SET-LRP of methyl acrylate to complete conversion with zero termination

Nga H. Nguyen, Martin E. Levere, Virgil Percec

Research output: Contribution to journalArticle

109 Citations (Scopus)

Abstract

The single electron transfer-living radical polymerization of methyl acrylate (MA) initiated by bis(2-bromopropionyl)ethane (BPE) in dimethyl sulfoxide was carried out to 100% monomer conversion and complete absence of bimolecular termination under the following reaction conditions: [MA]/[BPE]/[Me 6-TREN]/[CuBr 2] = 60/1/0.21/0.01 and [MA]/[BPE]/[TREN]/[CuBr 2] = 60/1/0.25/0.05. These polymerizations were mediated by 0.5 cm of hydrazine-activated Cu(0) wire of 20 gauge (0.812 cm in diameter), corresponding to a surface area of 0.14 cm 2 of Cu(0) per 3 mL reaction volume (2/1 v/v monomer/solvent). A higher extent of bimolecular termination (5-13%) was observed at complete conversion when longer lengths of Cu(0) wire were used. In the absence of CuBr 2 the activated Cu(0) wire/Me 6-TREN catalyst in dimethyl sulfoxide also allowed the synthesis of perfectly bifunctional and monofunctional PMAs at complete conversion. This was also demonstrated by the quantitative reinitiation experiments from the chain(s) end(s) of these macroinitiators.

Original languageEnglish
Pages (from-to)860-873
Number of pages14
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume50
Issue number5
DOIs
Publication statusPublished - 1 Mar 2012

Keywords

  • chain-end analysis
  • kinetics (polym.)
  • MALDI
  • single electron transfer-living radical polymerization (SET-LRP)
  • termination

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry

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