Oxidative degradation of polymers. II. Thermal oxidative degradation of atactic polypropylene in solution under pressure

Atactic polypropylene was oxidized in solution in the presence and absence of radical initiator over the temperature range of 140° to 200°C under oxygen pressure of 3.3 to 12.4 kg/cm², and the effects of metal catalyst and additives on the rate, products, and change in molecular weight distribution were measured. The synergistic effect was observed with cobalt and managanese salts. The deactivation of the metal catalyst was suppressed by the addition of acetic acid and acetic anhydride as solvent. The rate of oxidation increased with increasing temperature, but the decrease in molecular weight was nevertheless not so significant as to give many low-boiling products. However, the production of mixtures of acid, ketone, alcohol, and ester with molecular weights of several hundreds was promising. The refractive index of polypropylene decreased markedly as the oxidation proceeded, and the complications involved in the determination of the change in molecular weight distribution measured by gel permeation chromatography are discussed.