The Oxidative Polymerization of Vinyl Monomers in the Presence of N ‐Hydroxyphthalimide

The oxidation of vinyl compounds such as styrene, α ‐methylstyrene, methyl methacrylate, acrylonitrile with molecular oxygen in the presence of N ‐hydroxyphthalimide have been studied. It was shown that the N ‐hydroxyphthalimide is efficient in initiation of the oxidative polymerization of vinyl monomers. The products of the monomer oxidation at 66 °C and 1 atm of O 2 are corresponding polyperoxides and low molecular carbonyl compounds. IR‐ and 1 H NMR spectroscopy confirm the alternating copolymer structure of polyperoxides with –O–O– bonds in the main chain. In the oxidative polymerization of vinyl monomers initiated with the mixtures of N ‐hydroxyphthalimide and 2,2′‐azobisisobutyronitrile or benzoyl peroxide it was observed a synergistic effect of initiators’ action. N ‐hydroxyphthalimide reacts with molecular oxygen, initiator radicals or monomer to form the phthalimide‐ N ‐oxyl radical, which participates in the chain initiation stage and does not participate in the termination stages, which leads to a synergistic effect.