Cross-linked resins

Abstract

Cross-linked resins of good thermal stability useful inter alia for making multicellular materials, for bonding metals, and for making laminates and moulded articles are made by reacting, e.g. by heating together, an unsaturated bis-imide with a diprimary diamine in a ratio of 1.2:1 to 50:1.

We claim: 
     
       1. A cross-linked resin obtained by heating at 100° C. to 350° C. an unsaturated bis-imide selected from the group consisting of maleic N,N'-ethylene-bis-imide, maleic N,N'-hexamethylene-bis-imide, maleic N,N'-metaphenylene-bis-imide, maleic N,N'-paraphenylene-bis-imide, maleic N,N'-4,4'-diphenylmethane-bis-imide, maleic N,N'-4,4'-diphenylether-bis-imide, maleic N,N'-4,4'-diphenylsulphone-bis-imide, maleic N,N'-4,4'-dicyclohexylmethane-bis-imide, maleic N,N' -α,α'-4,4'-dimethylenecyclohexane-bis-imide, maleic N,N'-metaxylylene-bis-imide and maleic N,N'-4,4'-diphenylcyclohexane-bis-imide with a diamine selected from the group consisting of 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, metaphenylenediamine, paraphenylenediamine, 4,4'-diaminadiphenylmethane, 2,2-bis-(4-aminophenyl)-propane, benzidine, 4,4'-diaminophenyl oxide, 4,4'-diaminodiphenyl sulphide, 4,4'-diaminodiphenyl-sulphone, bis-(4-aminophenyl)diphenylsilane, bis-(4-aminophenyl)methylphosphine oxide, bis-(3-aminophenyl)methylphosphine oxide, bis-(4-aminophenyl)phenylphosphine oxide, bis-(4-aminophenyl)phenylamine, 1,5-diamino-naphthalene, metaxylylenediamine, paraxylene diamine, 1,1-bis(paraaminophenyl)phthalene, 1,1-bis(4-aminophenyl)cyclohexane, 1,1-bis(4-amino-3-methylphenyl)cyclohexane and hexamethylenediamine at a ratio of bis-imide to diamine of from 1.2:1 to 50:1. 
     
     
       2. The cross-linked resin of claim 1 wherein said unsaturated bis-imide is maleic N,N'-4,4'-diphenylmethane-bis-imide and said diamine is bis-(4-aminophenyl)methane. 
     
     
       3. The cross-linked resin of claim 1 wherein the ratio of bis-imide to diamine is from 1.3:1 to 5:1. 
     
     
       4. The cross-linked resin of claim 2 wherein the ratio of bis-imide to diamine is from 1.3:1 to 5:1. 
     
     
       5. The cross-linked resin of claim 2 wherein the ratio of bis-imide to diamine is from about 2.3 to about 3.6. .Iadd. 6. A resinous polymer soluble in inert polar organic solvent and containing amine and imide groups formed by reacting a bis-maleimide with a diprimary amine in a molar ratio of from 1.2:1 to 50:1 at a temperature of from about 100° C. to about 250° C. .Iaddend. .Iadd. 7. The resinous polymer of claim 6 wherein the bis-malemide is maleic N,N'-4,4'-diphenylmethane-bis-imide and said diprimary amine is bis-(4-aminophenyl)methane. .Iaddend..Iadd. 8. The resinous polymer of claim 6 wherein the ratio of bis-imide to diamine is from 1.3:1 to 5:1. .Iaddend..Iadd. 9. A lacquer comprising the resinous polymer of claim 6 in solution in an inert polar organic solvent. .Iaddend..Iadd. 10. The lacquer of claim 9 in which said solvent is selected from the group of dimethyl formamide, dimethyl-acetamide and N-methyl pyrrolidone. .Iaddend..Iadd. 11. A method for curing the resinous polymer of claim 6 wherein the said polymer is heated up to a temperature of about 350° C. .Iaddend. .Iadd. 12. A resinous polymer soluble in inert polar organic solvent and containing amine and imide groups formed by reacting a bis-maleimide with a diprimary amine in a molar ratio between 1.2 to 1 and 50:1, said reaction being carried out in solution in an inert polar organic solvent at a temperature of 100°  to 250° C. .Iaddend..Iadd. 13. A polymer as recited in claim 12 in which the ratio of said bis-maleimide to said diprimary amine is from 1.3:1 to 5:1. .Iaddend..Iadd. 14. A polymer as recited in claim 12 in which said maleimide is based on maleic anhydride. .Iaddend..Iadd. 15. A polymer as recited in claim 12 in which said diprimary amine is aromatic. .Iaddend..Iadd. 16. A polymer as recited in claim 12 in which the temperature of reaction is 150° C. .Iaddend. .Iadd. 17. A lacquer comprising the polymer of claim 12 in solution in an inert polar organic solvent. .Iaddend. .Iadd. 18. A method of forming a resinous polymer soluble in an inert polar organic solvent and containing amine and imide groups comprising reacting a bis-maleimide with a diprimary amine in a molar ratio of from 1.2:1 to 50:1 in an inert polar organic solvent medium at a temperature of 100° to 250° C. .Iaddend..Iadd. 19. A lacquer comprising a resinous polymer soluble in inert polar organic solvent and containing amine and imide groups formed by reacting a bis-maleimide with a diprimary amine in a molar ratio between 1.2:1 and 50:1, said reaction being carried out in solution in inert polar organic solvent at a temperature of 100° to 250° C., said resinous polymer being in solution in an inert polar organic solvent selected from the group of dimethyl formamide, dimethylacetamide and N-methyl pyrrolidone. .Iaddend. .Iadd. 20. A resinous moulded polymer soluble in polar organic solvent and containing amine and imide groups formed by reacting a bis-maleimide with a diprimary amine in a molar ratio of from 1.2:1 to 50:1 at a temperature of from about 100° C. to about 250° C. .Iaddend. .Iadd. 21. The product of the process as defined by claim 11. .Iaddend.