenylacetic, ortho-phthalic, terephthalic, isophthalic and trimellitic acid, an allyl ester of an acid selected from the group consisting of acetic, propionic, butyric, oxalic, malonic, succinic, adipic, sebacic, acrylic, methacrylic, phenylacrylic, crotonic, maleic, fumaric, citraconic, tetrahydrophthalic, itaconic, acetylene dicarboxylic, benzoic, phenylacetic, orthophthalic, terephthalic, isophthalic and trimellitic acid, methyl acrylate, methyl methacrylate, styrene, α-methylstyrene, para-chlorostyrene, divinylbenzene, diallylbenzene, vinyl toluene, a vinyl allyl ether, a methallyl ether, a vinyl pryidine, N-vinylpyrrolidone, allyl isocyanurate, allyl cyanurate, a silane containing a group selected from the group consisting of vinyl and allyl, a siloxane containing a group selected from the group consisting of vinyl and allyl, glycidyl acrylate, and glycidyl methacrylate.
Claim 3
Dependent Claim
15 words
The composition according to claim 1 in which the monomer (c) is an allylic compound.
Claim 4
Dependent Claim
30 words
The composition according to claim 1, in which the monomer (c) is present in an amount from 5% to 50% by weight of the total weight of bis-imide and polyamine.
Claim 5
Dependent Claim
28 words
The composition according to claim 1 in which the bis-imide is present in an amount from 0.6 to 2.5 mols per molar-- NH 2 group of the polyamine.
Claim 6
Dependent Claim
35 words
The composition according to claim 1 in which the polyamine is a di-primary diamine of general formula H.sub.2 N-- E-- NH.sub.2 in which E represents a divalent organic radical of 2 to 30 carbon atoms.
Claim 7
Dependent Claim
12 words
The composition according to claim 5 in which E represents a ##STR13##
Claim 8
Dependent Claim
12 words
The composition according to claim 1 in which Q represents a ##STR14##
Claim 9
Dependent Claim
22 words
The cured thermoset resin obtained by heating a composition as claimed in claim 1 to a temperature from 100° to 280° C.
Claim 10
Dependent Claim
156 words
The composition according to claim 3 in which Q represents a linear or branched alkylene radial having less than 13 carbon atoms, a phenylene or cyclohexylene radical, or a phenylene or cyclohexylene radical substituted by a methyl group, or a ##STR15## radical wherein n represents an integer from 1 to 3, or more than one phenylene, cyclohexylene, methyl-substituted phenylene or methyl-substituted cyclohexylene radical, linked together either by a simple valency bond or by an inert atom or group selected from the group consisting of --O--, --S--, an alkylene group having from 1 to 3 carbon atoms, --CO--, --SO 2 --, NR 1 --, --N═N--, --CONH--, --COO, --P(O)R 1 --, --CONH--X--NHCO--, ##STR16## wherein R 1 represents a hydrogen atom, an alkyl radical having from 1 to 4 carbon atoms, a phenyl or cyclohexyl radical, or a phenyl or cyclohexyl radical substituted by a methyl group, and X represents an alkylene radical having less than 13 carbon atoms.
Claim 11
Dependent Claim
36 words
The composition according to claim 3 in which the bis-imide is selected from the group consisting of N,N'-ethylene-bis-maleimide, N,N'-hexamethylene-bis-maleimide, N,N'-metaphenylene-bis-maleimide, N,N'-para-phenylene-bis-maleimide, N,N'-4,4'-diphenyl-methane-bis-maleimide, N,N'-4,4'-diphenylester-bis-maleimide, N,N'-4,4'-diphenylsulphone-bis-maleimide, N,N'-4,4'-dicyclohexylmethane-bis-maleimide, N,N'-α,α'-4,4'-dimethylene-cyclohexane-bis-maleimide, N,N'-meta-xylylene-bis-maleimide, N,N'-para-xylylene-bis-maleimide, N,N'-4,4'-diphenylcyclohexane-bis-maleimide, N,N'-meta-phenylene-bis-tetrahydrophthalimide, N,N'-4,4'-diphenylmethane-bis-citraconimide, N,N'-4,4'-(1,1-diphenyl-propane)-bis-maleimide, N,N'-4,4'-triphenylmethane-bis-maleimide, N,N'-4,4'-(1,1,1-triphenylethane)-bis-maleimide or N,N'-3,5-triazole-1,2,4-bis-maleimide.
Claim 12
Dependent Claim
161 words
The composition according to claim 5 in which E represents a linear or branched alkylene radical having less than 13 carbon atoms, a phenylene or cyclohexyleneradical, or phenylene or cyclohexylene radical substituted by a methyl group, or a ##STR17## radical wherein n represents an integer from 1 to 3, or more than one phenylene or cyclohexylene radical, or phenylene or cyclohexylene radical substituted by a methyl group, linked together either by a simple valency bond or by an inert atom or group selected from the group consisting of --O--, --S--, an alkylene group having from 1 to 3 carbon atoms, --CO--, --SO 2 --, --NR 1 --, --N=N--, --CONH--, --COO--, --P(O)R 1 --, --CONH--X--NHCO--, ##STR18## wherein R 1 represents a hydrogen atom, an alkyl radical having from 1 to 4 carbon atoms, a phenyl or a cyclohexyl radical, or a phenyl or cyclohexyl radical substituted by a methyl group, and X represents an alkylene radical having less than 13 carbon atoms.
