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Synthesis of Poly(glycerol malonate) Oligomers from Bio-based Sources Utilizing AlCl3 Catalyst

Year 2025, Volume: 8 Issue: 1, 41 - 46, 11.03.2025
https://doi.org/10.58692/jotcsb.1533994

Abstract

Due to the significant economic and environmental benefits, the demand for biomass-derived building blocks in polymer development has increased in recent years. Bio-based plastics, integral to advancing a circular economy, have consistently been a leading topic among emerging technologies. In this study, we aim to evaluate the effectiveness of different esterification catalysts. To achieve this, we synthesized a range of fully bio-based oligomers using glycerol and malonic acid as starting materials, along with three catalysts: tin(II) 2-ethylhexanoate (stannous octoate, Sn(Oct)2), stannous chloride dihydrate (SnCl2·2H2O), and aluminum chloride (AlCl3). The chemical structures of the synthesized oligomers were confirmed using NMR and FTIR spectroscopy. Thermal properties were assessed using DSC and TGA. FTIR analysis verified successful oligomer synthesis, and a glass transition temperature (Tg) of approximately -56 °C was determined via DSC. Additionally, the oligomers exhibited maximum working temperatures at around 278 °C, corresponding to a 50 wt% loss.

Supporting Institution

TUBITAK

Project Number

TUBITAK 220M112

Thanks

This work was financially supported by the TUBITAK (Project No: 220M112).

References

  • Acik, G. (2020). Bio-based poly (ɛ-caprolactone) from soybean-oil derived polyol via ring-opening polymerization. Journal of Polymers and the Environment, 28(2), 668-675.
  • Ansari, S., Sami, N., Yasin, D., Ahmad, N., & Fatma, T. (2021). Biomedical applications of environmental friendly poly-hydroxyalkanoates. International Journal of Biological Macromolecules, 183, 549-563.
  • Balla, E., Daniilidis, V., Karlioti, G., Kalamas, T., Stefanidou, M., Bikiaris, N. D.,…Bikiaris, D. N. (2021). Poly (lactic Acid): A versatile biobased polymer for the future with multifunctional properties—From monomer synthesis, polymerization techniques and molecular weight increase to PLA applications. Polymers, 13(11), 1822.
  • Bozell, J. J., & Petersen, G. R. (2010). Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited. Green Chemistry, 12(4), 539-554.
  • Doğan, E., & Küsefoğlu, S. (2008). Synthesis and in situ foaming of biodegradable malonic acid ESO polymers. Journal of Applied Polymer Science, 110(2), 1129-1135.
  • Fei, X., Wang, J., Zhang, X., Jia, Z., Jiang, Y., & Liu, X. (2022). Recent progress on bio-based polyesters derived from 2, 5-furandicarbonxylic acid (FDCA). Polymers, 14(3), 625.
  • Iwata, T. (2015). Biodegradable and Bio-Based Polymers: Future Prospects of Eco-Friendly Plastics. Angewandte Chemie International Edition, 54(11), 3210-3215. https://doi.org/https://doi.org/10.1002/anie.201410770
  • Jem, K. J., & Tan, B. (2020). The development and challenges of poly (lactic acid) and poly (glycolic acid). Advanced Industrial and Engineering Polymer Research, 3(2), 60-70.
  • Kasmi, N., Pinel, C., Perez, D. D. S., Dieden, R., & Habibi, Y. (2021). Synthesis and characterization of fully biobased polyesters with tunable branched architectures. Polymer Chemistry, 12(7), 991-1001.
  • Morinval, A., & Averous, L. (2022). Systems based on biobased thermoplastics: from bioresources to biodegradable packaging applications. Polymer Reviews, 62(4), 653-721.
  • Qiu, K., & Netravali, A. N. (2013). Halloysite nanotube reinforced biodegradable nanocomposites using noncrosslinked and malonic acid crosslinked polyvinyl alcohol. Polymer composites, 34(5), 799-809.
  • Tremblay-Parrado, K.-K., García-Astrain, C., & Avérous, L. (2021). Click chemistry for the synthesis of biobased polymers and networks derived from vegetable oils. Green Chemistry, 23(12), 4296-4327.
  • Wang, G., Hao, X., Dong, Y., Zhang, L., & Sun, R. (2022). Fully bio-based poly (butylene succinate-co-butylene 2, 5-thiophenedicarboxylate) with derived from 2, 5-thiophenedicarboxylic acid. Express Polymer Letters, 16(7), 772-784.
  • Zhang, Q., Song, M., Xu, Y., Wang, W., Wang, Z., & Zhang, L. (2021). Bio-based polyesters: Recent progress and future prospects. Progress in Polymer Science, 120, 101430.
  • Zhao, W., Nolan, B., Bermudez, H., Hsu, S. L., Choudhary, U., & van Walsem, J. (2020). Spectroscopic study of the morphology development of closed-cell polyurethane foam using bio-based malonic acid as chain extender. Polymer, 193, 122344.
Year 2025, Volume: 8 Issue: 1, 41 - 46, 11.03.2025
https://doi.org/10.58692/jotcsb.1533994

