REACTIVITY OF PRIMARY RADICALS IN THE RADICAL POLYMERIZATION OF DIALKYL FUMARATES INITIATED WITH DIMETHYL 2,2'-AZOBIS(ISOBUTYRATE) AND 2,2'-AZOBIS(ISOBUTYRONITRILE)

Radical polymerizations of some dialkyl fumarates (DRFs) and ordinary vinyl monomers(monosubstituted and 1,1-disubstituted ethylenes) were carried out with dimethyl 2,2'-azobis(isobutyrate) (MAIB) and 2,2'-azobis(isobutyronitrile) (AIBN) as initiators. The overall polymerization reactivities of the DRFs have been found to dramatically change depending on the structure of the primary radicals used, while polymerization of the vinyl monomers was not appreciably influenced by the initiators. To investigate the difference in the reactivities of the primary radicals (i.e., 2-(methoxycarbonyl)-2-propyl and 2-cyano-2-propyl) in polymerizations of DRFs initiated with MAIB and AIBN, radical copolymerizations of DRFs with methyl methacrylate (MMA) and methacrylonitrile (MAN) were examined. Furthermore, polymerizations of DRFs with MAIB and AIBN were carried out in the presence of trace amounts of MMA and MAN, and the polymerization behaviors were compared with those for the polymerizations in the absence of MMA and MAN.