Analysis of the Cu(0)-catalyzed polymerization of methyl acrylate in disproportionating and nondisproportionating solvents

Nga H. Nguyen, Martin E. Levere, Jakov Kulis, Michael J. Monteiro, Virgil Percec

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132 Citations (Scopus)

Abstract

The kinetic and structural analyses of the polymer resulting from the Cu(0)/Me 6-TREN-mediated polymerization of methyl acrylate (MA) initiated with methyl 2-bromopropionate (MBP) in solvents mediating different degrees of disproportionation are reported. Accurate analyses of the polymerization and of the resulting polymer demand a minimum combination of techniques that includes kinetics, GPC, 1H NMR, and MALDI-TOF both performed before and after chain-end functionalization via thio-bromo click chemistry and reinitiation experiments. At [MA] 0/[MBP] 0 = 222 the use of the disproportionating solvent DMSO generated first-order kinetics and 97% active chain ends of the polymer at 89% conversion. The less disproportionating solvent MeCN produced two linear first-order kinetics and a decrease of bromine chain-end functionality of the polymer with conversion, yielding 77% active chain ends at 89% conversion. The nondisproportionating solvent toluene, in the presence of TEMPO, produced two linear first-order kinetics with only 50% active chain ends of the polymer at 92% conversion.

Original languageEnglish
Pages (from-to)4606-4622
Number of pages17
JournalMacromolecules
Volume45
Issue number11
Early online date12 May 2012
DOIs
Publication statusPublished - 12 Jun 2012

ASJC Scopus subject areas

  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry

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