α,β-UNSATURATED SCHIFF-BASE CHAIN EXTENSION REACTIONS FOR POLYIMIDES AND POLYAMIDE-IMIDES

Claim 2

A composition of matter consisting essentially of a. a prepolymer selected from

Claim 3

a polyamide-acid of the formula ##EQU33## its corresponding polyimide,

Claim 4

a polyamide-acid of the formula ##EQU33## its corresponding polyimide,

Claim 5

a polyamide-amide acid of the formula ##EQU34## its corresponding polyamide-imide,

Claim 6

a polyamide-amide acid of the formula ##EQU34## its corresponding polyamide-imide,

Claim 7

a polyamide-amide acid of the formula ##EQU35## and its corresponding polyamide-imide, wherein n is a number from 1 to 20, a is a number from 0.1 to 2, R 1 , r 2 , r 3 and R 4 are independently hydrogen or a monovalent aliphatic, cycloaliphatic, or aromatic radical and R 5 and R 7 are independently a divalent organic radical containing from 2 to 30 carbon atoms and selected from aromatic, aliphatic, alkylaromatic, and cycloaliphatic radicals, and radicals with hetero-atom containing bridging groups where the heteroatom in the bridge is selected from oxygen, sulfur, nitrogen, phosphorus and silicon, and R 6 is a tetravalent aliphatic, cycloaliphatic, aromatic or heterocyclic radical containing at least 2 carbon atoms, or a combination of aromatic and aliphatic radicals, and b. from about 1 to 10 mole equivalents per mole equivalent of (a) of a bis-dienophile selected from

Claim 8

a polyamide-amide acid of the formula ##EQU35## and its corresponding polyamide-imide, wherein n is a number from 1 to 20, a is a number from 0.1 to 2, R 1 , r 2 , r 3 and R 4 are independently hydrogen or a monovalent aliphatic, cycloaliphatic, or aromatic radical and R 5 and R 7 are independently a divalent organic radical containing from 2 to 30 carbon atoms and selected from aromatic, aliphatic, alkylaromatic, and cycloaliphatic radicals, and radicals with hetero-atom containing bridging groups where the heteroatom in the bridge is selected from oxygen, sulfur, nitrogen, phosphorus and silicon, and R 6 is a tetravalent aliphatic, cycloaliphatic, aromatic or heterocyclic radical containing at least 2 carbon atoms, or a combination of aromatic and aliphatic radicals, and b. from about 1 to 10 mole equivalents per mole equivalent of (a) of a bis-dienophile selected from

Claim 9

a compound of the formula ##EQU36##

Claim 10

a compound of the formula ##EQU36##

Claim 11

a polyamide-acid of the formula ##EQU37##

Claim 12

a polyamide-acid of the formula ##EQU37##

Claim 13

its corresponding polyimide, 3. a polyamide-amide acid of the formula ##EQU38## it corresponding polyamide-imide, and

Claim 14

its corresponding polyimide, 3. a polyamide-amide acid of the formula ##EQU38## it corresponding polyamide-imide, and

Claim 15

a polyamide-amide acid of the formula ##EQU39## and its corresponding polyamide-imide, wherein R 5 , r 6 and R 7 are as defined above, m is a number from 1 to 20, and D is a divalent radical containing olefinic unsaturation having the formula ##EQU40## wherein R 16 is hydrogen, methyl, bromo or chloro; R 17 is hydrogen, bromo or chloro; Y 1 -y 6 inclusive is selected from hydrogen, bromine, chlorine, nitro, phenyl, alkyl of from 1 to 6 carbon atoms; and X is carbonyl, oxygen, sulfur, chloro or bromo substituted methylene,

Claim 16

a polyamide-amide acid of the formula ##EQU39## and its corresponding polyamide-imide, wherein R 5 , r 6 and R 7 are as defined above, m is a number from 1 to 20, and D is a divalent radical containing olefinic unsaturation having the formula ##EQU40## wherein R 16 is hydrogen, methyl, bromo or chloro; R 17 is hydrogen, bromo or chloro; Y 1 -y 6 inclusive is selected from hydrogen, bromine, chlorine, nitro, phenyl, alkyl of from 1 to 6 carbon atoms; and X is carbonyl, oxygen, sulfur, chloro or bromo substituted methylene,

