Synthesis of polyarylamines by vinylogous nucleophilic substitution polymerization of bis(4-chloro-3-nitrophenyl) sulfone with diamines

A series of new polyarylamines was prepared by the vinylogous nuclephilic substitution polymerization of bis(4-chloro-3-nitrophenyl) sulfone with both aromatic and aliphatic diamines. The synthesis involves the solution polycondensation in a polar aprotic solvent at elevated temperatures, a tertiary amine being used as an acid acceptor. Of these solvents, dimethyl sulfoxide and N-methyl-2-pyrrolidone were the most effective for the preparation of high molecular weight polymers. The polyarylamines having inherent viscosities in the range of 0.1–0.5 were all amorphous and highly soluble in polar aprotic solvents. Thermogravimetric analysis under both air and nitrogen atmospheres indicated that rapid decomposition began above 300°C for the polyarylamines from aromatic diamines.     

Synthesis of polyenamines by vinylogous nucleophilic substitution polymerization of 1,6-diethoxy-1,5-hexadiene-3,4-dione with diamines

Novel polyenamines with inherent viscosities in the 0.2–1.1 range were synthesized by the vinylogous, nucleophilic substitution polymerization of 1,6-diethoxy-1,5-hexadiene-3,4-dione with aromatic and aliphatic diamines in polar aprotic solvents at room temperature. The most effective polymerization medium was hexamethylphosphoramide for preparing high-molecular-weight polymers from aromatic diamines. The dilute solutions showed a marked decrease in viscosity with time. The aromatic polyenamines began to lose weight around 200°C under thermogravimetric analysis in air and nitrogen.