Synthesis of poly(vinyl alcohol) combs via MADIX/RAFT polymerization

Julien Bernard, Arnaud Favier, Thomas P. Davis, Christopher Barner-Kowollik, Martina H. Stenzel

Research output: Contribution to journalArticleResearchpeer-review

92 Citations (Scopus)


Poly(vinyl acetate) combs have been prepared via macromolecular design via interchange of xanthate (MADIX)/reversible addition-fragmentation chain-transfer (RAFT) polymerization using xanthate functionalized polymer cores. The comb backbones were prepared using well-defined poly(vinyl alcohol) PVA polymers with a degree of polymerization of 20, 100 and 170, respectively. Functionalization with xanthates via R-group or a Z-group approach resulted in the formation of macromolecular MADIX agents. While Z group designed macromolecular xanthate agents appeared to inhibit the polymerization of vinyl acetate (VAc), R group designed macromolecular xanthate agents achieved to mediate efficiently the bulk polymerization of VAc affording PVAc combs. However, the growth of the combs was accompanied at low conversions by the formation of linear polymer chains as a result of the constant initiation (AIBN) and shoulders, which can be attributed to intermolecular coupling reactions. The proportions of single chains and termination products were observed to increase with the degree of polymerization of the macromolecular MADIX agents broadening the molecular weight distribution. As a result of a stable ester link between the branches and the PVA backbone, the branched PVAc architectures were finally hydrolyzed to afford poly(vinyl alcohol) combs.

Original languageEnglish
Pages (from-to)1073-1080
Number of pages8
Issue number4
Publication statusPublished - 8 Feb 2006
Externally publishedYes


  • Combs
  • Poly(vinyl alcohol)
  • RAFT polymerization

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