Curing 1,2-epoxy with prepolymer based on polyamines and oligomers possessing imide groups

Claim 2

A process for curing a 1,2-epoxy resin which comprises mixing the epoxy resin with a curing amount of a prepolymer composition, said composition being prepared by heating (a) an oligomer having the average general formula: in which x represents a number from 0.1 to about 2, R represents a divalent hydrocarbon radical with 1 to 8 carbon atoms, which is derived from an aldehyde or a ketone of the general formula: O = R (II) in which the oxygen atom is bonded to a carbon atom of the radical R, and T represents a divalent organic radical possessing 2 to 24 carbon atoms, the free valencies of which are on adjacent carbon atoms and which is derived from an internal anhydride of the general formula: ##STR32##at least 60% of the T radicals in the oligomer containing a polymerisable carbon-carbon double bond, the remaining T radicals, if any, being alkylene, cycloalkylene, phenylene or naphthylene radicals with (b) a polyamine of the general formula: Q(NH.sub.2).sub.y in which y represents an integer at least equal to 2 and Q represents:

Claim 3

a divalent organic radical E selected from the group consisting of a linear or branched alkylene radical with less than 13 carbon atoms, a phenylene radical, a cyclohexylene radical, a phenylene radical substituted by a methyl radical, a cyclohexylene radical substituted by a methyl radical, radicals of the formulae: ##STR33## wherein n represents an integer from 1 to 3, a radical consisting of a plurality of phenylene, cyclohexylene, phenylene substituted by methyl or cyclohexylene substituted by methyl, radicals connected to one another by a simple valency bond or by --O-- or --S--, an alkylene group with 1 to 3 carbon atoms, --CO--, --SO 2 --, --CONH--, --COO--, --P(O)R 1 --, --CONH--X--NHCO--, ##STR34##wherein R 1 represents a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, a phenyl radical or a cyclohexyl radical, and X represents an alkylene radical with less than 13 carbon atoms, and a 2- to 4-valent radical of the formula: ##STR35##in which x represents a number from 0.1 to 2, the relative amounts being such that the oligomer supplies 1.1 to 50 T radicals containing a polymerisable carbon-carbon double bond per --NH 2 group supplied by the polyamine at a temperature from about 80° C. to about 200° C. until a homogeneous liquid or paste-like mixture is obtained, and the mixture of prepolymer and epoxy resin is then cured by subsequent heating at between 150° C. and 300° C.

Claim 4

a divalent organic radical E selected from the group consisting of a linear or branched alkylene radical with less than 13 carbon atoms, a phenylene radical, a cyclohexylene radical, a phenylene radical substituted by a methyl radical, a cyclohexylene radical substituted by a methyl radical, radicals of the formulae: ##STR33## wherein n represents an integer from 1 to 3, a radical consisting of a plurality of phenylene, cyclohexylene, phenylene substituted by methyl or cyclohexylene substituted by methyl, radicals connected to one another by a simple valency bond or by --O-- or --S--, an alkylene group with 1 to 3 carbon atoms, --CO--, --SO 2 --, --CONH--, --COO--, --P(O)R 1 --, --CONH--X--NHCO--, ##STR34##wherein R 1 represents a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, a phenyl radical or a cyclohexyl radical, and X represents an alkylene radical with less than 13 carbon atoms, and a 2- to 4-valent radical of the formula: ##STR35##in which x represents a number from 0.1 to 2, the relative amounts being such that the oligomer supplies 1.1 to 50 T radicals containing a polymerisable carbon-carbon double bond per --NH 2 group supplied by the polyamine at a temperature from about 80° C. to about 200° C. until a homogeneous liquid or paste-like mixture is obtained, and the mixture of prepolymer and epoxy resin is then cured by subsequent heating at between 150° C. and 300° C.

Claim 5

A process according to claim 1 in which the oligomer supplies 1.2 to 5 T radicals possessing a polymerisable carbon-carbon double bond per --NH 2 group supplied by the polyamine.

