Experimental and Theoretical Comparison of Addition-Fragmentation Pathways of Diseleno-and Dithiocarbamate RAFT Agents

Dimitri Matioszek, Stéphane Mazières, Oleksii Brusylovets, Ching Yeh Lin, Michelle L. Coote, Mathias Destarac, Simon Harrisson

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

Theoretical studies suggest that identically substituted dithio-and diselenocarbamate reversible addition-fragmentation chain transfer (RAFT) agents will have similar reactivity but that diselenocarbamate RAFT agents are more likely to undergo intermediate radical termination. These results are supported by an experimental study of polymerizations of vinyl acetate mediated by Se-cyanomethyl N,N-dimethyldiselenocarbamate (1Se) and its sulfur analog, S-cyanomethyl N,N-dimethyldithiocarbamate (1S). While the two polymerizations had similar interchain transfer constants (3.2 for 1S and 3.9 for 1Se), significant retardation was observed for 1Se-mediated polymerizations. External chain transfer constants were also measured for 1S (5.4) and 1Se (45). The low apparent value of the chain transfer constant of 1S is attributed to the selective formation of a single monomer adduct in the early stages of the reaction.

Original languageEnglish
Pages (from-to)3376-3386
Number of pages11
JournalMacromolecules
Volume52
Issue number9
DOIs
Publication statusPublished - 14 May 2019
Externally publishedYes

Keywords

  • diselenocarbamate RAFT agents
  • addition-fragmentation pathways
  • intermediate radical termination
  • polymerization
  • vinyl acetate
  • Se-cyanomethyl N,N-dimethyldiselenocarbamate (1Se)
  • S-cyanomethyl N,N-dimethyldithiocarbamate (1S)
  • interchain transfer constants(3.2 for 1S and 3.9 for 1Se)

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