Dependence of transfer reaction on solvent in the free radical polymerization of styrene: Application to the synthesis of PS/PEO copolymers using PEO-based transfer agents

Laurent Businelli, Yves Gnanou*, Bernard Maillard

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

The ability of thiols, dithiobisthioformates and unsaturated peroxyketals to induce transfer in the free radical polymerization of styrene was investigated in various solvents. An increase of the polarity of the solvent resulted in the rise of the chain transfer coefficient in the thiol and dithiobisthioformate cases, while the behavior of unsaturated peroxyacetals was unaffected by the change of solvent. The ability of the two former transfer agents to exist in a polarized transition state in polar media accounted for this result Taking advantage of these features, these transferring functions were introduced at the end of PEO chains and the resulting transfer agents were subsequently used to obtain PEO-b-PS copolymers. Among all hydrophilic transfer agents tried, methyl ether of ω-mercaptoacetate PEO with a molar mass of 2000 g · mol -1 was found particularly interesting, exhibiting a transfer coefficient (C 1 ) close to the ideal value of 1 in acetonitrile/water (95/5) solution. Under these conditions and in the presence of the latter transfer agent, well-defined PS-b-PEO copolymers could be obtained by mere dispersion polymerization of styrene taken to completion.

Original languageEnglish (US)
Pages (from-to)2805-2810
Number of pages6
JournalMacromolecular Chemistry and Physics
Volume201
Issue number18
DOIs
StatePublished - Dec 29 2000

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

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