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Tuning the thermal and mechanical properties of poly(vinyl alcohol) with 2,5-furandicarboxylic acid acting as a biobased crosslinking agent

Polymer Journal volume 54, pages 335–343 (2022)Cite this article

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Abstract

In this study, poly(vinyl alcohol) (PVA) was crosslinked via catalyst-free solid-state esterification at 120 °C with 2,5-furandicarboxylic acid (FDCA) at concentrations ranging from 1 to 10%. The structural characterization of the obtained products was carried out by attenuated total reflection Fourier transform infrared spectroscopy. The effects of ester crosslinks on the water absorption properties of the modified products were investigated through swelling degree analysis. The improvement in thermal properties of the obtained products was confirmed by thermal gravimetric analysis/differential thermal analysis, which showed that thermal stability was optimal for low concentrations of FDCA, i.e., 1 and 5%, where degradation maximums occurred at 354 and 371 °C, respectively, compared to 267 °C for unmodified PVA. The mechanical properties of the products were also studied via tensile testing, where the tensile strength of the crosslinked PVA using 5% FDCA (48.2 ± 2.6 MPa), doubled when compared to untreated PVA (25.5 ± 1.2 MPa).

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References

  1. Muthuraj R, Misra M, Mohanty AK. Biodegradable compatibilized polymer blends for packaging applications: a literature review. J Appl Polym Sci. 2018;135:45726.

    Article  Google Scholar 

  2. Scaffaro R, Maio A, Sutera F, Gulino EF, Morreale M. Degradation and recycling of films based on biodegradable polymers: a short review. Polymers. 2019;11:651.

    Article  CAS  PubMed Central  Google Scholar 

  3. Jayanth D, Kumar PS, Nayak GC, Kumar JS, Pal SK, Rajasekar R. A review on biodegradable polymeric materials striving towards the attainment of green environment. J Polym Environ. 2018;26:838–65.

    Article  CAS  Google Scholar 

  4. Narancic T, O’Connor KE. Plastic waste as a global challenge: are biodegradable plastics the answer to the plastic waste problem? Microbiology. 2019;165:129–37.

    Article  CAS  PubMed  Google Scholar 

  5. Shen M, Song B, Zeng G, Zhang Y, Huang W, Wen X, et al. Are biodegradable plastics a promising solution to solve the global plastic pollution? Environ Pollut. 2020;263:114469.

    Article  CAS  PubMed  Google Scholar 

  6. Manfra L, Marengo V, Libralato G, Costantini M, De Falco F, Cocca M, et al. Biodegradable polymers: a real opportunity to solve marine plastic pollution? J Hazard Mater. 2021;416:125763.

    Article  CAS  PubMed  Google Scholar 

  7. Halima NB. Poly (vinyl alcohol): review of its promising applications and insights into biodegradation. RSC Adv. 2016;6:39823–32.

    Article  Google Scholar 

  8. Aslam M, Kalyar MA, Raza ZA. Polyvinyl alcohol: a review of research status and use of polyvinyl alcohol based nanocomposites. Polym Eng Sci. 2018;58:2119–32.

    Article  CAS  Google Scholar 

  9. Feldman D. Poly (vinyl alcohol) recent contributions to engineering and medicine. J Compos Sci. 2020;4:175.

    Article  CAS  Google Scholar 

  10. Shimao M. Biodegradation of plastics. Curr Opin Biotechnol. 2001;12:242–7.

    Article  CAS  PubMed  Google Scholar 

  11. Kawai F, Hu X. Biochemistry of microbial polyvinyl alcohol degradation. Appl Microbiol Biotechnol. 2009;84:227–37.

    Article  CAS  PubMed  Google Scholar 

  12. Sonker AK, Tiwari N, Nagarale RK, Verma V. Synergistic effect of cellulose nanowhiskers reinforcement and dicarboxylic acids crosslinking towards polyvinyl alcohol properties. J Polym Sci Part A: Polym Chem. 2016;54:2515–25.

