High‐temperature degradation of polymers. Thermal gradients and diffusion‐controlled reactions

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Abstract
Poly(methyl methacrylate) films of various thicknesses were degraded in stainless‐steel closed reaction vessels and in closed quartz vessels of different wall thicknesses over a range of temperatures from 350 to 500°C. Above certain temperatures monomer formation becomes diffusion‐controlled. The degree of this diffusion control depends on the type of reaction vessel, wall thickness of the vessel, and film thickness. The rates of monomer formation for a definite percentage of conversion depend on the thermal history of the polymer sample. Thus, for the same percentage of conversion and the same film temperature the rates can become quite different.

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