UV-mediated Thiol-ene Polyol Functionalization for Synthesis of Biobased Waterborne Polyurethanes
Jevgenij Lazko （ Materia Nova Research Center, Laboratory of Polymeric and Composite Materials (SMPC), Avenue Copernic 3, 7000 Mons, Belgium. ）
Loïc Poussard （ Materia Nova Research Center, Laboratory of Polymeric and Composite Materials (SMPC), Avenue Copernic 3, 7000 Mons, Belgium. ）
Jérôme Mariage （ Materia Nova Research Center, Laboratory of Polymeric and Composite Materials (SMPC), Avenue Copernic 3, 7000 Mons, Belgium. ）
Fouad Laoutid
Jean Marie Raquez （ a Materia Nova Research Center, Laboratory of Polymeric and Composite Materials (SMPC), Avenue Copernic 3, 7000 Mons, Belgium. b Center of Innovation and Research in Materials & Polymers (CIRMAP), University of Mons (UMons), Place du Parc 23, 7000 Mons, Belgium. ）
Philippe Dubois （ a Materia Nova Research Center, Laboratory of Polymeric and Composite Materials (SMPC), Avenue Copernic 3, 7000 Mons, Belgium. b Center of Innovation and Research in Materials & Polymers (CIRMAP), University of Mons (UMons), Place du Parc 23, 7000 Mons, Belgium. ）
https://doi.org/10.37155/2717-526X-0201-1Abstract
Developing waterborne polyurethane coatings from biobased polyols represents an interesting alternative, allowing at the same time to increase the use of sustainable renewable raw materials and to reduce volatile organic compounds emissions. In this work, biobased Veopur polyol was first functionalized with mercaptopropionic acid (MPA) using solvent-free UV-mediated thiol-ene reaction performed in bulk. Grafted carboxylic moieties were then neutralized by triethylamine (TEA) in order to obtain the required amphiphilic behavior. In the final step, functionalized water dispersible polyol was polymerized with water soluble polyisocyanate to form waterborne polyurethane (WPU). The influence of key-process parameters on grafting efficiency was investigated by iodometric titration, Fourier-transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (1H NMR). Particle size measurements and stress-strain tests were carried out to characterize WPU water dispersions and corresponding materials, respectively.
Keywords
Waterborne polyurethane; biobased polyol; thiol-ene grafting; soft segment; functionalization; UV; dispersionFull Text
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[2] DIETERICH, D. 1981. Aqueous emulsions, dispersions and solutions of polyurethanes; synthesis and properties. Progress in Organic Coatings, 9, 281-340.
[3] DESROCHES, M., ESCOUVOIS, M., AUVERGNE, R., CAILLOL, S. & BOUTEVIN, B. 2012. From Vegetable Oils to Polyurethanes: Synthetic Routes to Polyols and Main Industrial Products. Polymer Reviews, 52, 38-79.
[4] LLIGADAS, G., RONDA, J. C., GALIÀ, M. & CÁDIZ, V. 2013. Renewable polymeric materials from vegetable oils: a perspective. Materials Today, 16, 337-343.
[5] NOREEN, A., ZIA, K. M., ZUBER, M., TABASUM, S. & ZAHOOR, A. F. 2016. Bio-based polyurethane: An efficient and environment friendly coating systems: A review. Progress in Organic Coatings, 91, 25-32.
[6] LI, Y., LUO, X. & HU , S. 2015. Polyols and Polyurethanes from Vegetable Oils and Their Derivatives. SpringerBriefs in Green Chemistry for Sustainability, 15-43.
[7] ALAM, M., AKRAM, D., SHARMIN, E., ZAFAR, F. & AHMAD, S. 2014. Vegetable oil based eco-friendly coating materials: A review article. Arabian Journal of Chemistry, 7, 469-479.
[8] ZAFAR, F., GHOSAL, A., SHARMIN, E., CHATURVEDI, R. & NISHAT, N. 2019. A review on cleaner production of polymeric and nanocomposite coatings based on waterborne polyurethane dispersions from seed oils. Progress in Organic Coatings, 131, 259-275.
[9] LIANG, H., FENG, Y., LU, J., LIU, L., YANG, Z., LUO, Y., ZHANG, Y. & ZHANG, C. 2018a. Bio-based cationic waterborne polyurethanes dispersions prepared from different vegetable oils. Industrial Crops and Products, 122, 448-455.
[10] GHASEMLOU, M., DAVER, F., IVANOVA, E. P. & ADHIKARI, B. 2019. Polyurethanes from seed oil-based polyols: A review of synthesis, mechanical and thermal properties. Industrial Crops and Products, 142, 111841.
