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Fabrication of thermally cross-linked poly(methacrylic acid)-based sponges with nanolayered structures and their degradation

Polymer Journal volume 55, pages 163–170 (2023)Cite this article

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Abstract

Water-insoluble poly(methacrylic acid) (poly(MAAc)) sponges with nanolayered structures were fabricated via thermal cross-linking with poly(vinyl alcohol) (PVA). The cross-linked water-insoluble sponges contained up to 75 wt% poly(MAAc) when the molecular weight of PVA and the cross-linking time were adjusted appropriately. After immersion in a NaClO·5H2O aqueous solution for 24 h, all poly(MAAc)/PVA_50 wt% sponges with different PVA molecular weights were completely dissolved, and their residual weights were approximately 0%. The molar ratio of NaClO·5H2O was 3.6 times that of the vinyl alcohol units in the sponges. The molecular weight (Mn) and molecular weight distribution (Mw/Mn) of poly(MAAc) observed after immersion in the NaClO·5H2O aqueous solution were similar to those of the original poly(MAAc) (Mn: 46200 g/mol, Mw/Mn: 1.65). In contrast, the gel permeation chromatography (GPC) curves for PVA were shifted to lower molecular weights with increasing NaClO·5H2O concentrations. These results suggested that only the PVA in the poly(MAAc)/PVA sponges was decomposed. Multilayer films of poly(MAAc)/PVA with different physicochemical properties were also fabricated. The first and third layers were made of a poly(MAAc)/PVA_10wt% film, and the second layer was made of a poly(MAAc)/PVA _50wt% sponge.

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References

  1. Cornwall W. The plastic eaters. Science. 2021;373:36–9.

    Article  CAS  Google Scholar 

  2. Korley LTJ, Epps TH III, Helms BA, Ryan AJ. Toward polymer upcycling-adding valueand tackling circularity. Science. 2021;373:66–9.

    Article  CAS  Google Scholar 

  3. Stubbins A, Law KL, Muñoz SE, Bianchi TS, Zhu L. Plastics in the earth system. Science. 2021;373:51–5.

    Article  CAS  Google Scholar 

  4. Soares CTM, Ek M, Östmark E, Gällstedt M, Karlsson S. Recycling of multi-material multilayer plastic packaging: Current trends and future scenarios. Resour Conserv Recycl. 2022;176:105905.

    Article  Google Scholar 

  5. Qu Z, Xu H, Gu H. Synthesis and biomedical applications of poly((meth)acrylic acid) brushes. ACS Appl Mater Interfaces. 2015;7:14537–51.

    Article  CAS  Google Scholar 

  6. Veith C, Diot-Néant F, Miller SA, Allais F. Synthesis and polymerization of bio-based acrylates: a review. Polym Chem. 2020;11:7452–70.

    Article  CAS  Google Scholar 

  7. Li Q, Bao Y, Wang H, Du F, Li Q, Jin B, et al. A facile and highly efficient strategy for esterification of poly(meth)acrylic acid with halogenated compounds at room temperature promoted by 1,1,3,3-tetramethylguanidine. Polym Chem. 2013;4:2891–7.

    Article  CAS  Google Scholar 

  8. Shevtsov VY, Hsin T-Y, Shieh Y-T. Preparation of amphiphilic copolymers via base-catalyzed hydrolysis of quaternizedpoly[2-(dimethylamino)ethyl methacrylate]. Polym Chem. 2022;13:1429–36.

    Article  CAS  Google Scholar 

  9. Elladiou M, Patrickios CS. 2-(Pyridin-2-yl)ethanol asa protecting group for carboxylic acids: chemical and thermal cleavage, andconversion of poly[2-(pyridin-2-yl)ethyl methacrylate] to poly(methacrylicacid). Polym Chem. 2012;3:3228–31.

    Article  CAS  Google Scholar 

  10. Hermens JGH, Jensma A, Feringa BL. Highly efficient biobased synthesis of acrylic acid. Angew Chem Int Ed. 2022;61:e202112618.

    Article  CAS  Google Scholar 

  11. Fujimoto K, Yamawaki-Ogata A, Narita Y, Kotsuchibashi Y. Fabrication of cationic poly(vinyl alcohol) films cross-linked using copolymers containing quaternary ammonium cations, benzoxaborole, and carboxy groups. ACS Omega. 2021;6:17531–44.

    Article  CAS  Google Scholar 

  12. Fujimoto K, Saito A, Kotsuchibashi Y. Cicada-wing-inspired nanopillar hydrogels consisting of poly(vinyl alcohol) and poly(methacrylic acid) for capturing bacteria through their flexibility and wide range of motion. ACS Macro Lett. 2022;11:727–32.

    Article  CAS  Google Scholar 

  13. Hassan CM, Peppas NA. Structure and applications of poly(vinyl alcohol) hydrogels produced by conventional crosslinking or by freezing/thawing methods. Adv Polym Sci. 2000;153:37–65.

