ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Synthesis of Sequence-Specific Polymers with Amide Side Chains via Regio-/Stereoselective Ring-Opening Metathesis Polymerization of 3-Substituted cis-Cyclooctene

View Author Information
Department of Biochemical Engineering, Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan
Institute for Materials Chemistry and Engineering, Kyushu University, CE41 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
*E-mail: [email protected] (S.K.).
*E-mail: [email protected] (M.T.).
Cite this: Macromolecules 2016, 49, 21, 8154–8161
Publication Date (Web):October 20, 2016
https://doi.org/10.1021/acs.macromol.6b01829
Copyright © 2016 American Chemical Society

    Article Views

    1426

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    Highly regio-/stereoregular (trans-head-to-tail) polymers with amide side chains on every eighth backbone carbon were successfully synthesized by ring-opening metathesis polymerization (ROMP) of 3-substituted cis-cyclooctene (3RCOE) using Grubbs second-generation catalyst (G2). Regioregular linear ethylene–acrylamide copolymers were also prepared via hydrogenation of the obtained poly(3RCOE)s. The thermal properties and solubility of the obtained polymers were strongly influenced by the presence of amide hydrogen in the side chains, the presence of unsaturated bonds in the carbon backbone, and the side chain density. The presence of amide hydrogen in the side chains resulted in the formation of crystalline polymers and the lack of solubility of these polymers in common organic solvents. In contrast, the absence of amide hydrogen in the side chains led to the formation of amorphous polymers exhibiting good solubility in common organic solvents, and decreasing values of Tg were observed for amorphous polymers as a result of the saturation of double bonds in the backbone via hydrogenation.

    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. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.6b01829.

    • Experimental details, characterization details data, and NMR spectra for obtained products (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 27 publications.

