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Synthesis of Isohexide Diyne Polymers and Hydrogenation to Their Saturated Polyethers

Cite this: ACS Macro Lett. 2021, 10, 8, 1068–1072
Publication Date (Web):August 3, 2021
https://doi.org/10.1021/acsmacrolett.1c00422
Copyright © 2021 American Chemical Society

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    Abstract

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    The incorporation of renewable feedstocks into polymer backbones is of great importance in modern polymer science. We report the synthesis of 1,3-diyne polymers derived from the bispropargyl ethers of isosorbide, isomannide, and isoidide. The dialkyne monomers can be polymerized through an adaptation of the Glaser–Hay coupling using a nickel(II) cocatalyst. These well-defined diyne polymers bear an iodoalkyne end group, afforded through an unanticipated reductive elimination pathway, and display glass transition temperatures (Tg) from 55 to 64 °C. Fully saturated, analogous polyethers can be prepared from the hydrogenation of the diyne polymers, and these show Tg values between −10 and −2 °C. Both the 1,3-diyne polymers and the saturated analogues display similar trends in their Tg values vis-à-vis the stereochemical features of the isohexide unit within the backbone. This polymerization provided access to two series of isohexide-based polyethers, the thermal properties of which are influenced by the nature of the 2,4-hexadiynyl and hexamethylene linkers as well as the relative configuration of the bicyclic subunit in the backbone. The reported method represents an important step toward accessing well-defined polyethers from renewable feedstocks using readily available catalysts and convenient ambient conditions.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsmacrolett.1c00422.

    • Experimental details and characterization data for all monomers, model compounds, and polymers (PDF)

    • FAIR NMR data, including the primary 1H and 13C NMR FID files for compounds 2a, 2b, 2c, 3, 4, 5, 6, 7, 2a-RR, poly(2a), poly(2b), poly(2c), poly(2a-RR), poly(2a)-[H], poly(2b)-[H], poly(2c)-[H], S1, S2, S3, and S5 (ZIP)

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    Cited By

    This article is cited by 5 publications.

    1. Joshua C. Worch, Andrew P. Dove. Click Step-Growth Polymerization and E/Z Stereochemistry Using Nucleophilic Thiol–yne/–ene Reactions: Applying Old Concepts for Practical Sustainable (Bio)Materials. Accounts of Chemical Research 2022, 55 (17) , 2355-2369. https://doi.org/10.1021/acs.accounts.2c00293
    2. Connor J. Stubbs, Joshua C. Worch, Hannah Prydderch, Zilu Wang, Robert T. Mathers, Andrey V. Dobrynin, Matthew L. Becker, Andrew P. Dove. Sugar-Based Polymers with Stereochemistry-Dependent Degradability and Mechanical Properties. Journal of the American Chemical Society 2022, 144 (3) , 1243-1250. https://doi.org/10.1021/jacs.1c10278
    3. Jingbo Ma, Xinhong Wang, Zhenting Liu, Xiangping Hu. Highly Diastereo‐ and Enantioselective Copper‐Catalyzed Dipropargylic Amination to Access Bispropargylic Diamines. Asian Journal of Organic Chemistry 2022, 11 (10) https://doi.org/10.1002/ajoc.202200385
    4. Shannon R. Petersen, Hannah Prydderch, Joshua C. Worch, Connor J. Stubbs, Zilu Wang, Jiayi Yu, Maria C. Arno, Andrey V. Dobrynin, Matthew L. Becker, Andrew P. Dove. Ultra‐Tough Elastomers from Stereochemistry‐Directed Hydrogen Bonding in Isosorbide‐Based Polymers. Angewandte Chemie 2022, 134 (17) https://doi.org/10.1002/ange.202115904
    5. Shannon R. Petersen, Hannah Prydderch, Joshua C. Worch, Connor J. Stubbs, Zilu Wang, Jiayi Yu, Maria C. Arno, Andrey V. Dobrynin, Matthew L. Becker, Andrew P. Dove. Ultra‐Tough Elastomers from Stereochemistry‐Directed Hydrogen Bonding in Isosorbide‐Based Polymers. Angewandte Chemie International Edition 2022, 61 (17) https://doi.org/10.1002/anie.202115904

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