    Article  CAS  Google Scholar 

  13. Falqi FH, Bin-Dahman OA, Hussain M, Al-Harthi MA. Preparation of miscible PVA/PEG blends and effect of graphene concentration on thermal, crystallization, morphological, and mechanical properties of PVA/PEG (10 wt%) blend. Int J Polym Sci. 2018;2018:8527693.

  14. Sonker AK, Rathore K, Nagarale RK, Verma V. Crosslinking of polyvinyl alcohol (PVA) and effect of crosslinker shape (aliphatic and aromatic) thereof. J Polym Environ. 2018;26:1782–94.

    Article  CAS  Google Scholar 

  15. Kim K-J, Lee S-B, Han N-W. Kinetics of crosslinking reaction of PVA membrane with glutaraldehyde. Korean J Chem Eng. 1994;11:41–47.

    Article  CAS  Google Scholar 

  16. Figueiredo KCS, Alves TLM, Borges CP. Poly (vinyl alcohol) films crosslinked by glutaraldehyde under mild conditions. J Appl Polym Sci. 2009;111:3074–80.

    Article  CAS  Google Scholar 

  17. Liu L, Kentish SE. Pervaporation performance of crosslinked PVA membranes in the vicinity of the glass transition temperature. J Membr Sci. 2018;553:63–69.

    Article  CAS  Google Scholar 

  18. Ji W, Afsar NU, Wu B, Sheng F, Shehzad MA, Ge L, et al. In-situ crosslinked SPPO/PVA composite membranes for alkali recovery via diffusion dialysis. J Membr Sci. 2019;590:117267.

    Article  CAS  Google Scholar 

  19. Zhang Y, Zhu PC, Edgren D. Crosslinking reaction of poly (vinyl alcohol) with glyoxal. J Polym Res. 2010;17:725–30.

    Article  CAS  Google Scholar 

  20. Leone G, Consumi M, Pepi S, Pardini A, Bonechi C, Tamasi G, et al. Poly-vinyl alcohol (PVA) crosslinked by trisodium trimetaphosphate (STMP) and sodium hexametaphosphate (SHMP): effect of molecular weight, pH and phosphorylating agent on length of spacing arms, crosslinking density and water interaction. J Mol Struct. 2020;1202:127264.

    Article  CAS  Google Scholar 

  21. Miyazaki T, Takeda Y, Akane S, Itou T, Hoshiko A, En K. Role of boric acid for a poly (vinyl alcohol) film as a cross-linking agent: Melting behaviors of the films with boric acid. Polymer. 2010;51:5539–49.

    Article  CAS  Google Scholar 

  22. Bolto B, Tran T, Hoang M, Xie Z. Crosslinked poly (vinyl alcohol) membranes. Prog Polym Sci. 2009;34:969–81.

    Article  CAS  Google Scholar 

  23. Heydari M, Moheb A, Ghiaci M, Masoomi M. Effect of cross‐linking time on the thermal and mechanical properties and pervaporation performance of poly (vinyl alcohol) membrane cross‐linked with fumaric acid used for dehydration of isopropanol. J Appl Polym Sci. 2013;128:1640–51.

    CAS  Google Scholar 

  24. Jose J, Al-Harthi MA. Citric acid crosslinking of poly (vinyl alcohol)/starch/graphene nanocomposites for superior properties. Iran Polym J. 2017;26:579–87.

    Article  CAS  Google Scholar 

  25. Sonker AK, Teotia AK, Kumar A, Nagarale RK, Verma V. Development of polyvinyl alcohol based high strength biocompatible composite films. Macromol Chem Phys. 2017;218:1700130.

    Article  Google Scholar 

  26. Sonker AK, Rathore K, Teotia AK, Kumar A, Verma V. Rapid synthesis of high strength cellulose–poly (vinyl alcohol)(PVA) biocompatible composite films via microwave crosslinking. J Appl Polym Sci. 2019;136:47393.

