Kinetic study on reversible addition-fragmentation chain transfer (RAFT) process for block and random copolymerizations of styrene and methyl methacrylate

Keiji Kubo, Atsushi Goto, Koichi Sato, Yungwan Kwak, Takeshi Fukuda*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

43 Citations (Scopus)

Abstract

The degenerative (exchange) chain transfer constant Cex was determined for the dithioacetate-mediated living radical block and random copolymerizations of styrene (St) and methyl methacrylate (MMA) at 40 °C. The addition of the polystyrene (PSt) radical to a polymer-dithioacetate adduct (P-X) to form the intermediate radical (PSt-(X.)-P) was (about twice) faster than that of the poly(methyl methacrylate) (PMMA) radical to form the intermediate radical PMMA-(X.)-P. The fragmentation (release) of the PMMA radical from the PSt-(X.)-PMMA intermediate formed at the initiating stage of block copolymerization was much (about 100 times) faster than the release of the PSt radical, explaining why the block copolymerization of MMA from a PSt-dithiocarbonate adduct is not so satisfactory as that of St from a PMMA-dithiocarbonate adduct. In the random copolymerization, there was implicit penultimate unit effect on the exchange chain transfer process, which appeared in the addition process but not in the fragmentation process.

Original languageEnglish
Pages (from-to)9762-9768
Number of pages7
JournalPolymer
Volume46
Issue number23
DOIs
Publication statusPublished - Nov 14 2005
Externally publishedYes

ASJC Scopus Subject Areas

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

Keywords

  • Copolymerization
  • Living radical polymerization
  • Reversible addition-fragmentation chain transfer (RAFT)

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