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Simple preparation, properties, and functions of vitrimer-like polyacrylate elastomers using trans-N-alkylation bond exchange

Polymer Journal volume 53, pages 835–840 (2021)Cite this article

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Abstract

Herein, we report the preparation of polyacrylate-based vitrimer-like elastomers with dynamic bond-exchangeable cross-links. The component polymer is a poly(ethyl acrylate)-based copolymer that bears pyridine groups randomly and was cross-linked by a quaternization reaction with dibromo cross-linkers (dibromo hexane). In this system, bond exchange is induced via trans-N-alkylation at high temperatures, which is revealed by elongational creep and stress-relaxation tests. Some useful functions of the present material, such as reprocessability, recyclability, and unique solubility, were also demonstrated.

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References

  1. Brunsveld L, Folmer BJB, Meijer EW, Sijbesma RP. Supramolecular polymers. Chem Rev. 2001;101:4071–97.

    Article  CAS  Google Scholar 

  2. Jin YH, Yu C, Denman RJ, Zhang W. Recent advances in dynamic covalent chemistry. Chem Soc Rev. 2013;42:6634–54.

    Article  CAS  Google Scholar 

  3. Noro A, Hayashi M, Matsushita Y. Design and properties of supramolecular polymer gels. Soft Matter. 2012;8:6416–29.

    Article  CAS  Google Scholar 

  4. Herbst F, Dohler D, Michael P, Binder WH. Self-healing polymers via supramolecular forces. Macromol Rapid Commun. 2013;34:203–20.

    Article  CAS  Google Scholar 

  5. Chakma P, Konkolewicz D. Dynamic covalent bonds in polymeric materials. Angew Chem Int Ed. 2019;58:9682–95.

    Article  CAS  Google Scholar 

  6. Scheutz GM, Lessard JJ, Sims MB, Sumerlin BS. Adaptable crosslinks in polymeric materials: resolving the intersection of thermoplastics and thermosets. J Am Chem Soc. 2019;141:16181–96.

    Article  CAS  Google Scholar 

  7. Chen X, Dam MA, Ono K, Mal A, Shen H, Nutt SR. A thermally re-mendable cross-linked polymeric material. Science. 2002;295:1698–702.

    Article  CAS  Google Scholar 

  8. Obadia MM, Mudraboyina BP, Serghei A, Montarnal D, Drockenmuller E. Reprocessing and recycling of highly cross-linked ion-conducting networks through transalkylation exchanges of C-N bonds. J Am Chem Soc. 2015;137:6078–83.

    Article  CAS  Google Scholar 

  9. Obadia MM, Jourdain A, Cassagnau P, Montarnal D, Drockenmuller E. Tuning the viscosity profile of ionic vitrimers incorporating 1,2,3-triazolium cross-links. Adv Funct Mater. 2017;27:1703258.

    Article  Google Scholar 

  10. Montarnal D, Capelot M, Tournilhac F, Leibler L. Silica-like malleable materials from permanent organic networks. Science. 2011;334:965–8.

    Article  CAS  Google Scholar 

  11. Capelot M, Unterlass MM, Tournilhac F, Leibler L. Catalytic control of the vitrimer glass transition. ACS Macro Lett. 2012;1:789–92.

    Article  CAS  Google Scholar 

  12. Capelot M, Montarnal D, Tournilhac F, Leibler L. Metal-catalyzed transesterification for healing and assembling of thermosets. J Am Chem Soc. 2012;134:7664–7.

    Article  CAS  Google Scholar 

  13. Demongeot A, Groote R, Goossens Han, Hoeks T, Tournilhac F, Leibler L. Cross-linking of poly(butylene terephthalate) by reactive extrusion using Zn(II) epoxy-vitrimer chemistry. Macromolecules. 2017;50:6117–27.

    Article  CAS  Google Scholar 

  14. Hayashi M, Yano R, Takasu A. Synthesis of amorphous low T-g polyesters with multiple COOH side groups and their utilization for elastomeric vitrimers based on post-polymerization cross-linking. Polym Chem. 2019;10:2047–56.

    Article  CAS  Google Scholar 

  15. Hayashi M, Yano R. Fair investigation of cross-link density effects on the bond-exchange properties for trans-esterification-based vitrimers with identical concentrations of reactive groups. Macromolecules. 2020;53:182–9.

    Article  CAS  Google Scholar 

  16. Hayashi M. Implantation of recyclability and healability into cross-linked commercial polymers by applying the vitrimer concept. Polymers. 2020;12:1322.

