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. 2021 Apr 13;13(8):1255.
doi: 10.3390/polym13081255.

Fully Bio-Based Thermosetting Polyurethanes from Bio-Based Polyols and Isocyanates

Roberto Morales-Cerrada  1 , Romain Tavernier  1 , Sylvain Caillol  1
Affiliations

Fully Bio-Based Thermosetting Polyurethanes from Bio-Based Polyols and Isocyanates

Roberto Morales-Cerrada et al. Polymers (Basel). .

Abstract

The trend towards the utilization of bioresources for the manufacturing of polymers has led industry players to bring to the market new monomers. In this work, we studied 3 polyisocyanates and 2 polyols with high renewable carbon contents, namely L-lysine ethyl ester diisocyanate (LDI), pentamethylene-diisocyanate (PDI) isocyanurate trimer, and hexamethylene-diisocyanate (HDI) allophanate as the isocyanates, as well as castor oil and polypropanediol as the polyols. These monomers are commercially available at a large scale and were used in direct formulations or used as prepolymers. Thermosetting polymers with Tg values ranging from -41 to +21 °C and thermal stabilities of up to 300 °C were obtained, and the polymerization was studied using NMR, DSC, and rheology. Cured materials were also characterized using FTIR, DMA, gel content, and swelling index determinations. These high bio-based content materials can successfully be obtained and could be used as alternatives to petro-based materials.

Keywords: allophanate; bio-based polymers; isocyanates; isocyanurate; lysine; polyols; polyurethanes.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Chemical structures of the commercial partially bio-based isocyanates. Green-colored moieties come from bio-based molecules and red-colored moiety atoms come from petro-sourced molecules.
Scheme 2
Scheme 2
Synthetic pathways for the obtention of polyurethanes from monomers disclosed in Table 1.
Scheme 3
Scheme 3
Idealized structures of prepolymers.
Figure 1
Figure 1
DSC images of uncured formulations at 40 °C·min−1.
Figure 2
Figure 2
Storage modulus (E’) and tan δ vs. temperature values for cured materials for entries L1, T1, and D1, obtained using DMA.
Figure 3
Figure 3
Storage modulus (E’) and tan δ vs. temperature values for cured materials for entries L2, T2, and D2, obtained using DMA.
Figure 4
Figure 4
DSC thermograms of cured materials for entries L1, L2, T1, T2, D1, and D2.
Figure 5
Figure 5
Photographs of cured materials: (a) L1; (b) L2; (c) T1; (d) T2; (e) D1; (f) D2.
See this image and copyright information in PMC

References

    1. Skoczinski P., Chinthapalli R., Carus M., Baltus W., Guzman d.D., Käb H., Raschka A., Ravenstijn J. Bio-Based Building Blocks and Polymers-Global Capacities, Production and Trends 2019–2024. Nova-Institute; Hurth, Germany: 2019.
    1. Álvarez-Chávez C.R., Edwards S., Moure-Eraso R., Geiser K. Sustainability of bio-based plastics: General comparative analysis and recommendations for improvement. J. Clean. Prod. 2012;23:47–56. doi: 10.1016/j.jclepro.2011.10.003. - DOI
    1. Caillol S., Boutevin B., Pascault J.-P. Handbook of Adhesive Technology. CRC Press; Boca Raton, FL, USA: 2017. Bio-Sourced Epoxy Monomers and Polymers.
    1. Nikafshar S., Zabihi O., Hamidi S., Moradi Y., Barzegar S., Ahmadi M., Naebe M. A renewable bio-based epoxy resin with improved mechanical performance that can compete with DGEBA. RSC Adv. 2017;7:8694–8701. doi: 10.1039/C6RA27283E. - DOI
    1. Rad E.R., Vahabi H., de Anda A.R., Saeb M.R., Thomas S. Bio-epoxy resins with inherent flame retardancy. Prog. Org. Coat. 2019;135:608–612. doi: 10.1016/j.porgcoat.2019.05.046. - DOI