Silicon-modified prepolymers

Claim 2

A silicon-modified polyamide, polyamide-acid or polyamide-amide-acid monomer or prepolymer with an inherent viscosity of 0.04 to 4.0, which have the formula I ##EQU26## wherein X represents a structural element of the formula II ##EQU27## a denotes a number from 0 to 100, and the individual m, R 1 , R 2 , R 3 , Q and Y independently of one another denote the following: m denotes the number 1 or 2, R 1 denotes a radical ##EQU28## with x denoting a number from 1 to 4, R 2 denotes a carbocyclic-aromatic or heterocyclic radical, wherein the carbonamide and carboxyl groups are bonded to different ring carbon atoms and the carboxyl groups are each in the ortho-position to a carbonamide group, R 3 denotes an aliphatic radical with at least 2 carbon atoms, or a cycloaliphatic, araliphatic, carbocyclic-aromatic or heterocyclic radical, Q denotes methyl, phenyl or a --OY radical, with Y having the meaning indicated below, and Y denotes an alkyl radical with 1 to 6 carbon atoms or a phenyl radical, and the corresponding cyclised derivatives.

Claim 3

A silicon-modified monomer or prepolymer of the formula I according to claim 1, wherein the individual R 2 independently of one another represent an unsubstituted monocyclic, fused polycyclic or non-fused bicyclic aromatic radical, the aromatic nucleii, in the latter case, being bonded to one another via the bridge member --O-- or --CO--, the individual R 3 independently of one another represent a monocyclic or non-fused bicyclic aromatic radical which is optionally substituted by halogen atoms or alkyl or alkoxy groups with 1-4 carbon atoms each, an unsubstituted monocyclic araliphatic radical or an unsubstituted aliphatic radical with 2-10 carbon atoms, and what has been stated in claim 1 applies to a, m, R 1 , Q and Y, and the corresponding cyclised derivatives.

Claim 4

A silicon-modified monomer or prepolymer of the formula I according to claim 1, wherein R 2 represents the 1,4- or 1,3-phenylene radical, a benzene ring or the benzophenone ring system and R 3 represents the 1,4- or 1,3-phenylene radical, the 4,4'-diphenylyl-ether radical or 4,4'-diphenylylmethane radical, with only one of R 2 and R 3 denoting a 1,4-phenylene radical, and what has been stated in claim 1 applies to a, m, R 1 , Q and Y, and the corresponding cyclised derivatives.

Claim 5

A silicon-modified prepolymer of the formula I according to claim 1, wherein, if a ≧ 1, the individual R 2 and R 3 have the same meaning, m is the same for each radical R 2 , and what has been stated in claim 1 applies to R 1 , Q and Y, and the corresponding cyclised derivatives.

Claim 6

A silicon-modified prepolymer of the formula I according to claim 1, wherein X represents a structural element of the formula IIb ##EQU29## in which a 1 denotes a number from 1 to 99 and the two R 2 ' each represent a benzene ring, with the carbonamide and carboxyl groups being bonded to different ring carbon atoms and the carboxyl groups each being in the ortho-position to the --CO-NH-R 1 -- grouping, and the individual R 1 , R 2 , R 3 , Q and Y are identical, and the corresponding derivatives with cyclised terminal carboxylic acid groups.

Claim 7

A silicon-modified prepolymer of the formula I according to claim 1, wherein X represents a structural element of the formula IIc ##EQU30## in which a 1 denotes a number from 1 to 99 and the two R 2 " each denote a benzene ring, with the carbonamide groups and carboxyl groups being bonded to different ring carbon atoms and the carboxyl groups being each in the ortho-position to the --CO-NH-R 3 -- grouping, and the individual R 1 , R 2 , R 3 , Q and Y are identical, as well as the corresponding derivatives with cyclised terminal carboxylic acid groups.

Claim 8

A silicon-modified prepolymer of the formula I according to claim 5, wherein R 1 in each case denotes a ##EQU31## radical, the individual R 2 and R 3 are identical and one of R 2 and R 3 represents the 1,4-phenylene radical and the other the 1,3-phenylene radical or R 2 and R 3 each represent the 1,3-phenylene radical, Q represents the methyl group and Y represents a propyl group or Q represents the ethoxy group and Y represents the ethyl group and what has been stated under claim 5 applies to a 1 and R 2 ', as well as the corresponding derivatives with cyclised terminal carboxylic acid groups.

