Thermal Decomposition and Glass Transition Temperature of Poly(phenyl Methacrylate) and Poly(cyclohexyl Methacrylate)

The thermal decomposition and the glass transition temperature T_g of poly(phenyl methacrylate) (PPhMA) and poly(cyclohexyl methacrylate) (PcHU) were studied with a differential scanning calorimeter (DSC). The undecomposed and decomposed polymers were analyzed by gel permeation chromatography (GPC) for molecular weight distributions and by DSC for changes in the thermal properties, e.g., T_g. For all values of weight-loss α, the thermal stability of the polymers follows the order: Poly-(methyl methacrylate) (PMMA) = PcHMA > poly(ethyl methacrylate) (PEMA) > PPhMA > poly(n-butyl methacrylate) (PnBuMA) > poly(isobutyl methacrylate) (PiBuMA). In the depolymerization reactions that occur during the isothermal decomposition of PPhMA, there is no specific preference for longer or shorter chains although a minor fraction of the volatilized fraction with an Mbar]_w 10^?5 of 2.5 and an Mbar] _n |MX 10.^?5 of 1.5 does undergo chain recombination yielding high molecular weight products with an M_w × 10^?6 of 1.35 and an M_n × 10^?6 of 1.0 to 1.23. In the case of PcHMA, depolymerizations did show a preference for longer chains. No chain recombination, however, was found to take place. Activation energy of decomposition for substituted poly-methacrylates follows the order: PnBuMA = PiBuMA >; PEMA >; PcHMA >; PMMA >; PPhMA. T_{g e} values of PPhMA samples varied from 362 K for undecomposed polymers to 396 K for a polymer treated at 300° C. The literature value of 383 K does fall within this range. In the case of PcHMA, an average T_ge of 356 f 6.0 ± is not far removed from the reported value of 359 K.