Mechanisms of thermal decompositions of polysulfones: A DFT and CBS-QB3 study

作者：Zhao YL; Jones WH; Monnat F; Wudl F; Houk KN^*

来源：Macromolecules, 2005, 38(24): 10279-10285.

DOI：10.1021/ma051503y

The thermal stabilities of polysulfones with different lengths of the carbon-linker between sulfone groups have been explored. B3LYP and CBS-QB3 calculations on possible thermal decomposition mechanisms of model compounds show that even carbon-linked polysulfones-copolymers of alkenes and SO2-decompose by a radical chain mechanism involving facile depolymerization after initial homolysis. Sulfinate impurities [-S(=O)-O-CH2-], formed as a minor component in polysulfone synthesis, can serve as good initiators for the radical mechanism. Polysulfones with odd-carbon linkers do not readily depolymerize in this fashion owing to high barriers of depropagation; these polymers undergo thermal degradation by the slower cyclic beta-elimination processes.

• 出版日期2005-11-29