journal article·2025-12-02Open access

Effects of alkylene spacer length of 2-pyrone-4,6-dicarboxylic acid polyesters on biodegradability and metal adhesive properties

Yijie Jin, Keiju Yoshida, Suzuha Kimura, Atsushi Isobe, Keiichi Kuboyama, Masaya Fujita, Takuma Araki, Yuzo Suzuki, Yuichiro Otsuka, Naofumi Kamimura, Eiji Masai, Masaya Nakamura, Tsuyoshi Michinobu

NPG Asia Materials· Volume 17· Issue 1

Abstract

Abstract 2-Pyrone-4,6-dicarboxylic acid (PDC) is a lignin-derived biometabolic intermediate that can be produced on a large scale by using transforming bacteria and can be directly polymerized by polycondensation with diols to produce biomass polyesters. In the present study, a variety of PDC-based polyesters were successfully synthesized by direct polymerization between PDC and diols with different alkyl chain lengths. The thermal, crystalline, and mechanical properties of a series of PDC polyesters were fully characterized. The biodegradability of the PDC polyesters was investigated by biodegradation tests in a confined simulated environment using pond water. There was a clear correlation between the biodegradation rate, alkylene spacer length, and polymer hydrophilicity. In addition, the PDC polyesters exhibited excellent adhesive properties to various metals, and their adhesive properties gradually decreased with a decrease in the PDC content in the polymers. The excellent adhesion to an aluminum plate with the lap-shear strength of up to 15.26 MPa was demonstrated and this value is comparable to those of the-state-of-the-art commercial quick-drying metal adhesives.
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Research context

OpenAlex topics: Lignin and Wood Chemistry · Polymer composites and self-healing · Synthesis and properties of polymers

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (37)

