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Facile synthesis of linear–hyperbranched polyphosphoesters via one‐pot tandem ROMP and ADMET polymerization and their transformation to architecturally defined nanoparticles
Authors:Liang Ding  Ling Lin  Chengshuang Wang  Jun Qiu  Zhenshu Zhu
Institution:1. School of Materials Engineering, Yancheng Institute of Technology, Yancheng, China;2. Key Laboratory of Eco‐Textile, Ministry of Education, Jiangnan University, Wuxi, China;3. Key Laboratory of Drug Quality Control and Pharmacovigilance, Ministry of Education, China Pharmaceutical University, Nanjing, China;4. Department of Pharmaceutical Analysis, China Pharmaceutical University, Nanjing, China;5. Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore
Abstract:A convenient one‐pot synthesis of linear–hyperbranched polyphosphoesters (l–HBPPEs) was accomplished by a tandem ring‐opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polymerization procedure. A linear monotelechelic poly(norbornene) with a terminal acrylate and many pendent thiol groups is first prepared through adding an internal cis‐olefin terminating agent to the reaction mixture immediately after the completion of the living ROMP, and then utilized as a macromolecular chain stopper in subsequent ADMET polymerization of a phosphoester functional AB2 monomer, yielding l–HBPPEs as the reaction time prolonged. These l–HBPPEs bearing lots of pendent thiol groups in linear poly(norbornene) and peripheral acrylate groups in HBPPE could be self‐crosslinked in ultradilute solution through thiol‐Michael addition click reaction between acrylate and thiol to give single‐molecule nanoparticles with comparatively uniform size. This facile approach can be extended toward the fabrication of novel nanomaterials with sophisticated structures and tunable multifunctionalities. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 964–972
Keywords:crosslinking  hyperbranched  linear–  hyperbranched polyphosphoesters  metathesis polymerization  nanoparticles  nanostructure  one‐pot process  polyolefins  ROMP  self‐crosslinked
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