Direct observation of polyvinylchloride degradation in water at temperatures up to 500 deg C and at pressures up to 700 MPa

• Published in: Journal of applied polymer science 2007-10, Vol.106 (2), p.1075-1086
• Main Authors: Nagai, Yorihiko, Smith Jr, Richard L, Inomata, Hiroshi, Arai, Kunio
• Format: Article
• Language: English
• ISSN: 0021-8995; 1097-4628
• DOI: 10.1002/app.26790

Degradation of polyvinylchloride (PVC) in high-temperature and supercritical water was studied with a hydrothermal diamond anvil cell to determine phase change characteristics of the reacting polymer with respect to water density. During the reaction period of 500 s, at temperatures between 400 and 500 deg C and at water densities from 0 to 930 kg/m3, PVC particles exhibited clearly defined spreading on the anvil surface that was defined as spread time, St. The spread times decreased with increasing temperature and the values increased with increasing water density. Analysis of the residues with infrared spectroscopy showed the presence of both polyenes and polyols, whose formation was correlated with water density. From the analyses, nucleophilic substitution of PVC in water was found to be promoted at low temperatures ( 400 deg C) and high water densities (830 kg/m3), whereas the ionic chain dechlorination was promoted at high temperatures ( 450 deg C) and low water densities ( 750 kg/m3). A reaction pathway is proposed that shows OH nucleophilic substitution in competition with ionic chain reaction for dechlorination both of which vary with water density.