    1. Devavrat Sathe, Seiyoung Yoon, Zeyu Wang, Hanlin Chen, Junpeng Wang. Deconstruction of Polymers through Olefin Metathesis. Chemical Reviews 2024, Article ASAP.
    2. Chase B. Thompson, Sara V. Orski. Synthesis and Dilute Solution Properties of Precision Short-Chain Branched Poly(ethylene) Block Copolymers Derived from Ring-Opening Metathesis Polymerization. Macromolecules 2023, 56 (14) , 5575-5587. https://doi.org/10.1021/acs.macromol.3c00191
    3. Ernest O. Nachaki, Fedra M. Leonik, Daniel G. Kuroda. Effect of the N-Alkyl Side Chain on the Amide–Water Interactions. The Journal of Physical Chemistry B 2022, 126 (41) , 8290-8299. https://doi.org/10.1021/acs.jpcb.2c04988
    4. Gina A. Guillory, Stephanie F. Marxsen, Rufina G. Alamo, Justin G. Kennemur. Precise Isotactic or Atactic Pendant Alcohols on a Polyethylene Backbone at Every Fifth Carbon: Synthesis, Crystallization, and Thermal Properties. Macromolecules 2022, 55 (15) , 6841-6851. https://doi.org/10.1021/acs.macromol.2c01090
    5. Mark R. Yarolimek, Heather R. Bookbinder, Brianna M. Coia, Justin G. Kennemur. Ring-Opening Metathesis Polymerization of δ-Pinene: Well-Defined Polyolefins from Pine Sap. ACS Macro Letters 2021, 10 (6) , 760-766. https://doi.org/10.1021/acsmacrolett.1c00284
    6. Toshiki Sonoda, Shingo Kobayashi, Masaru Tanaka. Periodically Functionalized Linear Polyethylene with Tertiary Amino Groups via Regioselective Ring-Opening Metathesis Polymerization. Macromolecules 2021, 54 (6) , 2862-2872. https://doi.org/10.1021/acs.macromol.0c02611
    7. Masato Miyajima, Kotaro Satoh, Takahiro Horibe, Kazuaki Ishihara, Masami Kamigaito. Multifactor Control of Vinyl Monomer Sequence, Molecular Weight, and Tacticity via Iterative Radical Additions and Olefin Metathesis Reactions. Journal of the American Chemical Society 2020, 142 (44) , 18955-18962. https://doi.org/10.1021/jacs.0c09289
    8. Jessica K. Su, So Young Lee, Benjamin R. Elling, Yan Xia. Ring-Opening Metathesis Polymerization of 1,1-Disubstituted 1-Methylcyclopropenes. Macromolecules 2020, 53 (14) , 5833-5838. https://doi.org/10.1021/acs.macromol.0c00837
    9. Dylan J. Walsh, Michael G. Hyatt, Susannah A. Miller, Damien Guironnet. Recent Trends in Catalytic Polymerizations. ACS Catalysis 2019, 9 (12) , 11153-11188. https://doi.org/10.1021/acscatal.9b03226
    10. Wesley S. Farrell and Kathryn L. Beers . Ring-Opening Metathesis Polymerization of Butyl-Substituted trans-Cyclooctenes. ACS Macro Letters 2017, 6 (8) , 791-795. https://doi.org/10.1021/acsmacrolett.7b00420
    11. Maosheng Li, Fengchao Cui, Yunqi Li, Youhua Tao, and Xianhong Wang . Crystalline Regio-/Stereoregular Glycine-Bearing Polymers from ROMP: Effect of Microstructures on Materials Performances. Macromolecules 2016, 49 (24) , 9415-9424. https://doi.org/10.1021/acs.macromol.6b02244
    12. Zhongqi Guo, Wenxu Fan, Keyume Ablajan. N-acetylation of Aromatic Amines by One-pot Route. Letters in Organic Chemistry 2024, 21 (4) , 362-368. https://doi.org/10.2174/0115701786266810231005103940
    13. Shingo Kobayashi, Masaru Tanaka. Design of biomaterials through direct ring-opening metathesis polymerisation of functionalised cyclic alkenes. Molecular Systems Design & Engineering 2023, 8 (8) , 960-991. https://doi.org/10.1039/D3ME00063J
    14. O. A Adzhieva, A. V Finko, A. V Roenko, Yu. I. Denisova, Y. V Kudryavtsev. Functional derivatization of 3- and 5-substituted cyclooctenes. Журнал органической химии 2023, 59 (5) , 633-639. https://doi.org/10.31857/S0514749223050105
    15. O. A. Adzhieva, A. V. Finko, A. V. Roenko, Yu. I. Denisova, Y. V. Kudryavtsev. Functional Derivatization of 3- and 5-Substituted Cyclooctenes. Russian Journal of Organic Chemistry 2023, 59 (5) , 807-812. https://doi.org/10.1134/S107042802305010X
    16. Sebla Onbulak, Marc A. Hillmyer. Precision ethylene-styrene copolymers through the ring opening metathesis polymerization of 3-phenyl cyclododecenes. Polymer Chemistry 2021, 12 (11) , 1681-1691. https://doi.org/10.1039/D0PY01721C
    17. Masaru Tanaka, Shigeaki Morita, Tomohiro Hayashi. Role of interfacial water in determining the interactions of proteins and cells with hydrated materials. Colloids and Surfaces B: Biointerfaces 2021, 198 , 111449. https://doi.org/10.1016/j.colsurfb.2020.111449
    18. Feilong Liu, Nannan Xu, Li Ling, Jianfeng Hu, Hao Zhang. Regio- and stereoselective ring-opening metathesis polymerization of 3-ferrocenyl substituted cyclooctenes and copolymerization with norbornene derivatives. European Polymer Journal 2020, 124 , 109472. https://doi.org/10.1016/j.eurpolymj.2020.109472
    19. Masaru Tanaka, Shingo Kobayashi, Daiki Murakami, Fumihiro Aratsu, Aki Kashiwazaki, Takashi Hoshiba, Kazuki Fukushima. Design of Polymeric Biomaterials: The “Intermediate Water Concept”. Bulletin of the Chemical Society of Japan 2019, 92 (12) , 2043-2057. https://doi.org/10.1246/bcsj.20190274
    20. Gina A. Guillory, Justin G. Kennemur. Investigating the effects of bulky allylic substituents on the regioregularity and thermodynamics of ROMP on cyclopentene. European Polymer Journal 2019, 120 , 109251. https://doi.org/10.1016/j.eurpolymj.2019.109251
    21. Masaru Tanaka. Development of Biocompatible Materials : Bio and Material Interactions. Seikei-Kakou 2019, 31 (11) , 404-407. https://doi.org/10.4325/seikeikakou.31.404
    22. Chulu Zhou, Yang Wang, Lanxiao Zhao, Zhizhou Liu, Jianhua Cheng. Regioselective ring-opening metathesis polymerization of limonene oxide-substituted cyclooctene: The highly functional ethylene/vinyl ester copolymers. European Polymer Journal 2019, 112 , 60-66. https://doi.org/10.1016/j.eurpolymj.2018.12.025
    23. Masaru Tanaka. Design of Multifunctional Soft Biomaterials: Based on the Intermediate Water Concept. 2019, 423-432. https://doi.org/10.1007/978-981-13-2889-3_23
    24. James W. Herndon. The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2016. Coordination Chemistry Reviews 2018, 356 , 1-114. https://doi.org/10.1016/j.ccr.2017.09.003
    25. Stefan Brits, William J. Neary, Goutam Palui, Justin G. Kennemur. A new echelon of precision polypentenamers: highly isotactic branching on every five carbons. Polymer Chemistry 2018, 9 (13) , 1719-1727. https://doi.org/10.1039/C7PY01922J
    26. Xianwang Shen, Honghong Gong, Yang Zhou, Yucheng Zhao, Jun Lin, Mao Chen. Unsymmetrical difunctionalization of cyclooctadiene under continuous flow conditions: expanding the scope of ring opening metathesis polymerization. Chemical Science 2018, 9 (7) , 1846-1853. https://doi.org/10.1039/C7SC04580H
    27. Michio Mineshima. . Nihon Toseki Igakkai Zasshi 2017, 50 (6) , 363-399. https://doi.org/10.4009/jsdt.50.363

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect