Free-Radical Polymerization of Dimethyl Vinylbenzylphosphonate Controlled by Tempo

The free radical polymerization of a phosphonated styrene, dimethyl vinylbenzylphosphonate (VBP), in the presence of stable nitroxide 2,2,6,6-tetramethyl-1-piperidinyloxyl radical (TEMPO), initiated by dicumyl peroxide (DCP) at 125 °C, has been studied. The apparent rate of polymerization Kp[M•] is eight times higher than that of styrene, but the “living” character of the polymerization could not be verified by SEC. So, a macromolecular initiator PS−TEMPO was used in order to follow the evolution of average number molecular weights by 1H NMR. Under these conditions, the “living” character of the polymerization could be checked and various block copolymers (11000/7500; 11000/11000) were prepared. As for vinylbenzyl chloride and other monomers bearing electroattractive groups, the polymerization was shown to be much faster than that of styrene.