Polyanhydrides. I. Preparation of high molecular weight polyanhydrides

Polyanhydrides composed of the following diacids–sebacic acid, bis(p‐carboxyphenoxy)propane, bis(p‐carboxyphenoxy)hexane, isophthalic acid, 1,4‐phenylene dipropionic acid, and dodecanedioic acid–were synthesized by a melt polycondensation process. Polymers of molecular weight up to 137,010 (weight average) and intrinsic viscosity of 0.92 dL/g were achieved. These high molecular weight polymers were reached by using pure isolated mixed anhydrides of diacids and acetic acid, under optimized reaction conditions (temperature of 180°C for 90 min under vacuum of 10^‐4 mm Hg). Polymers of higher molecular weights were synthesized in shorter times by using heterogenic coordination catalysts: cadmium acetate, ZnEt₂‐H₂O (1:1), barium oxide, calcium oxide, and calcium carbonate. By using these catalysts molecular weights of up to 245,000 were reached in 30 min of reaction. Films made of high molecular weight bis(p‐carboxyphenoxy)propane–sebacic acid copolymers showed tensile strengths of 40–160 kg/cm²; the strength increased as a function of the bis(p‐carboxyphenoxy)propane content and molecular weight.