Indene, α‐methylstyrene, and styrene were polymerized in liquid sulfur dioxide in the presence of hydroperoxides and peracids. With indene, depending on the molar ratio of the monomer to sulfur dioxide, homopolymerization and polysulfone formation could be observed. With α‐methylstyrene spontaneous polymerization in liquid sulfur dioxide was observed; the addition of hydroperoxide increased the yield and molecular weight. Styrene was polymerized in this solvent with hydroperoxides and peracids, the latter being a more effective initiator. The initiation in these systems could be explained by the formation of a mixed anhydride between sulfuric acid and m‐chlorobenzoic acid.
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