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ROMP of supramolecular norbornene monomers containing β-cyclodextrin–ferrocene (/adamantane) inclusion complexes

Polymer Journal volume 52, pages 1333–1347 (2020)Cite this article

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Abstract

Through the use of N-[2′-ferrocenylformamido-ethyl]-cis-5-norbornene-exo-2,3-dicarboximide (NFc) and N-[2′-adamantylformamido-ethyl]-cis-5-norbornene-exo-2,3-dicarboximide (NAd), we report the fabrication of two novel supramolecular norbornene monomers, NFc@β-CD and NAd@β-CD, through β-cyclodextrin (β-CD)/ferrrocene(Fc)- and β-CD/adamantane (Ad)-based host–guest complexation. The formation and structure of the two monomers were verified by various techniques, such as 1H and 13C NMR, 2D NOESY, IR and UV–vis spectroscopic methods. The ROMP (ring-opening metathesis polymerization) feasibility of the two supramolecular monomers was further confirmed by the successful preparation of two homopolymers (P(NFc@β-CD) and P(NAd@β-CD)) and two diblock copolymers (PNFc-b-P(NAd@β-CD) and P(NFc@β-CD)-b-P(NAd@β-CD)). The prepared polymers were adequately analyzed using 1H and 13C NMR, IR, UV–vis, end-group analysis and GPC methods. Based on the obtained results, we believe that (1) both supramolecular monomers exhibited “living” and “controlled” ROMP reactions; (2) the β-CD/Fc and β-CD/Ad inclusion complexes were not disassembled during the ROMP reactions of the two supramolecular monomers; and (3) the functional groups of β-CD had a negligible effect on the catalytic activity of the third-generation Grubbs’ catalyst. In short, this work indicated that the direct ROMP of β-CD-containing supramolecular monomers was a feasible route for preparing supramolecular polynorbornene-based homopolymers and copolymers, and this route is expected to have great potential for the preparation of various supramolecular polynorbornenes and functional materials.

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Acknowledgements

Financial support for this work is from the National Natural Science Foundation of China (No. 21978180) and the Science & Technology Department of Sichuan Province (No. 2018HH0038). BS and HL were funded by the Innovation Training Program for college students at Sichuan University (C2020107809). We are grateful for Zhonghui Wang (College of Biomass Science and Engineering, Sichuan University) and her help with the IR measurements.

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Authors and Affiliations

  1. Key Laboratory of Leather Chemistry and Engineering of Ministry of Education, Sichuan University, 610065, Chengdu, China

    Bin Song, Li Zhang, Hongming Liang, Jinwei Zhang & Haibin Gu

  2. Rongcheng Customs of Fuzhou Customs District of China, 350015, Fuzhou, China

    Honglei Yin

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Correspondence to Haibin Gu.

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Song, B., Zhang, L., Yin, H. et al. ROMP of supramolecular norbornene monomers containing β-cyclodextrin–ferrocene (/adamantane) inclusion complexes. Polym J 52, 1333–1347 (2020). https://doi.org/10.1038/s41428-020-00398-3

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