Solution and aqueous miniemulsion polymerizations of vinyl chloride (VC) mediated by (3,3,4,4,5,5,6,6,7, 7,8,8,8-tridecafluorooctyl-2-((ethoxycarbonothioyl)thio) propanoate) (X1) were studied. The living characters of X1-mediated solution and miniemulsion polymerizations of VC were confirmed by polymerization kinetics. The miniemulsion polymerization exhibits higher rate than solution polymerization. Final conversions of VC in the reversible addition-fragmentation chain transfer (RAFT) miniemulsion polymerization reach as high as 87% and are independent of X1 concentration. Initiation process of X1-mediated RAFT miniemulsion polymerization is controlled by the diffusion-adsorption process of prime radicals. Due to the heterogeneity of polymerization environments and concentration fluctuation of RAFT agent in droplets or latex particles, PVCs prepared in RAFT miniemulsion exhibit relatively broad molecular weight distribution. Furthermore, chain extensions of living PVC (PVC-X) with VC, vinyl acetate (VAc), and N-vinylpyrrolidone (NVP) reveal that PVC-X can be reinitiated and extended, further confirming the living nature of VC RAFT polymerization. PVC-b-PVAc diblock copolymer is successfully synthesized by the chain extension of PVC-X in RAFT miniemulsion polymerization.

Reversible addition–fragmentation chain transfer miniemulsion (co)polymerizations of vinyl acetate (VAc) and vinyl chloride (VC) are conducted in the presence of a fluorinated xthanate (X1). VAc miniemulsion polymerization can be well controlled by X1, and PVAc with small polydispersity index (PDI, <1.20) are obtained. X1 also shows well mediative effect to VC‐VAc miniemulsion copolymerization, while the PDI of VC‐VAc copolymer is greater than that of PVAc since a chain transfer rate to VC is greater than that to VAc. PVAc‐b‐PVC copolymers are synthesized by VC miniemulsion polymerizations mediated by X1‐terminated PVAc. PDIs of PVAc‐b‐PVC copolymers are greater than that of PVAc and VC‐VAc random copolymers with close monomer compositions, and increase with the increase of VC conversion. This is caused by the increased chain transfer to monomer and the formation of monomer‐rich and polymer‐rich phases during the VC polymerization stage. As‐prepared PVAc‐b‐PVC copolymers exhibit a micro‐phase separated morphology. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45074.