Issue 9, 2024

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

Abstract

An 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.

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

Supplementary files

Article information

Article type
Paper
Submitted
30 Apr 2024
Accepted
19 Jul 2024
First published
22 Jul 2024
This article is Open Access
Creative Commons BY license

RSC Sustain., 2024,2, 2515-2523

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

M. Pin-Nó, P. L. Jacob, V. Taresco, M. Kastelijn, T. Nabuurs, C. Surti, J. Bilney, J. Daly, D. J. Keddie, S. M. Howdle and R. A. Stockman, RSC Sustain., 2024, 2, 2515 DOI: 10.1039/D4SU00210E

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