Three xanthates with different structures were prepared and employed in vinyl chloride (VC) solution and miniemulsion polymerizations as reversible addition-fragmentation chain transfer (RAFT) agents. It was found that VC polymerization could be well controlled by using O-ethyl-S-(1-ethoxycarbonyl) ethyl dithiocarbonate as the RAFT agent. The rate of VC RAFT miniemulsion polymerization was obviously higher than that of RAFT solution polymerization

and the conversion of VC was higher than 90% for the miniemulsion polymerization running for 12 h

while the molecular weight distribution of poly(vinyl chloride) (PVC) prepared by RAFT miniemulsion polymerization was wider than that of PVC prepared by RAFT solution polymerization. The 1H NMR and UV-Vis absorption spectroscopy analysis of PVC-xanthate proved the presence of chain-end functional groups and the absence of structural defects. PVC-xanthate could be further used as macro-RAFT agent for VC and vinyl acetate polymerization

to prepare chain extended PVC and poly(vinyl chloride)-b-poly(viny acetate) copolymer

respectively. Combined with polymerization kinetics study

the living characters of xanthate-mediated solution and miniemulsion polymerizations of VC were verified.