[11] SAHOO, S., MOHANTY, S. & NAYAK, S. K. 2018. Biobased polyurethane adhesive over petroleum based adhesive: Use of renewable resource. Journal of Macromolecular Science, Part A, 55, 36-48.
[12] CHANG, C.-W. & LU, K.-T. 2012. Natural castor oil based 2-package waterborne polyurethane wood coatings. Progress in Organic Coatings, 75, 435-443.
[13] FU, C., ZHENG, Z., YANG, Z., CHEN, Y. & SHEN, L. 2014. A fully bio-based waterborne polyurethane dispersion from vegetable oils: From synthesis of precursors by thiol-ene reaction to study of final material. Progress in Organic Coatings, 77, 53-60.
[14] LIANG, H., LIU, L., LU, J., CHEN, M. & ZHANG, C. 2018b. Castor oil-based cationic waterborne polyurethane dispersions: Storage stability, thermo-physical properties and antibacterial properties. Industrial Crops and Products, 117, 169-178.
[15] PHILIPP, C. & ESCHIG, S. 2012. Waterborne polyurethane wood coatings based on rapeseed fatty acid methyl esters. Progress in Organic Coatings, 74, 705-711.
[16] BULLERMANN, J., FRIEBEL, S., SALTHAMMER, T. & SPOHNHOLZ, R. 2013. Novel polyurethane dispersions based on renewable raw materials—Stability studies by variations of DMPA content and degree of neutralisation. Progress in Organic Coatings, 76, 609-615.
[17] SAALAH, S., ABDULLAH, L. C., AUNG, M. M., SALLEH, M. Z., AWANG BIAK, D. R., BASRI, M. & JUSOH, E. R. 2015. Waterborne polyurethane dispersions synthesized from jatropha oil. Industrial Crops and Products, 64, 194-200.
[18] LU, Y. & LAROCK, R. C. 2010. Soybean oil-based, aqueous cationic polyurethane dispersions: Synthesis and properties. Progress in Organic Coatings, 69, 31-37.
[19] LU, Y. & LAROCK, R. C. 2008. Soybean-Oil-Based Waterborne Polyurethane Dispersions: Effects of Polyol Functionality and Hard Segment Content on Properties. Biomacromolecules, 9, 3332-3340.
[20] CHANG, C.-W. & LU, K.-T. 2013. Linseed-oil-based waterborne UV/air dual-cured wood coatings. Progress in Organic Coatings, 76, 1024-1031.
[21] WICKS JR, Z. W., WICKS, D. A. & ROSTHAUSER, J. W. 2002. Two package waterborne urethane systems. Progress in Organic Coatings, 44, 161-183.
[22] POUSSARD, L., LAZKO, J., MARIAGE, J., RAQUEZ, J. M. & DUBOIS, P. 2016. Biobased waterborne polyurethanes for coating applications: How fully biobased polyols may improve the coating properties. Progress in Organic Coatings, 97, 175-183.
[23] HOYLE, C. E., LEE, T. Y. & ROPER, T. 2004. Thiol–enes: Chemistry of the past with promise for the future. Journal of Polymer Science Part A: Polymer Chemistry, 42, 5301-5338.
[24] LOWE, A. B. 2010. Thiol-ene "click" reactions and recent applications in polymer and materials synthesis. Polymer Chemistry, 1, 17-36.
[25] MACHADO, T. O., SAYER, C. & ARAUJO, P. H. H. 2017. Thiol-ene polymerisation: A promising technique to obtain novel biomaterials. European Polymer Journal, 86, 200-215.
[26] IONESCU, M., RADOJČIĆ, D., WAN, X., PETROVIĆ, Z. S. & UPSHAW, T. A. 2015. Functionalized vegetable oils as precursors for polymers by thiol-ene reaction. European Polymer Journal, 67, 439-448.
[27] WANG, Z., LIANG, H., YANG, H., XIONG, L., ZHOU, J., HUANG, S., ZHAO, C., ZHONG, J. & FAN, X. 2019. UV-curable self-healing polyurethane coating based on thiol-ene and Diels-Alder double click reactions. Progress in Organic Coatings, 137, 105282.
[28] AOYAGI, S., SHIMASAKI, T., TERAMOTO, N. & SHIBATA, M. 2018. Bio-based polymer networks by thiol-ene photopolymerization of allylated l-glutamic acids and l-tyrosines. European Polymer Journal, 101, 151-158.
[29] XU, D., CAO, Z., WANG, T., ZHONG, J., ZHAO, J., GAO, F., LUO, X., FANG, Z., CAO, J., XU, S. & SHEN, L. 2019. An ambient-cured coating film obtained via a Knoevenagel and Michael addition reactions based on modified acetoacetylated castor oil prepared by a thiol-ene coupling reaction. Progress in Organic Coatings, 135, 510-516.
