Investigation of the effects of nonisothermal suspension polymerization of vinyl chloride on the fusion and degradation behavior of poly(vinyl chloride)

Thermal stability of poly(vinyl chloride) (PVC) samples polymerized under a temperature trajectory was studied from the point of view of morphological and microstructural characteristics. The results are compared with those of the PVC samples obtained by polymerization at constant temperature having the same K value. The Brabender^® plastograph data indicated that the final PVC synthesized with the temperature trajectory showed lower fusion time and higher thermal stability time. The nonisothermal condition also increased the degree of fusion of the final PVC resin, reflecting lower temperature/time required to process it. It was found that the thermal stability of nonisothermally produced PVC as characterized by dehydrochlorination rate decreased (improved) with the increasing monomer conversion until a minimum value was reached that corresponded to the conversion at the pressure drop. However, the dehydrochlorination rate remains almost constant with conversion for an isothermal grade PVC resin. Although the evolution of the number of internal double bonds as well as extent of discoloration of PVC with conversion shows a decreasing trend, the labile chlorine concentration exhibits a maximum at early conversion. The reason for the former can be explained by the temperature dependence of reactions forming defect structures, which are kinetically controlled and thus favored at higher temperatures. The latter, however, can be explained because of the increasing importance of transfer reactions to polymer with increasing polymer concentration. Finally, the results from differential thermogravimetry verify an improvement in thermal stability of the final PVC prepared by using a temperature trajectory during vinyl chloride monomer suspension polymerization. J. VINYL ADDIT. TECHNOL., 23:259–266, 2017. © 2015 Society of Plastics Engineers