Thermal volatilization analysis: A versatile platform for spectroscopic investigations of polymer degradation processes

The thermal volatilization analysis (TVA) and subambient thermal volatiliza tion analysis (SATVA) techniques are described. In addition to rate profili ng of the volatile product flux of thermal degradation under high-vacuum co nditions through measurement of pressure in the vacuum line as a function o f sample temperature, the TVA technique is shown to afford a convenient met hod for an isolation, on the basis of volatility under high-vacuum conditio ns, of product fractions of thermal degradation for subsequent spectroscopi c analysis. The capacity and flexibility of TVA as a platform for these ana lyses are illustrated in a case study format by degrading poly(bisphenol A, 2-hydroxy propylether). The overall degradation process is quantified, and most significant pathways of thermolysis are identified through subsequent spectroscopic analysis of products of decomposition. The design and constr uction of a modified vacuum-tight long-path gas IR cell, as an interface al lowing for the application of Fourier transform infrared spectroscopy (FT-I R) for the on-line analysis of volatile products of polymer degradation, is detailed. Proof of concept and application of this new analytical techniqu e, subsequently referred to as TVA/FT-IR, is illustrated through the examin ation of appropriate aspects of the thermal degradation of polymethyl metha crylate polymers.