ACS Publications. Most Trusted. Most Cited. Most Read
Backbone-Degradable Polymers via Radical Copolymerizations of Pentafluorophenyl Methacrylate with Cyclic Ketene Acetal: Pendant Modification and Efficient Degradation by Alternating-Rich Sequence

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:ACS Macro Lett. 2021, 10, 10, 1223-1228
    Letter

    Backbone-Degradable Polymers via Radical Copolymerizations of Pentafluorophenyl Methacrylate with Cyclic Ketene Acetal: Pendant Modification and Efficient Degradation by Alternating-Rich Sequence
    Click to copy article linkArticle link copied!

    Other Access OptionsSupporting Information (1)

    ACS Macro Letters

    Cite this: ACS Macro Lett. 2021, 10, 10, 1223–1228
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsmacrolett.1c00513
    Published September 23, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    This work deals with syntheses of backbone-degradable polymers via the radical copolymerization of pentafluorophenyl methacrylate (PFMA) with 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), which undergoes ring-opening propagation to afford an ester-bonded backbone. The combination of the electron-deficient methacrylate with the electron-rich cyclic monomer allowed high crossover copolymerization, and the electronic effect was clarified by the comparison with the copolymerization of methyl methacrylate (MMA) and BMDO. The PFMA units of the resultant copolymer underwent quantitative alcoholysis or aminolysis transformation into methacrylate or methacrylamide units along with the pendant functionalization. The alternating-rich sequence was achieved by feeding an excess ratio of BMDO, which was supported by MALDI-TOF-MS of the copolymer obtained by the RAFT copolymerization. The methanolysis-transformed copolymer carrying MMA units was decomposed under basic condition, and the degradation efficiency was superior to that of the copolymer obtained via radical copolymerization of MMA with BMDO because of the alternating-rich sequence.

    Copyright © 2021 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsmacrolett.1c00513.

    • Experimental details, protocols for polymerizations, PPM, and degradation, and additional results including with other alcohols and amine (PDF)

    Terms & Conditions

    Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machine-readable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 18 publications.