Claim 13
Dependent Claim
28 words
A composition according to claim 1 in which the monomer (c) is selected from the group consisting of allyl ortho-phthalate, allyl cyanurate, triallyl mellitate and phenyl allyl dimethylsilane.
Claim 14
Dependent Claim
23 words
A composition according to claim 1 in which the monomer (c) is selected from the group consisting of 4-vinylpyridine, N-vinyl pyrrolidone and styrene.
Claim 15
Dependent Claim
23 words
A composition according to claim 1 in which the monomer (c) is selected from the group consisting of glycidyl acrylate and glycidyl methacrylate.
Claim 16
Dependent Claim
6 words
The filled composition of claim 14.
Claim 17
Dependent Claim
153 words
A composition according to claim 1 in which the polyamine contains 3 to 5 --NH 2 groups per molecule and less than 50 carbon atoms, said --NH 2 groups being carried by a benzene nucleus, a benzene nucleus which is substituted by methyl groups or by a naphthalene, pyridine or triazine nucleus or by several benzene nuclei linked to one another by a valency bond or by an inert atom or group selected from the group consisting of --O--, --S--, an alkylene group having from 1 to 3 carbon atoms, --CO--, --SO 2 --, --NR 1 --, --N═N--, --CONH--, --COO--, --P(O)R 1 --, --CONH--X--NHCO--, ##STR19## wherein R 1 represents a hydrogen atom, an alkyl radical having from 1 to 4 carbon atoms, a phenyl or a cyclohexyl radical or a phenyl or cyclohexyl radical substituted by a methyl group, and X represents an alkylene radical having less than 13 carbon atoms or ##STR20##
Claim 18
Dependent Claim
65 words
A composition according to claim 1 in which the polyamine is an oligomer of the formula: ##STR21## wherein y represents a number from 0.1 to about 2, R represents a divalent hydrocarbon radical having from 1 to 8 carbon atoms derived from an aldehyde or ketone of the formula: R═O in which the oxygen atom is attached to a carbon atom of the radical R.
Claim 19
Dependent Claim
44 words
A composition according to claim 1 which also contains up to 10% by weight of an aromatic compound (d) containing 2 to 4 benzene rings having a boiling point above 250° C. and which is not sublimable up to 250° C. at atmospheric pressure.
Claim 20
Dependent Claim
13 words
The composition according to claim 1 in which component (c) is tri-allyl isocyanurate.
Claim 21
Dependent Claim
22 words
The composition according to claim 1 in which component (a) is N,N'-4,4'-diphenylmethane-bis-maleimide, component (b) is 4,4'-diaminodiphenylmethane and component (c) is tri-allyl isocyanurate.
Claim 22
Dependent Claim
150 words
A resinous composition consisting essentially of the polyimide reaction product of bis-imide having the formula: ##STR22## wherein T represents a divalent organic radical containing a carbon-carbon double bond derived from an ethylenic dicarboxylic acid anhydride of the formula: ##STR23## Q is a member selected from the class consisting of divalent organic radicals of at least 2 carbon atoms, and divalent groups consisting of two phenyl residues attached to each other through the medium of a member selected from the class consisting of an alkylene radical having from 1 to 3 carbon atoms, ##STR24## and a polyamine having the formula: R(NH.sub.2).sub.n where R is an organic radical of valency n and n is an integer of at least 2, and monomer selected from the group consisting of diallyl phthalate and N-vinylpyrrolidone and mixtures thereof, said monomer being less than 60% by weight based on the weight of the bis-imide and polyamine.
Claim 23
Dependent Claim
150 words
A resinous composition consisting essentially of the polyimide reaction product of bis-imide having the formula: ##STR22## wherein T represents a divalent organic radical containing a carbon-carbon double bond derived from an ethylenic dicarboxylic acid anhydride of the formula: ##STR23## Q is a member selected from the class consisting of divalent organic radicals of at least 2 carbon atoms, and divalent groups consisting of two phenyl residues attached to each other through the medium of a member selected from the class consisting of an alkylene radical having from 1 to 3 carbon atoms, ##STR24## and a polyamine having the formula: R(NH.sub.2).sub.n where R is an organic radical of valency n and n is an integer of at least 2, and monomer selected from the group consisting of diallyl phthalate and N-vinylpyrrolidone and mixtures thereof, said monomer being less than 60% by weight based on the weight of the bis-imide and polyamine.
Claim 24
Dependent Claim
7 words
The cured thermoset composition of claim 14.
Claim 25
Dependent Claim
26 words
A composition according to claim 21 in which said monomer comprises from 5 to 50% by weight based on the weight of the bis-imide and polyamine.
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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) | 1980-07-11 | 1981-01-10 | 1981-07-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-07-11 | 1985-01-10 | 1985-07-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-07-11 | 1989-01-10 | 1989-07-12 | $7700.00 | Window Closed / Lapsed |