Polymerization Mechanism of Styrene Initiated by 2,2-Bis(t-butyldioxy)alkanes

Article abstract of DOI:10.1246/bcsj.64.1231

The radical polymerization mechanism of styrene initiated by 2,2-bis(t-butyldioxy)alkanes (1) has been studied in benzene.The decomposition products of 1 are acetone, alkyl methyl ketone, t-butyl alcohol, and t-butyl peracetate.Styrene monomer converts to polystyrene along with styrene oxide.The peroxides 1 cleave homolytically at one of dioxy bonds to yield intermediate alkoxy radicals with α-t-butyldioxy group, which undergo β-scission to afford t-butyldioxy or alkyl radicals.The resulting t-butyldioxy radical reacts with styrene to form 2-(t-butyldiox<)-1-phenylethyl radical, which decomposes subsequently to styrene oxide and t-butoxyl radical via γ-scission.Alternatively, a part of t-butyldioxy radical adds to styrene to afford polystyrene containing dioxy bond.