Claim 9

A silicon-modified monomer or prepolymer of the formula I according to claim 1, wherein m in each case denotes the number 1, R 1 in each case represents a ##EQU32## radical, the individual R 2 and R 3 are identical and one of R 2 and R 3 represents the 1,4-phenylene radical and the other the 1,3-phenylene radical or R 2 and R 3 each represent the 1,3-phenylene radical, Q represents the methyl group and Y represents a propyl group or Q represents the ethoxy group and Y represents the ethyl group and what has been stated in claim 1 applies to a.

Claim 10

A silicon-modified monomer or prepolymer of the formula I according to claim 1, wherein m in each case denotes the number 2, R 1 in each case represents a ##EQU33## radical, R 2 in each case denotes a benzene ring or the benzophenone ring system, R 3 in each case denotes the 4,4'-diphenylyl-ether or the 4,4'-diphenylylmethane radical, Q denotes the methyl group and Y denotes a propyl group or Q denotes the ethoxy group and Y denotes the ethyl group and what has been stated in claim 1 applies to a, as well as the corresponding cyclised derivatives.

Claim 11

A silicon-modified monomer or prepolymer of the formula I according to claim 1, wherein X represents a structural element of the formula IId ##EQU34## in which R 1 in each case represents a ##EQU35## radical, R 2 in each case denotes a benzene ring and R 3 in each case denotes the 4,4'-diphenylyl-ether or the 4,4'-diphenylylmethane radical, Q denotes the methyl group and Y denotes a propyl group or Q denotes the ethoxy group and Y denotes the ethyl group, and what has been stated in claim 1 applies to a, as well the corresponding cyclised derivatives.

Claim 12

Silicon-modified prepolymers of the formula I according to claim 6, wherein R 1 in each case represents a ##EQU36## radical, the individual R 2 and R 3 are respectively identical and one of R 2 and R 3 denotes the 1,4-phenylene radical and the other the 1,3-phenylene radical, or R 2 and R 3 each denote the 1,3-phenylene radical, Q denotes the methyl group and Y denotes a propyl group or Q denotes the ethoxy group and Y denotes the ethyl group and what has been stated in claim 6 applies to a 1 and R 2 ", as well as the corresponding derivatives with cyclised terminal carboxylic acid groups.

Claim 13

A process for the manufacture of a silicon-modified polyamide, polyamide-acid or polyamide-amide-acid monomer or prepolymer with an inherent viscosity of 0.04 to 4.0, which has the formula I ##EQU37## wherein X represents a structural element of the formula II ##EQU38## a denotes a number from 0 to 100, and the individual m, R 1 , R 2 , R 3 , Q and Y independently of one another denote the following: m denotes the number 1 or 2, R 1 denotes a radical --CH 2 -- x ' ##EQU39## with x denoting a number from 1 to 4, R 2 denotes a carbocyclic-aromatic or heterocyclic radical, wherein the carbonamide and carboxyl groups are bonded to different ring carbon atoms and the carboxyl groups are each in the ortho-position to a carbonamide group, R 3 denotes an aliphatic radical with at least 2 carbon atoms, or a cycloaliphatic, araliphatic, carbocyclic-aromatic or heterocyclic radical, Q denotes methyl, phenyl or a --OY radical, with Y having the meaning indicated below, and Y denotes an alkyl radical with 1 to 6 carbon atoms or a phenyl radical, and the corresponding cyclised derivative, characterised in that, if a = o, one mole of a dicarboxylic acid dichloride of the formula ##EQU40## a tricarboxylic acid anhydride-chloride of the formula ##EQU41## or a tetracarboxylic acid dianhydride of the formula ##EQU42## or, if a ≧ 1, one mole of a polyamide or a polyamide-amide-acid with two acid chloride end groups, a polyamide-acid or a polyamide-amide-acid with two anhydride end groups or a polyamide-amide-acid with one acid chloride end group and one anhydride end group, all these, apart from said end groups, corresponding to the formula II, or corresponding cyclised derivative is reacted with two moles, a stoichiometric amount, of an aminosilane of the formula III ##EQU43## at a temperature between -20°C and + 50°C in an anhydrous aprotic organic solvent wherein what has been stated under formula I applies to a, m, R 1 , R 2 , R 3 , Q and Y, and the silicon-modified polyamide-acid or polyamide-amide-acid monomer or prepolymer is optionally subsequently cyclised chemically.

