Synthesis of isomeric bis(amine anhydride)s for novel poly(amine imide)s by Pd-catalyzed amination of 4-chlorophthalic anhydride

Abstract

Two novel bis(amine anhydride) monomers, N,N′-bis(3,4-dicarboxyphenyl)-1,4-phenylenediamine dianhydride I and N,N′-bis(3,4-dicarboxyphenyl)-1,3-phenylenediamine dianhydride II, were prepared via palladium-catalyzed amination reaction of 4-chloro-N-methylphthalimide with 1,4-phenylenediamine or 1,3-phenylenediamine, followed by alkaline hydrolysis of the intermediate bis(amine imide)s and subsequent dehydration of the resulting tetraacids. A series of new poly(amine imide)s were prepared from the synthesized dianhydride monomers with various diamines in NMP via conventional two-step method. FT-IR spectra of the poly(amine imide)s revealed that in the solid state, intermolecular and intramolecular hydrogen bonding (N–H⋯OC) are present. These polymers had glass transition temperatures in the range of 250–295°C. The 10% weight loss temperature of the resulting poly(amine imide)s ranged from 539 to 560°C in nitrogen. The poly(amine imide)s have the peel strength values ranging from 283 to 358N/m. The poly(amine imide)s films were found to be transparent, flexible, and tough. The films had a tensile strength, elongation at break, and tensile modulus in the ranges 102–152MPa, 11.3–19.6%, and 1.04–2.08GPa, respectively.