Reactions of poly(methyl methacrylate) radicals with some p-quinones in the presence of tri-n-butylboron in methyl methacrylate polymerization

The polymerization of methyl methacrylate initiated by dicyclohexyl peroxydicarbonate at 30 °C was studied in the presence of tri-n-butylboron and a series of quinones, namely, p-benzoquinone, chloranil, and 2,5-di-tert-butyl-p-benzoquinone, whose concentration changed from 0.25 to 2.00 mol.%. The initial polymerization rate and molecular weight of poly(methyl methacrylate) depend on the structure and concentration of quinone. The growth radicals react with p-benzoquinone and chloranil predominantly at the C=C bond, while they react at the C=O bond of 2,5-di-tert-butyl-p-benzoquinone. The terminal stable oxygen-centered radicals that formed react with alkylborane, terminating reaction chains and generating alkyl radicals into the bulk. The latter are involved in chain initiation.