Claim 14

A process for the manufacture of a silicon-modified polyamide, polyamide-acid or polyamide-amide-acid monomer or prepolymer with an inherent viscosity of 0.04 to 4.0, which has the formula I ##EQU37## wherein X represents a structural element of the formula II ##EQU38## a denotes a number from 0 to 100, and the individual m, R 1 , R 2 , R 3 , Q and Y independently of one another denote the following: m denotes the number 1 or 2, R 1 denotes a radical --CH 2 -- x ' ##EQU39## with x denoting a number from 1 to 4, R 2 denotes a carbocyclic-aromatic or heterocyclic radical, wherein the carbonamide and carboxyl groups are bonded to different ring carbon atoms and the carboxyl groups are each in the ortho-position to a carbonamide group, R 3 denotes an aliphatic radical with at least 2 carbon atoms, or a cycloaliphatic, araliphatic, carbocyclic-aromatic or heterocyclic radical, Q denotes methyl, phenyl or a --OY radical, with Y having the meaning indicated below, and Y denotes an alkyl radical with 1 to 6 carbon atoms or a phenyl radical, and the corresponding cyclised derivative, characterised in that, if a = o, one mole of a dicarboxylic acid dichloride of the formula ##EQU40## a tricarboxylic acid anhydride-chloride of the formula ##EQU41## or a tetracarboxylic acid dianhydride of the formula ##EQU42## or, if a ≧ 1, one mole of a polyamide or a polyamide-amide-acid with two acid chloride end groups, a polyamide-acid or a polyamide-amide-acid with two anhydride end groups or a polyamide-amide-acid with one acid chloride end group and one anhydride end group, all these, apart from said end groups, corresponding to the formula II, or corresponding cyclised derivative is reacted with two moles, a stoichiometric amount, of an aminosilane of the formula III ##EQU43## at a temperature between -20°C and + 50°C in an anhydrous aprotic organic solvent wherein what has been stated under formula I applies to a, m, R 1 , R 2 , R 3 , Q and Y, and the silicon-modified polyamide-acid or polyamide-amide-acid monomer or prepolymer is optionally subsequently cyclised chemically.

Claim 15

A process according to claim 12 for the manufacture of a silicon-modified polyamide, polyamide-acid and polyamide-amide-acid monomer or prepolymer of the formula I, wherein X represents a structural element of the formula IIa ##EQU44## a 1 denotes a number from 0 to 99, k denotes the number 2 and p denotes the number 1 or 2 and what has been stated in claim 12 applies to m, R 1 , R 2 , R 3 , Q and Y, and of the corresponding cyclised derivative, characterised in that two moles, a stoichiometric amount, of a compound of the formula IV ##EQU45## wherein p is the number 1 or 2, the radical --COOH is in the ortho-position to the grouping --CO-NH-R 1 and the anhydride grouping is bonded to adjacent C atoms of the radical R 2 , is reacted, if a 1 = 0, with one mole of a diamine of the formula H 2 N-R 3 -NH 2 , or, if a 1 .sup.≠ 1, with one mole of a polyamide, a polyamide-acid or a polyamide-amide-acid of the formula V ##EQU46## or the corresponding cyclised derivative, in which formulae what has been stated under formula IIa or in claim 12 applies to a 1 , m, p, R 1 , R 2 , R 3 , Q and Y, and the silicon-modified polyamide-acid or polyamide-amide-acid monomer or prepolymer is optionally subsequently cyclised chemically.

Claim 16

Process according to claim 12, characterised in that an aminosilane of the formula III is used, wherein R 1 denotes ##EQU47## radical, Q denotes the methyl group and Y denotes a propyl group or Q denotes the ethoxy group and Y denotes the ethyl group.

Claim 17

Process according to claim 13, characterised in that a compound of the formula IV is used, wherein R 1 denotes a ##EQU48## radical, R 2 denotes a benzene ring, p denotes the number 1, Q denotes the methyl group and Y denotes a propyl group or Q denotes the ethoxy group and Y denotes the ethyl group.