Synthesis of Graft Copolymers by the Combination of ATRP and Enzymatic ROP in scCO2

A simple strategy is reported for the synthesis of well-defined graft copolymers of poly(methyl methacrylate-co-2-hydroxyethyl methacrylate) P(MMA-co-HEMA) with poly(ε-caprolactone) (PCL) grafted chains. Using scCO2 as the only solvent, a one-step synthetic approach is adopted to prepare copolymer b...

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Bibliographic Details
Published in:Macromolecules 2006-12, Vol.39 (26), p.9080-9086
Main Authors: Villarroya, Silvia, Zhou, Jiaxiang, Thurecht, Kristofer J, Howdle, Steven M
Format: Article
Language:English
Subjects:
Applied sciences
Copolymerization
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Preparation, kinetics, thermodynamics, mechanism and catalysts
Online Access:Get full text
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Summary:A simple strategy is reported for the synthesis of well-defined graft copolymers of poly(methyl methacrylate-co-2-hydroxyethyl methacrylate) P(MMA-co-HEMA) with poly(ε-caprolactone) (PCL) grafted chains. Using scCO2 as the only solvent, a one-step synthetic approach is adopted to prepare copolymer backbones via atom transfer radical polymerization (ATRP), and grafted chains are added via enzymatic ring-opening polymerization (eROP). Exhaustive study of the enzymatic grafting efficiency showed that only the hydroxyl groups in the backbone initiated the polymerization of ε-CL, resulting in an exceptional polymer architecture which is not accessible by conventional chemical polymerization methodology. The lower grafting density obtained (ca. 30−40%) with the enzymatic polymerization of ε-CL indicates that the system is likely limited by steric hindrance.
ISSN:0024-9297
1520-5835
DOI:10.1021/ma061068n