Combining ATRP of methacrylates and ROP of L,L-dilactide and ε-caprolactone

Isabelle Ydens, Philippe Degée, Philippe Dubois, Jan Libiszowski, Andrzej Duda, Stanislaw Penczek

Research output: Contribution to journalArticlepeer-review

Abstract

Coupling atom transfer radical polymerization (ATRP) and coordination-insertion ring-opening polymerization (ROP) provided a controlled two-step access to polymethacrylate-graft-polyaliphatic ester graft copolymers. In the first step, copolymerization of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) was carried out at 80°C at high MMA concentration by using ethyl 2-bromoisobutyrate and [NiBr2(PPh3)2] as initiator and catalyst, respectively. Kinetic and molar masses measurements, as well as 1H NMR spectra analysis of the resultingpoly(MMA-co-HEMA)s highlighted the controlled character of the radical copolymerization, while the determination of the reactivity ratios attested preferential incorporation of HEMA. The second step consisted of the ROP of e-caprolactone or L,L-dilactide, in THF at 80°C, promoted by tin octoate (Sn(Oct)2) and coinitiated by poly(MMA-co-HEMA)s obtained in the first step. Once again, kinetic, molar mass, and 1H NMR data demonstrated that the copolymerization was under control and started on the hydroxyl functions available on the poly(MMA-co-HEMA) multifunctional macroinitiator.

Original languageEnglish
Pages (from-to)171-179
Number of pages9
JournalMacromolecular Chemistry and Physics
Volume204
Issue number1
DOIs
Publication statusPublished - 30 Jan 2003
Externally publishedYes

Keywords

  • ε-caprolactone
  • Atom transfer radical polymerization
  • L,L-dilactide
  • Methyl methacrylate
  • Ring-opening polymerization

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