Show source-provided references
1. Vink, E. T., Rabago, K. R., Glassner, D. A. & Gruber, P. R. Applications of life cycle assessment to NatureWorks™ polylactide (PLA) production. Polym. Degrad. Stabil. 80, 403–419 (2003).10.1016/S0141-3910(02)00372-5 ↗
2. Hirota, S. I., Sato, T., Tominaga, Y., Asai, S. & Sumita, M. The effect of high-pressure carbon dioxide treatment on the crystallization behavior and mechanical properties of poly (l-lactic acid)/poly (methyl methacrylate) blends. Polymer 47, 3954–3960 (2006).10.1016/j.polymer.2006.03.069 ↗
3. Mekonnen, T., Mussone, P., Khalil, H. & Bressler, D. Progress in bio-based plastics and plasticizing modifications. J. Mater. Chem. A 1, 13379–13398 (2013).10.1039/c3ta12555f ↗
4. Garrison, T. F., Murawski, A. & Quirino, R. L. Bio-based polymers with potential for biodegradability. Polymers 8, 262 (2016).10.3390/polym8070262 ↗
5. Iwata, T. Biodegradable and bio-based polymers: future prospects of eco-friendly plastics. Angew. Chem. Int. Ed. 54, 3210–3215 (2015).10.1002/anie.201410770 ↗
6. Zhang, Q. et al. Bio-based polyesters: recent progress and future prospects. Prog. Polym. Sci. 120, 101430 (2021).10.1016/j.progpolymsci.2021.101430 ↗
7. Zeng, C., Seino, H., Ren, J., Hatanaka, K. & Yoshie, N. Bio-based furan polymers with self-healing ability. Macromolecules 46, 1794–1802 (2013).10.1021/ma3023603 ↗
8. Wang, J. et al. Highly degradable bio-based plastic with water-assisted shaping process and exceptional mechanical properties. Carbohydr. Polym. 347, 122773 (2024).10.1016/j.carbpol.2024.122773 ↗
9. Yu, O. & Kim, K. H. Lignin to materials: a focused review on recent novel lignin applications. Appl. Sci. 10, 4626 (2019).10.3390/app10134626 ↗
10. Kun, D. & Pukánszky, B. Polymer/lignin blends: Interactions, properties, applications. Eur. Polym. J. 93, 618–641 (2017).10.1016/j.eurpolymj.2017.04.035 ↗
11. Rinaldi, R. et al. Paving the way for lignin valorisation: recent advances in bioengineering, biorefining and catalysis. Angew. Chem. Int. Ed. 55, 8164 (2016).10.1002/anie.201510351 ↗
12. Chung, Y. L. et al. A renewable lignin–lactide copolymer and application in biobased composites. ACS Sustain. Chem. Eng. 1, 1231–1238 (2013).10.1021/sc4000835 ↗
13. Rico-García, D. et al. Lignin-based hydrogels: synthesis and applications. Polymers 12, 81 (2020).10.3390/polym12010081 ↗
14. Ragauskas, A. J. et al. Lignin valorization: improving lignin processing in the biorefinery. Science 344, 1246843 (2014).10.1126/science.1246843 ↗
15. Shi, Y. et al. Lignin hydrogel sensor with anti-dehydration, anti-freezing, and reproducible adhesion prepared based on the room-temperature induction of zinc chloride-lignin redox system. Int. J. Biol. Macromol. 279, 135493 (2024).10.1016/j.ijbiomac.2024.135493 ↗
16. Mei, Q., Shen, X., Liu, H. & Han, B. Selectively transform lignin into value-added chemicals. Chin. Chem. Lett. 30, 15–24 (2019).10.1016/j.cclet.2018.04.032 ↗
17. Li, C., Zhao, X., Wang, A., Huber, G. W. & Zhang, T. Catalytic transformation of lignin for the production of chemicals and fuels. Chem. Rev. 115, 11559–11624 (2015).10.1021/acs.chemrev.5b00155 ↗
18. Mahmood, N., Yuan, Z., Schmidt, J. & Xu, C. C. Depolymerization of lignins and their applications for the preparation of polyols and rigid polyurethane foams: a review. Renew. Sustain. Energy Rev. 60, 317–329 (2016).10.1016/j.rser.2016.01.037 ↗
19. Schutyser, W. et al. Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading. Chem. Soc. Rev. 47, 852–908 (2018).10.1039/C7CS00566K ↗
20. Bugg, T. D., Ahmad, M., Hardiman, E. M. & Rahmanpour, R. Pathways for degradation of lignin in bacteria and fungi. Nat. Prod. Rep. 28, 1883–1896 (2011).10.1039/c1np00042j ↗
21. Otsuka, Y. et al. High-level production of 2-pyrone-4,6-dicarboxylic acid from a lignin-derived aromatic compound by metabolically engineered fermentation to realize industrial valorization processes of lignin. Bioresour. Technol. 377, 128956 (2023).10.1016/j.biortech.2023.128956 ↗
22. Jia, H. et al. Ion conductive organogels based on cellulose and lignin-derived metabolic intermediate. ACS Sustain. Chem. Eng. 12, 501–511 (2024).10.1021/acssuschemeng.3c06488 ↗
23. Shimura, T. et al. Improved thermal properties of polydimethylsiloxane by copolymerization and thiol-ene crosslinking of 2-pyrone-4,6-dicarboxylic acid moiety. Polym. Chem. 16, 45–51 (2025).10.1039/D4PY01051E ↗
24. Cheng, Y. et al. Accelerated development of novel biomass-based polyurethane adhesives via machine learning. ACS Appl. Mater. Interfaces 17, 15959–15968 (2025).10.1021/acsami.4c20371 ↗
25. Michinobu, T. et al. Fusible, elastic, and biodegradable polyesters of 2-pyrone-4,6-dicarboxylic acid (PDC). Polym. J. 41, 1111–1116 (2009).10.1295/polymj.PJ2009045R ↗
26. Michinobu, T. et al. Synthesis and characterization of hybrid biopolymers of L-lactic acid and 2-pyrone-4,6-dicarboxylic acid. J. Macromol. Sci. A 47, 564–570 (2010).10.1080/10601321003742121 ↗
27. Shikinaka, K. et al. Thermoplastic polyesters of 2-pyrone-4,6-dicarboxylic acid (PDC) obtained from a metabolic intermediate of lignin. Sen’i Gakkaishi 69, 39–47 (2013).10.2115/fiber.69.39 ↗
28. Patel, M. R., Shukla, J. M., Patel, N. K. & Patel, K. H. Biomaterial based novel polyurethane adhesives for wood to wood and metal to metal bonding. Mater. Res. 12, 385–393 (2009).10.1590/S1516-14392009000400003 ↗
29. Zhang, Y. et al. A high-performance bio-adhesive using hyperbranched aminated soybean polysaccharide and bio-based epoxide. Adv. Mater. Interfaces 7, 2000148 (2020).10.1002/admi.202000148 ↗
30. Westerman, C. R., McGill, B. C. & Wilker, J. J. Sustainably sourced components to generate high-strength adhesives. Nature 621, 306–311 (2023).10.1038/s41586-023-06335-7 ↗
31. Michinobu, T. et al. Click synthesis and adhesive properties of novel biomass-based polymers from lignin-derived stable metabolic intermediate. Polym. J. 43, 648–653 (2011).10.1038/pj.2011.40 ↗
32. Hishida, M. et al. Polyesters of 2-pyrone-4,6-dicarboxylic acid (PDC) as bio-based plastics exhibiting strong adhering properties. Polym. J. 41, 297–302 (2009).10.1295/polymj.PJ2008291 ↗
33. Jin, Y. et al. Click synthesis of triazole polymers based on lignin-derived metabolic intermediate and their strong adhesive properties to Cu plate. Polymers 15, 1349 (2023).10.3390/polym15061349 ↗
34. Cheng, Y. et al. Polyurethanes based on lignin-derived metabolic intermediate with strong adhesion to metals. Polym., Chem. 13, 6589–6598 (2022).10.1039/D2PY01128J ↗
35. Jin, Y. et al. Biodegradable and wood adhesive polyesters based on lignin-derived 2-pyrone-4, 6-dicarboxylic acid. RSC Sustain. 2, 1985–1993 (2024).10.1039/D4SU00163J ↗
36. Kanno, H. A simple derivation of the empirical rule TGTM=23. J. Non-Cryst. Solids 44, 409–413 (1981).10.1016/0022-3093(81)90047-8 ↗
37. Hasegawa, Y. et al. Tenacious epoxy adhesives prepared from lignin-derived stable metabolic intermediate. Sen’i Gakkaishi 65, 359–362 (2009).10.2115/fiber.65.359 ↗