Sustainable, upscaled synthesis of pinene-derived (meth)acrylates and their application as high Tg monomers in styrene/acrylic-based bioderived copolymer coatings

Pin-Nó, María; L. Jacob, Philippa; Taresco, Vincenzo; Kastelijn, Maud; Nabuurs, Tijs; Surti, Chandres; Bilney, John; Daly, John; J. Keddie, Daniel; M. Howdle, Steven; A. Stockman, Robert

Abstract

n improved synthesis of the pinene-derived monomers (3-pinanyl acrylate 1 and 3-pinanyl methacrylate 2), replacing hazardous and/or expensive reagents from established methods with cheaper, more innocuous and sustainable reagents, is reported; the monomers of high purity are obtained at up to 160 g scale, without the need for chromatographic separation. Subsequently, these monomers (1 and 2) were successfully copolymerized with n-butyl acrylate/methacrylic acid or styrene/methacrylic acid using a radical semi-batch emulsion copolymerization process. For comparison, materials incorporating the more established terpene-derived monomer iso-bornyl methacrylate 3 were also prepared in an analogous fashion. The obtained polymer latexes had particle sizes between 65 and 90 nm and very low polydispersities (<0.08) and were stable for several years without any coagulum formation. Gradient liquid chromatography indicated that all copolymers had relatively uniform chemical composition distributions. The n-butyl acrylate containing copolymers (P1–P3) were obtained with high molar masses (Mn > 40 000 and Mw > 400 000), very high dispersities (Ð > 9.5), and low glass transition temperatures (Tg < −5 °C). The styrene-based copolymers (P4–P6) had slightly lower molar masses (Mn > 40 000 and Mw > 150 000), lower dispersities (Ð > 3) and high glass transition temperatures (95 °C < Tg < 120 °C). Preliminary testing of the n-butyl acrylate-based materials demonstrated the potential of these copolymers for use in coating applications. The poly(n-butyl acrylate)/pinanyl methacrylate copolymer P2 was found to be harder (König hardness) and had better stain resistance properties towards water-based substances than the analogous n-butyl acrylate-based copolymers containing 3-pinanyl acrylate (P1) or iso-bornyl methacrylate (P3). Through further refinement of the copolymerization process we expect that the properties of these polymers may be further tailored towards a range of coating applications.

Citation

Pin-Nó, M., L. Jacob, P., Taresco, V., Kastelijn, M., Nabuurs, T., Surti, C., Bilney, J., Daly, J., J. Keddie, D., M. Howdle, S., & A. Stockman, R. (2024). Sustainable, upscaled synthesis of pinene-derived (meth)acrylates and their application as high Tg monomers in styrene/acrylic-based bioderived copolymer coatings. RSC Sustainability, 2(9), 2515-2523. https://doi.org/10.1039/D4SU00210E

• Journal Article Type: Article
• Acceptance Date: Jul 19, 2024
• Online Publication Date: Jul 22, 2024
• Publication Date: Sep 1, 2024
• Deposit Date: Sep 11, 2024
• Publicly Available Date: Sep 11, 2024
• Journal: RSC Sustainability
• Print ISSN: 2753-8125
• Electronic ISSN: 2753-8125
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 2
• Issue: 9
• Pages: 2515-2523
• DOI: https://doi.org/10.1039/D4SU00210E
• Public URL: https://nottingham-repository.worktribe.com/output/37942026
• Publisher URL: https://pubs.rsc.org/en/content/articlelanding/2024/su/d4su00210e