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Atom Transfer Radical Polymerization of Styrene Using Multifunctional Iniferter Reagents as Initiators

Two multifunctional iniferters, 1,4-bis-(α-N,N-diethyldithiocarbamyl-isobutyryloxy)-benzene (BDCIB) and 1,3,5-tris-(α-N,N-diethyldithiocarbamyl-isobutyryloxy)-benzene (TDCIB), were successfully synthesized and used as initiators to initiate the polymerization of styrene in the presence of a CuBr/PMDETA complex. The polymerization results demonstrated that the kinetic plots in all cases were first-order to the monomer, the molecular weight of the polymers increased linearly with the monomer conversion; meanwhile, the molecular weight distribution of the polymer was kept to a very low value (M w /M n ≤1.35). Furthermore, the measured molecular weights were very close to the calculated values, which indicated the high efficiency of the initiator for the polymerization of styrene. The effect of catalyst concentration and initiator concentration was not obvious and the influence of polymerization temperature was apparent, and the polymerization rate increased with the polymerization temperature. The results of chain-extension and 1 H NMR analysis proved that the polymer obtained was capped with diethylthiocarbamoylthiy (DC) group.