Controlled Syntheses of Well-Defined Poly(thionophosphoester)s That Undergo Peroxide-Triggered Degradation

Controlled Syntheses of Well-Defined Poly(thionophosphoester)s That Undergo Peroxide-Triggered Degradation
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受过氧化物触发降解的明确聚硫代磷酸酯的受控合成

DOI:
10.1021/acs.macromol.9b00061
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发表时间:
2019-06-11
期刊:
影响因子:
5.5
通讯作者:
Wang, Yucai
Wang, Yucai
中科院分区:
化学1区
文献类型:
--
作者:
Liu, Yi;Bejjanki, Naveen Kumar;Wang, Yucai

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We reported the preparation of well-defined poly(thionophosphoester)s as oxidation-responsive materials that undergo peroxide-triggered degradation. The polymers were synthesized via the controlled ring-opening polymerization of cyclic thionophosphoesters initiated with hydroxyl terminal small molecule and macromolecular initiators and catalyzed with 1,5,7-triazabicyclo[4.4.0]dec-5-ene in tetrahydrofuran at room temperature. The resulting poly-(thionophosphoester)s were characterized in detail by NMR spectroscopy and size exclusion chromatography. Polymerization of cyclic oxophosphoester (P=O) monomers exhibited broad molecular weight distribution and severe side reactions, while narrow molecular weight distribution ((D) over bar (M) similar to 1.1) was achieved without significant transesterifications using thionophosphoester (P=S) monomers. The reaction kinetics of thionophosphoester monomers were in agreement with living polymerization characteristics. Furthermore, by replacing P=O bond by P=S, the polymers changed from hydrophilic to hydrophobic. These well-controlled sulfur-containing polymers are more resistant to hydrolytic degradation but undergo peroxide-triggered degradation. Poly(thionophosphoester)s are thus promising in the field of biomedical materials.