Citation:
LIU Chao, YANG Changzhen, LI Weixue, ZHANG Yonglin, YAO Junshan, LEI Liangcai, LI Haiying. Synthesis of Novel Cyclic Poly(ε-caprolactone-co-γ-triethylsilyloxy-ε-caprolactone)[J]. Chinese Journal of Applied Chemistry,
;2014, 31(10): 1135-1142.
doi:
10.3724/SP.J.1095.2014.30657
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Design and synthesis of well-defined polymers are of the utmost importance for the reliable establishment of macromolecular structure-properties relationships. This work reports a novel strategy to synthesize cyclic random copolyesters with triethylsilyloxy groups. The ring-opening polymerization of a mixture of εCL and functional monomer γ-triethylsilyloxy-ε-caprolactone(γ-Et3SiOεCL) was initiated by 2,2-dibutyl-2-stanna-1, 3-dioxepane(DSDOP) to obtain a precursor, i. e., a living cyclic copolyester(LCP(εCLcoγEt3SiOεCL)). When the comonomers were converted completely, a fresh feed of α-(1-acryloyloxyethyl)-ε-caprolactone(αAEεCL) was added to the polymerization medium to achieve a living cyclic block copolyester, poly((εCLcoγEt3SiOεCL)-b-(αAEεCL)). Finally, stable functional cyclic copolyester free of tin dialkoxides, i. e., cP(εCLcoγEt3SiOεCL)(Mn,NMR=28500), was synthesized by intramolecular photo cross-linking of acrylic unsaturations in the proximity of the living cyclic chain under the irradiation of ultraviolet light. The structure and properties of the copolymers were characterized by size-exclusion chromatography(SEC), proton nuclear magnetic resonance spectroscopy(1H NMR), and differential scanning calorimetry(DSC) technologies. The strategy herein disclosed has been successfully tested for the synthesis of functional cyclic copolyesters with high relative molecular mass in high efficiency.
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