Abstract

Project Number

TUBITAK 220M112

References

  • Acik, G. (2020). Bio-based poly (ɛ-caprolactone) from soybean-oil derived polyol via ring-opening polymerization. Journal of Polymers and the Environment, 28(2), 668-675.
  • Ansari, S., Sami, N., Yasin, D., Ahmad, N., & Fatma, T. (2021). Biomedical applications of environmental friendly poly-hydroxyalkanoates. International Journal of Biological Macromolecules, 183, 549-563.
  • Balla, E., Daniilidis, V., Karlioti, G., Kalamas, T., Stefanidou, M., Bikiaris, N. D.,…Bikiaris, D. N. (2021). Poly (lactic Acid): A versatile biobased polymer for the future with multifunctional properties—From monomer synthesis, polymerization techniques and molecular weight increase to PLA applications. Polymers, 13(11), 1822.
  • Bozell, J. J., & Petersen, G. R. (2010). Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited. Green Chemistry, 12(4), 539-554.
  • Doğan, E., & Küsefoğlu, S. (2008). Synthesis and in situ foaming of biodegradable malonic acid ESO polymers. Journal of Applied Polymer Science, 110(2), 1129-1135.
  • Fei, X., Wang, J., Zhang, X., Jia, Z., Jiang, Y., & Liu, X. (2022). Recent progress on bio-based polyesters derived from 2, 5-furandicarbonxylic acid (FDCA). Polymers, 14(3), 625.
  • Iwata, T. (2015). Biodegradable and Bio-Based Polymers: Future Prospects of Eco-Friendly Plastics. Angewandte Chemie International Edition, 54(11), 3210-3215. https://doi.org/https://doi.org/10.1002/anie.201410770
  • Jem, K. J., & Tan, B. (2020). The development and challenges of poly (lactic acid) and poly (glycolic acid). Advanced Industrial and Engineering Polymer Research, 3(2), 60-70.
  • Kasmi, N., Pinel, C., Perez, D. D. S., Dieden, R., & Habibi, Y. (2021). Synthesis and characterization of fully biobased polyesters with tunable branched architectures. Polymer Chemistry, 12(7), 991-1001.
  • Morinval, A., & Averous, L. (2022). Systems based on biobased thermoplastics: from bioresources to biodegradable packaging applications. Polymer Reviews, 62(4), 653-721.
  • Qiu, K., & Netravali, A. N. (2013). Halloysite nanotube reinforced biodegradable nanocomposites using noncrosslinked and malonic acid crosslinked polyvinyl alcohol. Polymer composites, 34(5), 799-809.
  • Tremblay-Parrado, K.-K., García-Astrain, C., & Avérous, L. (2021). Click chemistry for the synthesis of biobased polymers and networks derived from vegetable oils. Green Chemistry, 23(12), 4296-4327.
  • Wang, G., Hao, X., Dong, Y., Zhang, L., & Sun, R. (2022). Fully bio-based poly (butylene succinate-co-butylene 2, 5-thiophenedicarboxylate) with derived from 2, 5-thiophenedicarboxylic acid. Express Polymer Letters, 16(7), 772-784.
  • Zhang, Q., Song, M., Xu, Y., Wang, W., Wang, Z., & Zhang, L. (2021). Bio-based polyesters: Recent progress and future prospects. Progress in Polymer Science, 120, 101430.
  • Zhao, W., Nolan, B., Bermudez, H., Hsu, S. L., Choudhary, U., & van Walsem, J. (2020). Spectroscopic study of the morphology development of closed-cell polyurethane foam using bio-based malonic acid as chain extender. Polymer, 193, 122344.
There are 15 citations in total.

Details

Primary Language English
Subjects Polymer Science and Technologies
Journal Section Full-length articles
Authors

Ersan Eyiler 0000-0002-1754-6590

Project Number TUBITAK 220M112
Publication Date March 11, 2025
Submission Date August 15, 2024
Acceptance Date January 9, 2025
Published in Issue Year 2025 Volume: 8 Issue: 1

Cite

APA Eyiler, E. (2025). Synthesis of Poly(glycerol malonate) Oligomers from Bio-based Sources Utilizing AlCl3 Catalyst. Journal of the Turkish Chemical Society Section B: Chemical Engineering, 8(1), 41-46. https://doi.org/10.58692/jotcsb.1533994

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This piece of scholarly information is licensed under Creative Commons Atıf-GayriTicari-AynıLisanslaPaylaş 4.0 Uluslararası Lisansı.

J. Turk. Chem. Soc., Sect. B: Chem. Eng. (JOTCSB)