Abstract: | New halogen‐substituted aromatic–aliphatic and wholly aromatic polyamides with high inherent viscosities were synthesized by the direct polycondensation of 5‐halo‐m‐phenylenediamines, where the halogens were Cl, Br, and I, with both aliphatic and aromatic dicarboxylic acids in N‐methyl‐2‐pyrrolidone with a mixture of triphenyl phosphite and pyridine as a condensing agent. The solubility of the halogen‐substituted polyamides was much higher than that of the parent polyamides derived from m‐phenylenediamine. The glass‐transition temperatures of the substituted aromatic–aliphatic polyamides increased in the order Cl < Br < I, whereas the temperatures of 10% weight loss in air decreased in the reverse order. The limiting oxygen index values, as an indication of flammability, increased for the substituted aromatic–aliphatic polyamides in the order Cl < Br < I. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3911–3918, 2000 |