    Article  Google Scholar 

  27. Sonker AK, Verma V. Influence of crosslinking methods toward poly (vinyl alcohol) properties: microwave irradiation and conventional heating. J Appl Polym Sci. 2018;135:46125.

    Article  Google Scholar 

  28. Kudoh Y, Kojima T, Abe M, Oota M, Yamamoto T. Proton conducting membranes consisting of poly (vinyl alcohol) and poly (styrene sulfonic acid): crosslinking of poly (vinyl alcohol) with and without succinic acid. Solid State Ion. 2013;253:189–94.

    Article  CAS  Google Scholar 

  29. Dlamini DS, Wang J, Mishra AK, Mamba BB, Hoek EMV. Effect of cross-linking agent chemistry and coating conditions on physical, chemical, and separation properties of PVA-Psf composite membranes. Sep Sci Technol. 2014;49:22–29.

    Article  CAS  Google Scholar 

  30. Salgado‐Chavarría D, Palacios‐Alquisira J. Poly (vinyl alcohol) membranes cross‐linked with maleic anhydride and 2, 5‐furandicarboxylic acid: conventional heating and microwave irradiation. ChemistrySelect. 2020;5:4826–38.

    Article  Google Scholar 

  31. Sajid M, Zhao X, Liu D. Production of 2, 5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF): recent progress focusing on the chemical-catalytic routes. Green Chem. 2018;20:5427–53.

    Article  CAS  Google Scholar 

  32. Liguori F, Barbaro P, Calisi N. Continuous‐flow oxidation of HMF to FDCA by resin‐supported platinum catalysts in neat water. ChemSusChem. 2019;12:2558–63.

    Article  CAS  PubMed  Google Scholar 

  33. Liu X, Zhang M, Li Z. CoO x-MC (MC= mesoporous carbon) for highly efficient oxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-furandicarboxylic acid (FDCA). ACS Sustain Chem Eng. 2020;8:4801–8.

    Article  CAS  Google Scholar 

  34. Guan W, Zhang Y, Chen Y, Wu J, Cao Y, Wei Y, et al. Hierarchical porous bowl-like nitrogen-doped carbon supported bimetallic AuPd nanoparticles as nanoreactors for high efficient catalytic oxidation of HMF to FDCA. J Catal. 2021;396:40–53.

    Article  CAS  Google Scholar 

  35. Menegazzo F, Ghedini E, Signoretto M. 5-Hydroxymethylfurfural (HMF) production from real biomasses. Molecules. 2018;23:2201.

    Article  PubMed Central  Google Scholar 

  36. Sonsiam C, Kaewchada A, Jaree A. Synthesis of 5-hydroxymethylfurfural (5-HMF) from fructose over cation exchange resin in a continuous flow reactor. Chem Eng Process. 2019;138:65–72.

    Article  CAS  Google Scholar 

  37. Zhang Y, Li B, Guan W, Wei Y, Yan C, Meng M, et al. One-pot synthesis of HMF from carbohydrates over acid-base bi-functional carbonaceous catalyst supported on halloysite nanotubes. Cellulose. 2020;27:3037–54.

    Article  CAS  Google Scholar 

  38. El Fergani M, Candu N, Tudorache M, Bucur C, Djelal N, Granger P, et al. From useless humins by-product to Nb@graphite-like carbon catalysts highly efficient in HMF synthesis. Appl Catal A: Gen. 2021;618:118130.

    Article  CAS  Google Scholar 

  39. Fei X, Wang J, Zhu J, Wang X, Liu X. Biobased poly (ethylene 2, 5-furancoate): No longer an alternative, but an irreplaceable polyester in the polymer industry. ACS Sustain Chem Eng. 2020;8:8471–85.

    Article  CAS  Google Scholar 

  40. Terzopoulou Z, Papadopoulos L, Zamboulis A, Papageorgiou DG, Papageorgiou GZ, Bikiaris DN. Tuning the properties of furandicarboxylic acid-based polyesters with copolymerization: a review. Polymers. 2020;12:1209.