Claim 17

alkylidene of from 1 to 6 carbon atoms, and benzylidene. 2. A composition according to claim 1 where in the prepolymer of (a) and in the bisdienophile of (b) R 5 and R 7 are the same or different and each is an alkylene group containing from 2 to 12 carbon atoms, a cycloalkylene group containing from 4 to 6 carbon atoms; a xylylene group, an arylene group selected from ortho, meta or para phenylene, xylene, tolylene, biphenylene, naphthylene or anthrylene; a substituted arylene group of the formula ##SPC15## wherein W is a covalent bond, sulfur, carbonyl, --NH, --N--(lower)alkyl, O, S, SS, --N--phenyl, sulfonyl, a linear or branched alkylene group of from 1 to 3 carbon atoms, ##SPC16## arylene, a dialkyl or diaryl silyl group, ##EQU41## (lower) alkyl, said lower alkyl containing from 1 to 5 carbon atoms, --N=N--, or ##EQU42## R 8 and R 9 are independent and each is hydrogen, halogen, lower alkyl from 1 to 5 carbon atoms, lower alkoxy containing from 1 to 5 carbon atoms, aryl, a group having the formula ##SPC17## wherein R 11 is hydrogen, halogen or lower alkyl of from 1 to 5 carbon atoms, or a group having the formula ##SPC18## wherein Y is a covalent bond or NH- and R 10 is phenyl, piperidino, H,

Claim 18

diphenylamino, or a di(lower alkyl)amino group. 3. A composition according to claim 2 wherein the prepolymer is selected from 1. a polyamide-acid of the formula ##EQU43##

Claim 19

and 2. a polyimide of the formula ##EQU44##

Claim 20

and 2. a polyimide of the formula ##EQU44##

Claim 21

wherein the bis-dienophile is selected from 1. a compound of the formula ##EQU45##

Claim 22

wherein the bis-dienophile is selected from 1. a compound of the formula ##EQU45##

Claim 23

a polyamide-acid of the formula ##EQU46##

Claim 24

a polyamide-acid of the formula ##EQU46##

Claim 25

a polyimide of the formula ##EQU47##

Claim 26

a polyimide of the formula ##EQU47##

Claim 27

A composition according to claim 2 wherein a. the prepolymer is ##SPC19## b. the bis-dienophile is ##EQU48## wherein R 5 is ##SPC20## D is ##EQU49## and m is a number from 1 to 5.

Claim 28

A composition according to claim 2 wherein the prepolymer is the polyimide of the formula ##EQU50## wherein n is a number from 1 to 5, and the bis-dienophile is the compound of the formula ##EQU51##

Claim 29

A composition according to claim 2 wherein a. the prepolymer is the polyimide of the formula ##EQU52## wherein R 1 is hydrogen or phenyl, R 2 and R 3 are hydrogen and R 4 is phenyl, R 5 is selected from ##SPC21## R 6 is a group of the formula ##SPC22## n is a number from 1 to 5, and b. the bis-dienophile is the compound of the formula ##EQU53## wherein R 5 is as defined under clause (a) above, and D is a group having the formula ##EQU54##

Claim 30

A composition according to claim 6 wherein a. in the polyimide prepolymer R 1 , R 2 and R 3 are hydrogen, R 4 is phenyl, R 5 is a group of the formula ##SPC23## R 6 is a group of the formula ##SPC24## b. in the bis-dienophile R 5 is a group of the formula ##SPC25## D is a group of the formula ##EQU55##

Claim 31

A solution of a composition according to claim 1 in a volatile solvent for said composition.

Claim 32

A molding powder consisting essentially of the composition according to claim 1.

Claim 33

The crosslinked resin obtained by heating at 100° to 250°C, the composition according to claim 1.

Claim 34

A composition according to claim 6 wherein a. in the polyimide prepolymer R 1 , R 2 and R 3 are hydrogen, R 4 is phenyl, R 5 is ##SPC26## R 6 is ##SPC27## b. in the bis-dienophile R 5 is ##SPC28## D is ##EQU56##