[30] TAJIMA, K., IWAMOTO, K., SATOH, Y., SAKAI, R., SATOH, T. & DAIRI, T. 2016. Advanced functionalization of polyhydroxyalkanoate via the UV-initiated thiol-ene click reaction. Applied Microbiology and Biotechnology, 100, 4375-4383.
[31] AIMETTI, A. A., MACHEN, A. J. & ANSETH, K. S. 2009. Poly(ethylene glycol) hydrogels formed by thiol-ene photopolymerization for enzyme-responsive protein delivery. Biomaterials, 30, 6048-6054.
[32] OTTS, D. B., HEIDENREICH, E. & URBAN, M. W. 2005. Novel waterborne UV-crosslinkable thiol–ene polyurethane dispersions: Synthesis and film formation. Polymer, 46, 8162-8168.
[33] KILLOPS, K. L., CAMPOS, L. M. & HAWKER, C. J. 2008. Robust, Efficient, and Orthogonal Synthesis of Dendrimers via Thiol-ene “Click” Chemistry. Journal of the American Chemical Society, 130, 5062-5064.
[34] CLAUDINO, M., JOHANSSON, M. & JONSSON, M. 2010. Thiol–ene coupling of 1,2-disubstituted alkene monomers: The kinetic effect of cis/trans-isomer structures. European Polymer Journal, 46, 2321-2332.
[35] CLAUDINO, M., VAN DER MEULEN, I., TREY, S., JONSSON, M., HEISE, A. & JOHANSSON, M. 2012. Photoinduced thiol–ene crosslinking of globalide/ε-caprolactone copolymers: Curing performance and resulting thermoset properties. Journal of Polymer Science Part A: Polymer Chemistry, 50, 16-24.
[36] CLAUDINO, M., MATHEVET, J.-M., JONSSON, M. & JOHANSSON, M. 2014. Bringing d-limonene to the scene of bio-based thermoset coatings via free-radical thiol-ene chemistry: macromonomer synthesis, UV-curing and thermo-mechanical characterization. Polymer Chemistry, 5, 3245-3260.
[37] CAMPOS, L. M., KILLOPS, K. L., SAKAI, R., PAULUSSE, J. M. J., DAMIRON, D., DROCKENMULLER, E., MESSMORE, B. W. & HAWKER, C. J. 2008. Development of Thermal and Photochemical Strategies for Thiol−Ene Click Polymer Functionalization. Macromolecules, 41, 7063-7070.
[38] BOUTEVIN, G., AMEDURI, B., BOUTEVIN, B. & JOUBERT, J.-P. 2000. Synthesis and use of hydroxyl telechelic polybutadienes grafted by 2-mercaptoethanol for polyurethane resins. Journal of Applied Polymer Science, 75, 1655-1666.
[39] LOWE, A. B. 2014. Thiol-ene "click" reactions and recent applications in polymer and materials synthesis: a first update. Polymer Chemistry, 5, 4820-4870.
[40] HE, M., JIANG, S., XU, R., YANG, J., ZENG, Z. & CHEN, G. 2014. Facile functionalization of soybean oil by thiol-ene photo-click reaction for the synthesis of polyfunctional acrylate. Progress in Organic Coatings, 77, 868-871.
[41] ZHANG, Y., MAXTED, J., BARBER, A., LOWE, C. & SMITH, R. 2013. The durability of clear polyurethane coil coatings studied by FTIR peak fitting. Polymer Degradation and Stability, 98, 527-534.
[42] BHARGAVA, S., KUBOTA, M., LEWIS, R. D., ADVANI, S. G., PRASAD, A. K. & DEITZEL, J. M. 2015. Ultraviolet, water, and thermal aging studies of a waterborne polyurethane elastomer-based high reflectivity coating. Progress in Organic Coatings, 79, 75-82.
[43] PATEL, C. J. & MANNARI, V. 2014. Air-drying bio-based polyurethane dispersion from cardanol: Synthesis and characterization of coatings. Progress in Organic Coatings, 77, 997-1006.
[44] GARCÍA-PACIOS, V., COSTA, V., COLERA, M. & MARTÍN-MARTÍNEZ, J. M. 2011. Waterborne polyurethane dispersions obtained with polycarbonate of hexanediol intended for use as coatings. Progress in Organic Coatings, 71, 136-146.
Copyright © 2020 Jevgenij Lazko, Loïc Poussard, Jérôme Mariage, Fouad Laoutid, Jean Marie Raquez, Philippe Dubois
Publishing time:2020-06-30
This work is licensed under a Creative Commons Attribution 4.0 International License
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