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One-Pot Nonisocyanate Synthesis of Sequence-Controlled Poly(hydroxy urethane)s from a Bis(six-membered cyclic carbonate) and Two Different Diamines

Cite this: Macromolecules 2021, 54, 5, 2059–2067
Publication Date (Web):February 17, 2021
https://doi.org/10.1021/acs.macromol.1c00045
Copyright © 2021 American Chemical Society

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    Abstract

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    Sequence-controlled synthetic polymers have received increasing interest because of their great potential to develop next-generation functional materials. Here, we report a facile synthesis of a symmetric spiro bis(six-membered cyclic carbonate), 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-dione (1), its reactivity, and a one-pot, nonisocyanate synthesis of sequence-controlled poly(hydroxy urethane)s (PHUs) from 1 with two different symmetric diamines. The second-order rate constant for the ring-opening addition reaction of one of the two cyclic carbonates of 1 with 1-hexylamine is two orders of magnitude larger than that of the remaining one of the resulting intermediate due to a remarkable difference between their ring strain energies. This difference in the reactivity enables the selective formation of a diurethane-linked bis(six-membered cyclic carbonate) from the reaction of 1 with a diamine (0.5 equiv). The subsequent addition of a different diamine (0.5 equiv) to the same pot affords sequence-controlled PHUs with an ABAC sequence.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.macromol.1c00045.

    • Experimental and computational details; characterizations of 1, model compounds, and polymers; and additional spectroscopic data (PDF)

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    Cited By

    This article is cited by 8 publications.

    1. Victor Salvado, Marc Dolatkhani, Étienne Grau, Thomas Vidil, Henri Cramail. Sequence-Controlled Polyhydroxyurethanes with Tunable Regioregularity Obtained from Sugar-Based Vicinal Bis-cyclic Carbonates. Macromolecules 2022, 55 (16) , 7249-7264. https://doi.org/10.1021/acs.macromol.2c01112
    2. Péroline Helbling, Fabien Hermant, Morgane Petit, Thomas Vidil, Henri Cramail. Design of Plurifunctional Cyclocarbonates and their Use as Precursors of Poly(hydroxyurethane) Thermosets: A Review. Macromolecular Chemistry and Physics 2023, 224 (23) https://doi.org/10.1002/macp.202300300
    3. Shusuke Okamoto, Yuii Watanabe, Yoshiaki Yoshida, Takeshi Endo. Synthesis of water-soluble tetrafunctional urethane acrylate bearing a pentaerythritol core and its radical polymerization behaviors in an aqueous solution. Polymer 2023, 286 , 126402. https://doi.org/10.1016/j.polymer.2023.126402
    4. Tadashi Naito, Arihiro Kanazawa, Sadahito Aoshima. Alternating cationic copolymerizations of vinyl ethers and sequence-programmed cyclic trimer consisting of one vinyl ether and two aldehydes for ABCC-type periodic terpolymers. Polymer Chemistry 2023, 14 (23) , 2829-2837. https://doi.org/10.1039/D3PY00278K
    5. Tadashi Naito, Arihiro Kanazawa, Sadahito Aoshima. Two-step degradable ABAC-type periodic poly(cyclic acetal)s synthesized by sequence-programmed monomer formation and subsequent polyaddition based on cyclotrimerization of one vinyl monomer and two aldehydes. Giant 2023, 14 , 100159. https://doi.org/10.1016/j.giant.2023.100159
    6. Dinesh Kumar Chelike, Senthil A. Gurusamy Thangavelu. Biodegradable isocyanate-free polyurethane films via a noncatalytic route: facile modified polycaprolactone triol and biobased diamine as precursors. RSC Advances 2022, 13 (1) , 309-319. https://doi.org/10.1039/D2RA05710G
    7. Yasuyuki Mori, Takahiro Houda, Akihiko Tsuge, Takeshi Endo. Properties of poly(methacrylate)s bearing hydroxyurethane structures synthesized by various amines with poly(methacrylate)s containing five-membered cyclic carbonates obtained from poly(glycidyl methacrylate) and carbon dioxide. Polymer Bulletin 2022, 79 (11) , 9741-9751. https://doi.org/10.1007/s00289-021-03943-z
    8. Qingyong Chen, Jingtong Ye, Linlin Zhu, Jiye Luo, Xiuhua Cao, Zhen Zhang. Organocatalytic multicomponent polymerization of bis(aziridine)s, diols, and tosyl isocyanate toward poly(sulfonamide urethane)s. European Polymer Journal 2022, 180 , 111585. https://doi.org/10.1016/j.eurpolymj.2022.111585

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