    1. Yasuhiro Kohsaka, Kaho Toyama, Moe Kawauchi, Koki Naganuma. Fast and Selective Main-Chain Scission of Vinyl Polymers Using the Domino Reaction in the Alternating Sequence for Transesterification. ACS Macro Letters 2024, 13 (8) , 1016-1021. https://doi.org/10.1021/acsmacrolett.4c00295
    2. Yuyu Chen, Chaowei Yue, Bang An, Shuai Liu, Litao Zhou, Chong-Lei Ji, Yifan Li. Six Atom Elongated Radical Polymerization Enabled by 1,5-Hydrogen Atom Transfer. Macromolecules 2024, 57 (10) , 4918-4925. https://doi.org/10.1021/acs.macromol.4c00250
    3. Kwangwook Ko, David J. Lundberg, Alayna M. Johnson, Jeremiah A. Johnson. Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate). Journal of the American Chemical Society 2024, 146 (13) , 9142-9154. https://doi.org/10.1021/jacs.3c14554
    4. Hiroshi Makino, Tsuyoshi Nishikawa, Makoto Ouchi. Polymer Degradation by Synergistic Dual Stimuli: Base Interaction and Photocatalysis to Unlock a Boron Pendant Trigger for Main-Chain Scission. Macromolecules 2023, 56 (21) , 8776-8783. https://doi.org/10.1021/acs.macromol.3c01165
    5. Hai-Wang Lai, Makoto Ouchi. Backbone Degradable Polymers via Chain-growth Radical Polymerization. Chinese Journal of Polymer Science 2025, 4 https://doi.org/10.1007/s10118-025-3278-x
    6. Feiyang Ye, Chaowei Yue, Yifan Li. Radical Copolymerization of 2‐Thiocyanatoethyl Substituted Acrylate to Introduce Thiol‐Acrylate‐Based Dynamic Bonds as Degradable Linker. Journal of Polymer Science 2025, 63 (1) , 263-269. https://doi.org/10.1002/pol.20240545
    7. Akikazu Matsumoto. Development of heat-responsive adhesive materials that are stable during use and quickly deteriorate during dismantling. Polymer Journal 2024, 56 (4) , 223-247. https://doi.org/10.1038/s41428-023-00849-7
    8. Keita Kuroda, Makoto Ouchi. Umpolung Isomerization in Radical Copolymerization of Benzyl Vinyl Ether with Pentafluorophenylacrylate Leading to Degradable AAB Periodic Copolymers. Angewandte Chemie 2024, 136 (1) https://doi.org/10.1002/ange.202316875
    9. Keita Kuroda, Makoto Ouchi. Umpolung Isomerization in Radical Copolymerization of Benzyl Vinyl Ether with Pentafluorophenylacrylate Leading to Degradable AAB Periodic Copolymers. Angewandte Chemie International Edition 2024, 63 (1) https://doi.org/10.1002/anie.202316875
    10. Catherine Lefay, Yohann Guillaneuf. Recyclable/degradable materials via the insertion of labile/cleavable bonds using a comonomer approach. Progress in Polymer Science 2023, 147 , 101764. https://doi.org/10.1016/j.progpolymsci.2023.101764
    11. Zhuoqun Wang, Antoine Debuigne. Radical Polymerization of Methylene Heterocyclic Compounds: Functional Polymer Synthesis and Applications. Polymer Reviews 2023, 63 (4) , 805-851. https://doi.org/10.1080/15583724.2023.2181819
    12. Srinivasa Reddy Mothe, Lohitha Rao Chennamaneni, Jacqueline Tan, Freda C. H. Lim, Wenguang Zhao, Praveen Thoniyot. A Mechanistic Study on the Hydrolysis of Cyclic Ketene Acetal (CKA) and Proof of Concept of Polymerization in Water. Macromolecular Chemistry and Physics 2023, 224 (19) https://doi.org/10.1002/macp.202300221
    13. Mineto Uchiyama, Yukihiro Murakami, Kotaro Satoh, Masami Kamigaito. Synthesis and Degradation of Vinyl Polymers with Evenly Distributed Thioacetal Bonds in Main Chains: Cationic DT Copolymerization of Vinyl Ethers and Cyclic Thioacetals. Angewandte Chemie 2023, 135 (4) https://doi.org/10.1002/ange.202215021
    14. Mineto Uchiyama, Yukihiro Murakami, Kotaro Satoh, Masami Kamigaito. Synthesis and Degradation of Vinyl Polymers with Evenly Distributed Thioacetal Bonds in Main Chains: Cationic DT Copolymerization of Vinyl Ethers and Cyclic Thioacetals. Angewandte Chemie International Edition 2023, 62 (4) https://doi.org/10.1002/anie.202215021
    15. Yili Yang, Feiyue Xing, Yingshan Zhou, Pu Xiao. Hydrolysis/Photolysis Dual-Stimuli-Responsive Backbone-Degradable Copolymers Featuring Cyclic Ketene Acetal and ortho-Nitrobenzyl Pendants. European Polymer Journal 2022, 181 , 111659. https://doi.org/10.1016/j.eurpolymj.2022.111659
    16. Hiroshi Makino, Tsuyoshi Nishikawa, Makoto Ouchi. Incorporation of a boryl pendant as the trigger in a methacrylate polymer for backbone degradation. Chemical Communications 2022, 58 (85) , 11957-11960. https://doi.org/10.1039/D2CC04882E
    17. Philipp Gerdt, Armido Studer. Alternierende Terpolymere durch Cyclopolymerisation und anschließende orthogonale Funktionalisierung. Angewandte Chemie 2022, 134 (39) https://doi.org/10.1002/ange.202206964
    18. Philipp Gerdt, Armido Studer. Alternating Terpolymers through Cyclopolymerization and Subsequent Orthogonal Functionalization. Angewandte Chemie International Edition 2022, 61 (39) https://doi.org/10.1002/anie.202206964
    Download PDF
    Go to ACS Macro Letters
    Get e-Alerts
    Get e-Alerts

    ACS Macro Letters

    Cite this: ACS Macro Lett. 2021, 10, 10, 1223–1228
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsmacrolett.1c00513
    Published September 23, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

    Article Views

    3425

    Altmetric

    -

    Citations

    18
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.