Synthesis of adaptative and amphiphilic polymer model conetworks by versatile combination of ATRP,ROP, and “Click chemistry” |
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Authors: | Laetitia Mespouille Olivier Coulembier Dilyana Paneva Philippe Degée Iliya Rashkov Philippe Dubois |
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Institution: | 1. Center of Innovation and Research in MAterials and Polymers (CIRMAP), Laboratory of Polymeric and Composite Materials, University of Mons‐Hainaut, 20, Place du Parc, B‐7000 Mons, Belgium;2. Laboratory of Bioactive Polymers, Institute of Polymers, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria |
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Abstract: | Well‐defined adaptative and amphiphilic polymer conetworks based on hydrophilic poly(N,N‐dimethylamino‐2‐ethyl methacrylate) (PDMAEMA) and hydrophobic poly(ε‐caprolactone) (PCL) have been prepared by combination of ATRP, ROP, and “Click chemistry.” Telechelic α,ω‐alkyne terminated PCL crosslinker was obtained by ring‐opening polymerization (ROP) of CL in THF at 80 °C initiated by 1,4‐butanediol and catalyzed by tin(II) bis 2‐ethyl hexanoate (Sn(Oct)2), followed by the quantitative esterification of hydroxyl end‐groups by activated 4‐pentynoic acid. In parallel, an azido‐containing PDMAEMA‐based copolymer was obtained in a three‐step strategy involving primarily the copolymerization of DMAEMA with newly synthesized 2‐(2‐azidoethoxy)ethyl methacrylate (AEEMA) monomer. The latter was obtained by nucleophilic substitution of chloride atom from 2‐(2‐chloroethoxy)ethanol by an azide group followed by the esterification reaction of the hydroxyl group with methacrylic anhydride. The copolymerization was carried out in an equivolumic mixture of H2O and isopropanol at r.t. and initiated by a ω‐bromoisobutyryl oligo PEO macroinitiator in the presence of various ligated copper(I)‐based catalysts. In a last step, both polymer precursors were chemically linked by the Huisgen‐1,3‐dipolar cycloaddition in anhydrous THF at r.t. using CuBr complexed by 2,2′‐bipyridine ligand as catalyst. Final material was characterized by the means of DSC and SEM, both attesting of a homogeneous distribution of the PCL crosslinkers and a highly porous structure in this new amphiphilic model conetworks. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4997–5013, 2008 |
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Keywords: | adaptative amphiphilic atom transfer radical polymerization biocompatibility biodegradable Huisgen‐1 3‐dipolar cycloaddition model conetworks networks poly(N N‐dimethylamino‐2‐ethyl methacrylate) poly(ε ‐caprolactone) ring‐opening polymerization |
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