    Article  CAS  Google Scholar 

  17. Röttger M, Domenech T, van der Weegen R, Breuillac A. Nicolaÿ R, Leibler L. High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis. Science. 2017;356:62–65.

    Article  Google Scholar 

  18. Lessard JJ, Garcia LF, Easterling CP, Sims MB, Bentz KC, Arencibia S et al. Catalyst-free vitrimers from vinyl polymers. Macromolecules. 2019;52:2105–11.

    Article  CAS  Google Scholar 

  19. Lossada F, Jiao DJ, Yao XY, Walther A. Waterborne methacrylate-based vitrimers. ACS Macro Lett. 2020;9:70–76.

    Article  CAS  Google Scholar 

  20. Debnath S, Kaushal S, Ojha U. Catalyst-free partially bio-based polyester vitrimers. ACS Appl Polym Mater. 2020;2:1006–13.

    Article  CAS  Google Scholar 

  21. Huang J, Zhang LJ, Tang ZH, Wu SW, Guo BC. Reprocessable and robust crosslinked elastomers via interfacial C-N transalkylation of pyridinium. Compos Sci Technol. 2018;168:320–6.

    Article  CAS  Google Scholar 

  22. Hayashi M, Chen L. Functionalization of triblock copolymer elastomers by cross-linking the end blocks via trans-N-alkylation-based exchangeable bonds. Polym Chem. 2020;11:1713–9.

    Article  CAS  Google Scholar 

  23. Mun GA, Nurkeeva ZS, Beissegul AB, Dubolazov AV, Urkimbaeva PI, Park K, et al. Temperature-responsive water-soluble copolymers based on 2-hydroxyethyl acrylate and butyl acrylate. Macromol Chem Phys. 2007;208:979–87.

    Article  CAS  Google Scholar 

  24. Oba Y, Hayashi M, Takasu A. One-pot synthesis of dual supramolecular associative copolymers by using a novel acrylate monomer bearing urethane and pendant pyridine groups. Polym Chem. 2020;11:2318–24.

    Article  CAS  Google Scholar 

  25. Li GL, Shen JR, Zhu YL. A study of pyridinium-type functional polymers. III. Preparation and characterization of insoluble pyridinium-type polymers. J Appl Polym Sci. 2000;78;668–75.

    Article  CAS  Google Scholar 

  26. Liu CH, Xiao CB. Characterization of films from chitosan and quaternized poly(4-vinyl-N-butyl) pyridine solutions. J Appl Polym Sci. 2004;92;559–66.

    Article  CAS  Google Scholar 

  27. Tazuke S, Okamura S. Effects of metal salts on polymerization. Part III. Radical polymerizabilities and infrared spectra of vinylpyridines complexed with zinc and cadmium salts. J Polym Sci., Part A-1: Polym. Chem. 1967;5;1083–99.

    Article  CAS  Google Scholar 

  28. Kuo SW, Wu CH, Chang FC. Thermal properties, interactions, morphologies, and conductivity behavior in blends of poly(vinylpyridine)s and zinc perchlorate. Macromolecules. 2004;37;192–200.

    Article  CAS  Google Scholar 

  29. Shi Q, Yu K, Dunn ML, Wang TJ, Qi HJ. Solvent assisted pressure-free surface welding and reprocessing of malleable epoxy polymers. Macromolecules. 2016;49:5527–37.

    Article  CAS  Google Scholar 

  30. Kuang X, Shi Q, Zhou Y, Zhao Z, Wang T, Qi HJ. Dissolution of epoxy thermosets via mild alcoholysis: the mechanism and kinetics study. RSC Adv. 2018;8:1493–502.

    Article  CAS  Google Scholar 

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Acknowledgements

The authors thank Prof. K. Nagata for his assistance in performing the elongation creep tests. This work was supported by a grant from the TOYOAKI SCHOLARSHIP FOUNDATION (M.H.).

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Authors and Affiliations

  1. Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho Showa-ku Nagoya-city Aichi, Nagoya, 466-8555, Japan

    Mikihiro Hayashi, Yuta Oba, Takahiro Kimura & Akinori Takasu

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  1. Mikihiro Hayashi
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  2. Yuta Oba
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  3. Takahiro Kimura
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  4. Akinori Takasu
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Correspondence to Mikihiro Hayashi.

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Hayashi, M., Oba, Y., Kimura, T. et al. Simple preparation, properties, and functions of vitrimer-like polyacrylate elastomers using trans-N-alkylation bond exchange. Polym J 53, 835–840 (2021). https://doi.org/10.1038/s41428-021-00472-4

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