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Controlled Radical Polymerization of Vinyl Chloride Mediated by Xanthene-9-Thione

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journal contribution
posted on 13.11.2019, 13:09 by Peng Cui, Changtong Song, Xianhong Zhang, Dong Chen, Yuhong Ma, Wantai Yang
The controlled radical polymerization (CRP) of vinyl chloride monomer (VCM), a low activity monomer with high radical reactivity, is still a true challenge. In this study, a novel CRP of VCM with high monomer conversion at 45 °C with xanthene-9-thione (XT) as mediator and bis(4-tert-butylcyclohexyl)­peroxydicarbonate (TBCP) as initiator is achieved. The Mn of the produced poly­(vinyl chloride) (PVC) increases slightly with increasing monomer conversion and could be mediated in the range from 6k to 12k by simply changing the molar ratio of TBCP/XT while the dispersity maintains around 2.0. The fidelity of XT dormant groups of PVC-XT is about 60–80% and depends on the ratio of TBCP/XT. With the as-prepared PVC-XT as macroinitiator, block copolymerizations of methyl methacrylate (MMA), n-butyl acrylate (BA), and styrene (St) are carried out and the PVC-b-PMMA, PVC-b-PBA, and PVC-b-PSt block copolymers have been synthesized successfully.