Till Meissner, Peter Friedel, Joshua A. Carroll, Christopher Barner-Kowollik and Jens Gaitzsch
{"title":"光化学作用图证明紫外线促进了环烯酮缩醛的自由基开环聚合作用","authors":"Till Meissner, Peter Friedel, Joshua A. Carroll, Christopher Barner-Kowollik and Jens Gaitzsch","doi":"10.1039/D4PY00847B","DOIUrl":null,"url":null,"abstract":"<p >Radical ring-opening polymerisation (RROP) of cyclic ketene acetals (CKAs) is a powerful avenue for the synthesis of biodegradable polyesters with the potential to replace non-decomposable conventional polymers. The radical polymerisation of CKAs is – surprisingly – accelerated by UV light, yet to-date the cause of the acceleration is unknown. We herein demonstrate how highly wavelength-resolved photochemical action plots of the light-induced RROP of 2-methylene-1,3,6-trioxocane (MTC) provide key information for understanding the light-prompted acceleration. We showcase that two wavelengths, 275 and 350 nm, are critical for the acceleration, with the first one facilitating the ring-opening step of the key CKA-intermediate and the second one promoting free radical initiator decay in a wavelength-orthogonal fashion. In contrast to previous studies, we aimed at unravelling the photochemically-driven monomer conversion by performing RROP at room temperature. Computational studies on the MTC radical formed during RROP indicated the cause of the acceleration: a delocalisation of the radical within the ring, which are calculated to be excited by wavelengths close to those identified experimentally. Thus, remarkably, 275 nm light critically accelerates the rate-determining ring-opening step during RROP, suggesting that photons can be used as a traceless reagent in an unexpected fashion to expedite RROPs.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 6","pages":" 704-711"},"PeriodicalIF":4.1000,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py00847b?page=search","citationCount":"0","resultStr":"{\"title\":\"Photochemical action plots evidence UV-promoted radical ring-opening polymerisation of cyclic ketene acetals†\",\"authors\":\"Till Meissner, Peter Friedel, Joshua A. Carroll, Christopher Barner-Kowollik and Jens Gaitzsch\",\"doi\":\"10.1039/D4PY00847B\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Radical ring-opening polymerisation (RROP) of cyclic ketene acetals (CKAs) is a powerful avenue for the synthesis of biodegradable polyesters with the potential to replace non-decomposable conventional polymers. The radical polymerisation of CKAs is – surprisingly – accelerated by UV light, yet to-date the cause of the acceleration is unknown. We herein demonstrate how highly wavelength-resolved photochemical action plots of the light-induced RROP of 2-methylene-1,3,6-trioxocane (MTC) provide key information for understanding the light-prompted acceleration. We showcase that two wavelengths, 275 and 350 nm, are critical for the acceleration, with the first one facilitating the ring-opening step of the key CKA-intermediate and the second one promoting free radical initiator decay in a wavelength-orthogonal fashion. In contrast to previous studies, we aimed at unravelling the photochemically-driven monomer conversion by performing RROP at room temperature. Computational studies on the MTC radical formed during RROP indicated the cause of the acceleration: a delocalisation of the radical within the ring, which are calculated to be excited by wavelengths close to those identified experimentally. Thus, remarkably, 275 nm light critically accelerates the rate-determining ring-opening step during RROP, suggesting that photons can be used as a traceless reagent in an unexpected fashion to expedite RROPs.</p>\",\"PeriodicalId\":100,\"journal\":{\"name\":\"Polymer Chemistry\",\"volume\":\" 6\",\"pages\":\" 704-711\"},\"PeriodicalIF\":4.1000,\"publicationDate\":\"2024-12-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py00847b?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/py/d4py00847b\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/py/d4py00847b","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Radical ring-opening polymerisation (RROP) of cyclic ketene acetals (CKAs) is a powerful avenue for the synthesis of biodegradable polyesters with the potential to replace non-decomposable conventional polymers. The radical polymerisation of CKAs is – surprisingly – accelerated by UV light, yet to-date the cause of the acceleration is unknown. We herein demonstrate how highly wavelength-resolved photochemical action plots of the light-induced RROP of 2-methylene-1,3,6-trioxocane (MTC) provide key information for understanding the light-prompted acceleration. We showcase that two wavelengths, 275 and 350 nm, are critical for the acceleration, with the first one facilitating the ring-opening step of the key CKA-intermediate and the second one promoting free radical initiator decay in a wavelength-orthogonal fashion. In contrast to previous studies, we aimed at unravelling the photochemically-driven monomer conversion by performing RROP at room temperature. Computational studies on the MTC radical formed during RROP indicated the cause of the acceleration: a delocalisation of the radical within the ring, which are calculated to be excited by wavelengths close to those identified experimentally. Thus, remarkably, 275 nm light critically accelerates the rate-determining ring-opening step during RROP, suggesting that photons can be used as a traceless reagent in an unexpected fashion to expedite RROPs.
期刊介绍:
Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.