María Pin-Nó, Philippa L. Jacob, Vincenzo Taresco, Maud Kastelijn, Tijs Nabuurs, Chandres Surti, John Bilney, John Daly, Daniel J. Keddie, Steven M. Howdle and Robert A. Stockman
{"title":"可持续、大规模合成蒎烯衍生（甲基）丙烯酸酯及其作为高 Tg 单体在苯乙烯/丙烯酸生物共聚物涂料中的应用","authors":"María Pin-Nó, Philippa L. Jacob, Vincenzo Taresco, Maud Kastelijn, Tijs Nabuurs, Chandres Surti, John Bilney, John Daly, Daniel J. Keddie, Steven M. Howdle and Robert A. Stockman","doi":"10.1039/D4SU00210E","DOIUrl":null,"url":null,"abstract":"<p >An improved synthesis of the pinene-derived monomers (3-pinanyl acrylate <strong>1</strong> and 3-pinanyl methacrylate <strong>2</strong>), 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 (<strong>1</strong> and <strong>2</strong>) were successfully copolymerized with <em>n</em>-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 <em>iso</em>-bornyl methacrylate <strong>3</strong> 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 <em>n</em>-butyl acrylate containing copolymers (<strong>P1–P3</strong>) were obtained with high molar masses (<em>M</em><small><sub>n</sub></small> > 40 000 and <em>M</em><small><sub>w</sub></small> > 400 000), very high dispersities (<em>Ð</em> > 9.5), and low glass transition temperatures (<em>T</em><small><sub>g</sub></small> < −5 °C). The styrene-based copolymers (<strong>P4–P6</strong>) had slightly lower molar masses (<em>M</em><small><sub>n</sub></small> > 40 000 and <em>M</em><small><sub>w</sub></small> > 150 000), lower dispersities (<em>Ð</em> > 3) and high glass transition temperatures (95 °C < <em>T</em><small><sub>g</sub></small> < 120 °C). Preliminary testing of the <em>n</em>-butyl acrylate-based materials demonstrated the potential of these copolymers for use in coating applications. The poly(<em>n</em>-butyl acrylate)/pinanyl methacrylate copolymer <strong>P2</strong> was found to be harder (König hardness) and had better stain resistance properties towards water-based substances than the analogous <em>n</em>-butyl acrylate-based copolymers containing 3-pinanyl acrylate (<strong>P1</strong>) or <em>iso</em>-bornyl methacrylate (<strong>P3</strong>). 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.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00210e?page=search","citationCount":"0","resultStr":"{\"title\":\"Sustainable, upscaled synthesis of pinene-derived (meth)acrylates and their application as high Tg monomers in styrene/acrylic-based bioderived copolymer coatings†\",\"authors\":\"María Pin-Nó, Philippa L. Jacob, Vincenzo Taresco, Maud Kastelijn, Tijs Nabuurs, Chandres Surti, John Bilney, John Daly, Daniel J. Keddie, Steven M. Howdle and Robert A. Stockman\",\"doi\":\"10.1039/D4SU00210E\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >An improved synthesis of the pinene-derived monomers (3-pinanyl acrylate <strong>1</strong> and 3-pinanyl methacrylate <strong>2</strong>), 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 (<strong>1</strong> and <strong>2</strong>) were successfully copolymerized with <em>n</em>-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 <em>iso</em>-bornyl methacrylate <strong>3</strong> 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 <em>n</em>-butyl acrylate containing copolymers (<strong>P1–P3</strong>) were obtained with high molar masses (<em>M</em><small><sub>n</sub></small> > 40 000 and <em>M</em><small><sub>w</sub></small> > 400 000), very high dispersities (<em>Ð</em> > 9.5), and low glass transition temperatures (<em>T</em><small><sub>g</sub></small> < −5 °C). The styrene-based copolymers (<strong>P4–P6</strong>) had slightly lower molar masses (<em>M</em><small><sub>n</sub></small> > 40 000 and <em>M</em><small><sub>w</sub></small> > 150 000), lower dispersities (<em>Ð</em> > 3) and high glass transition temperatures (95 °C < <em>T</em><small><sub>g</sub></small> < 120 °C). Preliminary testing of the <em>n</em>-butyl acrylate-based materials demonstrated the potential of these copolymers for use in coating applications. The poly(<em>n</em>-butyl acrylate)/pinanyl methacrylate copolymer <strong>P2</strong> was found to be harder (König hardness) and had better stain resistance properties towards water-based substances than the analogous <em>n</em>-butyl acrylate-based copolymers containing 3-pinanyl acrylate (<strong>P1</strong>) or <em>iso</em>-bornyl methacrylate (<strong>P3</strong>). 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.</p>\",\"PeriodicalId\":74745,\"journal\":{\"name\":\"RSC sustainability\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-07-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00210e?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"RSC sustainability\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/su/d4su00210e\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"RSC sustainability","FirstCategoryId":"1085","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/su/d4su00210e","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Sustainable, upscaled synthesis of pinene-derived (meth)acrylates and their application as high Tg monomers in styrene/acrylic-based bioderived copolymer coatings†
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.
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