Coordination radical polymerization of methyl methacrylate, initiated by the azobis(isobutyronitrile)–tri- n -butylborane binary system

A procedure for coordination radical polymerization of methyl methacrylate in the bulk, initiated by the azobis(isobutyronitrile)–tri- n -butylborane binary system at 60°С, was developed. Butyl radicals participating in the initiation step were detected by EPR. These radicals are generated by complexation of cyanoisopropyl radicals with trialkylborane. The radical at the boron atom transforms from the C-centered to N-centered structure with the subsequent S R 2 reaction and fast generation of n -butyl radicals. As found by NMR and confirmed by kinetic studies, the tri- n -butylborane–initiator–monomer system stimulates generation of propagating poly(methyl methacrylate) radicals.