The thermal degradation of polyvinyl compounds. II. The degradation of benzoyl peroxide catalyzed polymethyl methacrylates
N. Grassie, Harry Work Melville
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Published: Oct 7, 1949
DOI: 10.1098/rspa.1949.0122
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Abstract The thermal degradation of polymethyl methacrylates prepared by means of benzoyl peroxide has been investigated. The rate of monomer evolution is independent of molecular size for a given weight of polymer except that it falls off when the molecular weight approaches 500,000. Similarly at sufficiently low molecular weights the number of molecules in the tray of the still continuously decreases while the average size remains constant. These facts point to the mechanism’s involving the fission of the molecule into radicals, the fission occurring at the end of the molecule. Thereafter the large radical rapidly undergoes degradation, monomer units being evolved until the radical is completely removed. With the larger radicals there is not time for complete degradation; instead these interact by disproportionation and thus become stabilized.
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