Effect of some additives on the photoxidation of rigid PVC

The photoxidative degradation of PVC was studied by i.r. and u.v. spectroscopy and gel permeation chromatography. It was found that the photoxidative degradation of unprocessed PVC is an auto-accelerating chain scission process. Carboxylic groups were found to be the main product formed during degradation. The molecular weights $\text{M}{}_{\mathrm{n}}$ and $\text{M}{}_{\mathrm{w}}$ both decreased, but the molecular weight distribution widened with increasing length of exposure. Single additives, such as calcium stearate. Wax E and a solid organotin stabilizer, altered the rate but not the mode of the degradation. Combination of the three additives changed the mode of the photoxidation from auto-accelerating to constant rate of degradation. Processing at 170° with the combined additives increased the rate constants.