The thermal degradation and oxidation of polybutadiene

Detailed studies have been made of the successive stages in the thermal degradation in air and nitrogen of carboxy-terminated polybutadiene (CTPB). During oxidation at high temperatures, a protective surface film is first formed; this film ruptures at temperatures where pyrolysis leads to the formation of volatile products in the bulk of the polymer. Thermogravimetric curves for the degradation of CTPB in nitrogen are complex in shape; it appears that the free-radical crosslinking and cyclisation reactions cause an increase in the thermal stability of the polymer during degradation.