Claim 6

A process according to claim 1 in which the polyamine is a diprimary diamine of the formula: H.sub.2 N-E-NH.sub.2 in which E is as defined in claim 1.

Claim 7

A process according to claim 1 in which the polyamine is a mixture of a diprimary diamine an an amine having an average of more than two amino groups per molecule, in an amount up to 90% by weight of the diamine.

Claim 8

A process according to claim 1 in which the polyamine consists of an oligomer of the average formula: ##STR36##in which x and R are as defined in claim 1.

Claim 9

A process according to claim 1 in which R represents a CH 2 radical.

Claim 10

A process according to claim 1 in which at least 60% of the T radicals are --CH=CH-- radicals.

Claim 11

A process according to claim 7 in which the remainder of the T radicals are ##STR37##radicals.

Claim 12

A process according to claim 1 in which at least 80% of the T radicals contain a polymerisable carbon-carbon double bond.

Claim 13

A process according to claim 1 in which, before curing, an aromatic compound possessing 2 to 4 benzene rings, which does not sublime at atmospheric pressure up to 250° C. and which has a boiling point above 250° C. is incorporated in an amount up to about 10% by weight based on the weight of the prepolymer and epoxy resin.

Claim 14

A process according to claim 1 in which an aromatic tricarboxylic or tetracarboxylic acid anhydride is added to the prepolymer, before curing, in an amount from about 1 to 5% by weight of the prepolymer.

Claim 15

A process according to claim 1 in which a monomer containing at least one polymerisable CH 2 =C< group of the vinyl, allyl or acrylic type is incorporated before curing in an amount up to 50% by weight based on the weight of the prepolymer and epoxy resin.

Claim 16

A process for curing a 1,2-epoxy resin which comprises mixing the epoxy resin with a curing amount of a prepolymer composition, said composition being prepared by heating (a) an oligomer having the average general formula: ##STR38## in which x represents a number from 0.1 to about 2, R represents a divalent hydrocarbon radical with 1 to 8 carbon atoms, which is derived from an aldehyde or a ketone of the general formula: O=R (II) in which the oxygen atom is bonded to a carbon atom of the radical R, and T represents a divalent organic radical possessing 2 to 24 carbon atoms, the free valencies of which are on adjacent carbon atoms and which is derived from an internal anhydride of the general formula: ##STR39##at least 60% of the T radicals in the oligomer containing a polymerisable carbon-carbon double bond, the remaining T radicals, if any, being alkylene, cycloalkylene, phenylene or naphthylene radicals, with (b) a polyamine of the general formula: Q(NH.sub.2).sub.y in which y represents an integer at least equal to 2 and Q represents: a divalent organic radical E selected from the group consisting of a linear or branched alkylene radical with less than 13 carbon atoms, a phenylene radical, a cyclohexylene radical, a phenylene radical substituted by a methyl radical, a cyclohexylene radical substituted by a methyl radical, radicals of the formulae: ##STR40## wherein n represents an integer from 1 to 3, a radical consisting of a plurality of phenylene, cyclohexylene, phenylene substituted by methyl or cyclohexylene substituted by methyl; radicals connected to one another by a simple valency bond or by --O-- or --S--, an alkylene group with 1 to 3 carbon atoms, --CO--, --SO 2 --, --CONH--, --COO--, --P(O)R 1 --, --CONH--X--NHCO--, ##STR41##wherein R 1 represents a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, a phenyl radical or a cyclohexyl radical, and X represents an alkylene radical with less than 13 carbon atoms, and a 2- to 4-valent radical of the formula: ##STR42## in which x represents a number from 0.1 to 2, the relative amounts being such that the oligomer supplies 1.1 to 50 T radicals containing a polymerisable carbon-carbon double bond per --NH 2 group supplied by the polyamine, in an inert polar solvent at a temperature from about 50° C. to about 180° C., and the mixture of prepolymer and epoxy resin is then cured by subsequent heating at between 150° C. and 300° C.

