SYNTHESIS OF POLY(ENAMINONITRILES) CONTAINING ARYLATE AND ARAMIDE UNITS, AND THEIR THERMAL-PROPERTIES

Various aromatic diamines with preformed arylate and aramide linkages were obtained by the reaction of p-nitrobenzoyl chloride with aromatic diols and diamines, and terephthaloyl chloride with p-nitrophenol and p-nitroaniline, followed by hydrogenation. New poly(enaminonitriles) containing arylate or aramide units in the main chain were prepared by reacting p-bis(1-chloro-2,2-dicyanovinyl)benzene (2) with the corresp onding ester- or amide-containing aromatic diamines. These polymers po ssess intrinsic Viscosities of 0.38-0.53 dL/g. They are easily soluble in polar aprotic solvents such as dimethyl sulfoxide, N,N-dimethylfor mamide and N-methyl-2-pyrrolidone. Hard and brittle films were easily cast from DMF solutions. These polymers show a broad exothermic peak i n differential scanning calorimetry and undergo a curing reaction arou nd 350 degrees C to form insoluble materials. Almost all the poly(enam inonitriles) exhibited no appreciable decomposition below 400 degrees C, 10% weight loss being recorded above 450 degrees C, and a good ther mal stability of 83-92% residual weight at 500 degrees C.