    Article  CAS  PubMed Central  Google Scholar 

  41. Trung NV, Nguyen MN, Ngoc ANT, Thi NP, Quang TT, Thi TT. Synthesis and characterizations of biobased copolymer poly (ethylene-co-butylene 2, 5-furandicarboxylate). Int J Polym Sci. 2021;2021:9104546.

  42. Zhang D, Dumont MJ. Advances in polymer precursors and bio‐based polymers synthesized from 5‐hydroxymethylfurfural. J Polym Sci Part A: Polym Chem. 2017;55:1478–92.

    Article  CAS  Google Scholar 

  43. Burgess SK, Karvan O, Johnson JR, Kriegel RM, Koros WJ. Oxygen sorption and transport in amorphous poly (ethylene furanoate). Polymer. 2014;55:4748–56.

    Article  CAS  Google Scholar 

  44. Burgess SK, Mikkilineni DS, Daniel BY, Kim DJ, Mubarak CR, Kriegel RM, et al. Water sorption in poly (ethylene furanoate) compared to poly (ethylene terephthalate). Part 1: equilibrium sorption. Polymer. 2014;55:6861–9.

    Article  CAS  Google Scholar 

  45. Burgess SK, Mikkilineni DS, Daniel BY, Kim DJ, Mubarak CR, Kriegel RM, et al. Water sorption in poly (ethylene furanoate) compared to poly (ethylene terephthalate). Part 2: kinetic sorption. Polymer. 2014;55:6870–82.

    Article  CAS  Google Scholar 

  46. Rimdusit N, Jubsilp C, Mora P, Hemvichian K, Thuy TT, Karagiannidis P, et al. Radiation graft-copolymerization of ultrafine fully vulcanized powdered natural rubber: effects of styrene and acrylonitrile contents on thermal stability. Polymers. 2021;13:3447.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  47. Yang M-H, Chu T-J. The determination of interaction parameter χ1 for polyvinyl alcohol and water from the diffusion data. Polym Test. 1993;12:57–64.

    Article  CAS  Google Scholar 

  48. Peng Z, Kong LX. A thermal degradation mechanism of polyvinyl alcohol/silica nanocomposites. Polym Degrad Stab. 2007;92:1061–71.

    Article  CAS  Google Scholar 

  49. Gilman JW, VanderHart Dl, Kashiwagi T. Thermal decomposition chemistry of poly(vinyl alcohol). In Fire and polymers II, 599. ACS Symposium Series. American Chemical Society; 1995. p. 161–85.

  50. Tsanaktsis V, Vouvoudi E, Papageorgiou GZ, Papageorgiou DG, Chrissafis K, Bikiaris DN. Thermal degradation kinetics and decomposition mechanism of polyesters based on 2,5-furandicarboxylic acid and low molecular weight aliphatic diols. J Anal Appl Pyrolysis. 2015;112:369–78.

    Article  CAS  Google Scholar 

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Acknowledgements

This research is funded by the Vietnam National Foundation for Science and Technology Development (NAFOSTED) under grant number 104.02-2019.12. The authors are grateful to Nigel Van de Velde for the valuable comments and corrections during the revision of the manuscript.

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  1. Hanoi University of Science and Technology, 1 Dai Co Viet street, 100000, Hanoi, Vietnam

    Nam Vu Trung, Ni Pham Thi, Thu Ha Nguyen, Mai Ngoc Nguyen, Dung Tran Anh, Thanh Nguyen Trung, Tung Tran Quang, Hau Than Van & Thuy Tran Thi

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Vu Trung, N., Pham Thi, N., Nguyen, T.H. et al. Tuning the thermal and mechanical properties of poly(vinyl alcohol) with 2,5-furandicarboxylic acid acting as a biobased crosslinking agent. Polym J 54, 335–343 (2022). https://doi.org/10.1038/s41428-021-00583-y

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