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Well-Defined Functional Linear Aliphatic Diblock Copolyethers: A Versatile Linear Aliphatic Polyether Platform for Selective Functionalizations and Various Nanostructures

Authors

  • Wonsang Kwon,

    1. Department of Chemistry, Division of Advanced Materials Science, Pohang Accelerator Laboratory, Center for Electro-Photo Behaviors in Advanced, Molecular Systems, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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  • Yecheol Rho,

    1. Department of Chemistry, Division of Advanced Materials Science, Pohang Accelerator Laboratory, Center for Electro-Photo Behaviors in Advanced, Molecular Systems, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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  • Kensuke Kamoshida,

    1. Polymer Chemistry Laboratory, Division of Biotechnology and Macromolecular Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan
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  • Kyung Ho Kwon,

    1. Department of Chemistry, Division of Advanced Materials Science, Pohang Accelerator Laboratory, Center for Electro-Photo Behaviors in Advanced, Molecular Systems, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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  • Youn Cheol Jeong,

    1. Department of Chemistry, Division of Advanced Materials Science, Pohang Accelerator Laboratory, Center for Electro-Photo Behaviors in Advanced, Molecular Systems, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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  • Jonghyun Kim,

    1. Department of Chemistry, Division of Advanced Materials Science, Pohang Accelerator Laboratory, Center for Electro-Photo Behaviors in Advanced, Molecular Systems, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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  • Hideki Misaka,

    1. Polymer Chemistry Laboratory, Division of Biotechnology and Macromolecular Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan
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  • Tae Joo Shin,

    1. SAXS Group, Beamline Division, Pohang Light Source-II (PLS-II), Pohang Accelerator Laboratory, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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  • Jehan Kim,

    1. SAXS Group, Beamline Division, Pohang Light Source-II (PLS-II), Pohang Accelerator Laboratory, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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  • Kwang-Woo Kim,

    1. SAXS Group, Beamline Division, Pohang Light Source-II (PLS-II), Pohang Accelerator Laboratory, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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  • Kyeong Sik Jin,

    1. SAXS Group, Beamline Division, Pohang Light Source-II (PLS-II), Pohang Accelerator Laboratory, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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  • Taihyun Chang,

    1. Department of Chemistry, Division of Advanced Materials Science, Pohang Accelerator Laboratory, Center for Electro-Photo Behaviors in Advanced, Molecular Systems, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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  • Heesoo Kim,

    1. Dongguk University College of Medicine and Dongguk Medical Institute, Gyeongju 780-714, Republic of Korea
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  • Toshifumi Satoh,

    Corresponding author
    1. Polymer Chemistry Laboratory, Division of Biotechnology and Macromolecular Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan
    • Polymer Chemistry Laboratory, Division of Biotechnology and Macromolecular Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan.
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  • Toyoji Kakuchi,

    Corresponding author
    1. Polymer Chemistry Laboratory, Division of Biotechnology and Macromolecular Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan
    • Polymer Chemistry Laboratory, Division of Biotechnology and Macromolecular Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan.
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  • Moonhor Ree

    Corresponding author
    1. Department of Chemistry, Division of Advanced Materials Science, Pohang Accelerator Laboratory, Center for Electro-Photo Behaviors in Advanced, Molecular Systems, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
    • Department of Chemistry, Division of Advanced Materials Science, Pohang Accelerator Laboratory, Center for Electro-Photo Behaviors in Advanced, Molecular Systems, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
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Abstract

Low-temperature anionic ring-opening homopolymerizations and copolymerizations of two glycidol derivatives (allyl glycidyl ether (AGE) and ethoxyethyl glycidyl ether (EEGE)) are studied using a metal-free catalyst system, 3-phenyl-1-propanol (PPA) (an initiator) and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris-(dimethylamino)phosphoranylidenamino]-2Λ5,4Λ5-catenadi(phosphazene) (t-Bu-P4) (a promoter) in order to obtain well-defined functional linear polyethers and diblock copolymers. With the aid of the catalyst system, AGE is found to successfully undergo anionic ring-opening polymerization (ROP) even at room temperature (low reaction temperature) without any side reactions, producing well-defined linear AGE-homopolymer in a unimodal narrow molecular weight distribution. Under the same conditions, EEGE also undergoes polymerization, producing a linear EEGE-homopolymer in a unimodal narrow molecular-weight distribution. In this case, however, a side reaction (i.e., chain-transfer reaction) is found to occur at low levels during the early stages of polymerization. The chemical properties of the monomers in the context of the homopolymerization reactions are considered in the design of a protocol used to synthesize well-defined linear diblock copolyethers with a variety of compositions. The approach, anionic polymerization via the sequential step feed of AGE and EEGE as the first and second monomers, is found to be free from side reactions at room temperature. Each block of the obtained linear diblock copolymers undergoes selective deprotection to permit further chemical modification for selective functionalization. In addition, thermal properties and structures of the polymers and their post-modification products are examined. Overall, this study demonstrates that a low-temperature metal-free anionic ROP using the PPA/t-Bu-P4 catalyst system is suitable for the production of well-defined linear AGE-homopolymers and their diblock copolymers with the EEGE monomer, which are versatile and selectively functionalizable linear aliphatic polyether platforms for a variety of post-modifications, nanostructures, and their applications.

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