    Article  CAS  Google Scholar 

  14. Chiellini E, Corti A, D’Antone S, Solaro R. Biodegradation of poly(vinyl alcohol) based materials. Prog Polym Sci. 2003;28:963–1014.

    Article  CAS  Google Scholar 

  15. DeMerlis CC, Schoneker DR. Review of the oral toxicity of polyvinyl alcohol (PVA). Food Chem Toxicol. 2003;41:319–26.

    Article  CAS  Google Scholar 

  16. Park J-A, Kang J-K, Lee S-C, Kim S-B. Electrospun poly(acrylic acid)/poly(vinyl alcohol) nanofibrous adsorbents for Cu(II) removal from industrial plating wastewater. RSC Adv. 2017;7:18075–84.

    Article  CAS  Google Scholar 

  17. Truong YB, Choi J, Mardel J, Gao Y, Maisch S, Musameh M, et al. Macromol Mater Eng. 2017;302:No.1700024.

    Article  Google Scholar 

  18. Su Y-K, Coxwell CM, Shen S, Miller SA. Polyvinyl alcohol modification with sustainable ketones. Polym Chem. 2021;12:4961–73.

    Article  CAS  Google Scholar 

  19. Hakuto N, Saito K, Kirihara M, Kotsuchibashi Y. Preparation of cross-linked poly(vinyl alcohol) films from copolymers with benzoxaborole and carboxylic acid groups, and their degradability in an oxidizing environment. Polym Chem. 2020;11:2469–74.

    Article  CAS  Google Scholar 

  20. Kirihara M, Okada T, Sugiyama Y, Akiyoshi M, Matsunaga T, Kimura Y. Sodium hypochlorite pentahydrate crystals (NaOCl·5H2O): A convenient and environmentally benign oxidant for organic synthesis. Org Process Res Dev. 2017;21:1925–37.

    Article  CAS  Google Scholar 

  21. Kirihara M, Osugi R, Saito K, Adachi K, Yamazaki K, Matsushima R, et al. Sodium hypochlorite pentahydrate as a reagent for the cleavage of trans-cyclic glycols. J Org Chem. 2019;84:8330–6.

    Article  CAS  Google Scholar 

  22. Hamad D, Mehrvar M, Dhib R. Experimental study of polyvinyl alcohol degradation in aqueous solution by UV/H2O2 process. Polym Degrad Stab. 2014;103:75–82.

    Article  CAS  Google Scholar 

  23. Su Y, Li M, Gao Q, Li X, Ju A, Lu Y, et al. Degradation and kinetic modeling of polyvinyl alcohol in aqueous solutions by a H2O2/Mn(II) system. Fibers Polym. 2017;18:2269–77.

    Article  CAS  Google Scholar 

  24. Ali U, Karim KJBA, Buang NA. A review of the properties and applications of poly (methyl methacrylate) (PMMA). Polym Rev. 2015;55:678–705.

    Article  CAS  Google Scholar 

  25. Ayre WN, Denyer SP, Evans SL. Ageing and moisture uptake in polymethyl methacrylate (PMMA) bone cements. J Mech Behav Biomed Mater. 2014;32:76–88.

    Article  CAS  Google Scholar 

  26. Mengel C, Esker AR, Meyer WH, Wegner G. Preparation and modification of poly(methacrylic acid) and poly(acrylic acid) multilayers. Langmuir 2002;18:6365–72.

    Article  CAS  Google Scholar 

  27. Mahmud HNME, Huq AKO, Yahya R. The removal of heavy metal ions from wastewater/ aqueous solution using polypyrrole-based adsorbents: a review. RSC Adv. 2016;6:14778–91.

    Article  Google Scholar 

  28. Zhao G, Huang X, Tang Z, Huang Q, Niu F, Wang X. Polymer-based nanocomposites for heavy metal ions removal from aqueous solution: a review. Polym Chem. 2018;9:3562–82.

    Article  CAS  Google Scholar 

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Acknowledgements

This work was partially supported by the technical research aid projects 2019 (JFE 21st Century Foundation) and research grant 2021 (Iketani Science and Technology Foundation). We are grateful to Nippon Light Metal Co., Ltd., for providing NaClO·5H2O. We are grateful to Mr. Kazuo Hayakawa, Dr. Yusuke Wakikawa, and Dr. Takeaki Koizumi of the Advanced Instrumental Analysis Center at the Shizuoka Institute of Science and Technology for their technical support.

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  1. Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka, 437-8555, Japan

    Daiki Kobayashi, Haruki Uchida, Misaki Ishibane, Erika Kurita, Masayuki Kirihara & Yohei Kotsuchibashi

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  1. Daiki Kobayashi
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  2. Haruki Uchida
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Correspondence to Yohei Kotsuchibashi.

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Kobayashi, D., Uchida, H., Ishibane, M. et al. Fabrication of thermally cross-linked poly(methacrylic acid)-based sponges with nanolayered structures and their degradation. Polym J 55, 163–170 (2023). https://doi.org/10.1038/s41428-022-00721-0

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