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Combining ATRP of Methacrylates and ROP of L , L ‐Dilactide and ε ‐Caprolactone
Author(s) -
Ydens Isabelle,
Degée Philippe,
Dubois Philippe,
Libiszowski Jan,
Duda Andrzej,
Penczek Stanislaw
Publication year - 2003
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200290071
Subject(s) - copolymer , polymer chemistry , atom transfer radical polymerization , methacrylate , methyl methacrylate , chemistry , molar mass , polymerization , ring opening polymerization , organic chemistry , polymer
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 [NiBr 2 (PPh 3 ) 2 ] as initiator and catalyst, respectively. Kinetic and molar masses measurements, as well as 1 H NMR spectra analysis of the resulting poly(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 ε ‐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 1 H NMR data demonstrated that the copolymerization was under control and started on the hydroxyl functions available on the poly(MMA‐ co ‐HEMA) multifunctional macroinitiator.Comparison of the SEC traces for the poly(MMA‐ co ‐HEMA) macroinitiator P2 (line only), the polymethacrylate‐ g ‐PLA copolymer C2 (line marked by ○), and the polymethacrylate‐ g ‐PLA C3 (line marked by ▵).