Claim 17

A process for curing a 1,2-epoxy resin which comprises mixing the epoxy resin with a curing amount of a prepolymer composition, said composition being prepared by heating (a) an oligomer having the average general formula: ##STR38## in which x represents a number from 0.1 to about 2, R represents a divalent hydrocarbon radical with 1 to 8 carbon atoms, which is derived from an aldehyde or a ketone of the general formula: O=R (II) in which the oxygen atom is bonded to a carbon atom of the radical R, and T represents a divalent organic radical possessing 2 to 24 carbon atoms, the free valencies of which are on adjacent carbon atoms and which is derived from an internal anhydride of the general formula: ##STR39##at least 60% of the T radicals in the oligomer containing a polymerisable carbon-carbon double bond, the remaining T radicals, if any, being alkylene, cycloalkylene, phenylene or naphthylene radicals, with (b) a polyamine of the general formula: Q(NH.sub.2).sub.y in which y represents an integer at least equal to 2 and Q represents: a divalent organic radical E selected from the group consisting of a linear or branched alkylene radical with less than 13 carbon atoms, a phenylene radical, a cyclohexylene radical, a phenylene radical substituted by a methyl radical, a cyclohexylene radical substituted by a methyl radical, radicals of the formulae: ##STR40## wherein n represents an integer from 1 to 3, a radical consisting of a plurality of phenylene, cyclohexylene, phenylene substituted by methyl or cyclohexylene substituted by methyl; radicals connected to one another by a simple valency bond or by --O-- or --S--, an alkylene group with 1 to 3 carbon atoms, --CO--, --SO 2 --, --CONH--, --COO--, --P(O)R 1 --, --CONH--X--NHCO--, ##STR41##wherein R 1 represents a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, a phenyl radical or a cyclohexyl radical, and X represents an alkylene radical with less than 13 carbon atoms, and a 2- to 4-valent radical of the formula: ##STR42## in which x represents a number from 0.1 to 2, the relative amounts being such that the oligomer supplies 1.1 to 50 T radicals containing a polymerisable carbon-carbon double bond per --NH 2 group supplied by the polyamine, in an inert polar solvent at a temperature from about 50° C. to about 180° C., and the mixture of prepolymer and epoxy resin is then cured by subsequent heating at between 150° C. and 300° C.

Claim 18

A process according to claim 13 in which the oligomer supplies 1.2 to 5 T radicals possessing a polymerisable carbon-carbon double bond per --NH 2 group supplied by the polyamine.

Claim 19

A process according to claim 13 in which the polyamine is a diprimary diamine of the formula: H.sub.2 N--E--NH.sub.2 in which E is as defined in claim 13.

Claim 20

A process according to claim 13 in which the polyamine is a mixture of a diprimary diamine and an amine having an average of more than two amino groups per molecule, in an amount up to 90% by weight of the diamine.

Claim 21

A process according to claim 13 in which the polyamine consists of an oligomer of the average formula: ##STR43##in which x and R are as defined in claim 13.

Claim 22

A process according to claim 13 in which R represents a CH 2 radical.

Claim 23

A process according to claim 13 in which at least 60% of the T radicals are --CH=CH-- radicals.

Claim 24

A process according to claim 19 in which the remainder of the T radicals are ##STR44##radicals.

Claim 25

A process according to claim 13 in which at least 80% of the T radicals contain a polymerisable carbon-carbon double bond.

Claim 26

A process according to claim 13 in which, before curing, an aromatic compound possessing 2 to 4 benzene rings, which does not sublime at atmospheric pressure up to 250° C. and which has a boiling point above 250° C. is incorporated in an amount up to about 10% by weight based on the weight of the prepolymer and epoxy resin.

Claim 27

A process according to claim 13 in which an aromatic tricarboxylic or tetracarboxylic acid anhydride is added to the prepolymer, before curing, in an amount from about 1 to 5% by weight of the prepolymer.

Claim 28

A process according to claim 13 in which a monomer containing at least one polymerisable CH 2 =C< group of the vinyl, allyl or acrylic type is incorporated before curing in an amount up to 50% by weight based on the weight of the prepolymer and epoxy resin.