Synthesis and characterization of crystalline graft polymer poly(ethylene oxide)‐g‐poly(ɛ‐caprolactone)2 with modulated grafting sites |
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Authors: | Yingying Ma Jian Huang Kunyan Sui Guowei Wang |
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Affiliation: | 1. Department of Polymer Science and Engineering, State Key Laboratory Cultivating Base for New Fiber Materials and Modern Textiles, Qingdao University, , Qingdao, 266071 China;2. Department of Macromolecular Science, State Key Laboratory of Molecular Engineering of Polymers, Fudan University, , Shanghai, 200433 China |
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Abstract: | The graft polymer poly(ethylene oxide)‐g‐poly(?‐caprolactone)2 (PEO‐g‐PCL2) with modulated grafting sites was synthesized by the combination of ring‐opening polymerization (ROP) mechanism, efficient Williamson reaction, with thiol–ene addition reaction. First, the precursor of PEO‐Allyl‐PEO with two terminal hydroxyl groups and one middle allyl group was prepared by ROP of EO monomers. Then, the macroinitiator [PEO‐(OH)2‐PEO]s was synthesized by sequential Williamson reaction between terminal hydroxyl groups and thiol–ene addition reaction on pendant allyl groups. Finally, the graft polymer PEO‐g‐PCL2 was obtained by ROP of ?‐CL monomers using [PEO‐(OH)2‐PEO]s as macroinitiator. The target graft polymer and all intermediates were well characterized by the measurements of gel permeation chromatography, 1H NMR, and thermal gravimetric analysis. The crystallization behavior was investigated by the measurements of differential scanning calorimetry, wide‐angle X‐ray diffraction and polarized optical microscope. The results showed that when the PCL content of side chains reached 59.2%, the crystalline structure had been dominated by PCL part and the crystalline structure formed by PEO part can be almost neglected. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2239–2247 |
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Keywords: | crystallization graft polymer poly(ɛ ‐caprolactone) (PCL) poly(ethylene oxide) (PEO) ring‐opening polymerization (ROP) Williamson reaction thiol‐ene addition reaction |
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