{"title":"评估 [{Cu(PMDETA)}2(O22-)]2+ 在甲基丙烯酸甲酯的露天光 ATRP 中的作用","authors":"Arumugam Ramu, and , Kannapiran Rajendrakumar*, ","doi":"10.1021/acsomega.4c0277310.1021/acsomega.4c02773","DOIUrl":null,"url":null,"abstract":"<p >Herein, we report an open-air, photo accelerated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) without employing any deoxygenating agent. Under open-air photo ATRP conditions, oxygen reversibly binds with [{Cu (PMDETA)}<sub>2</sub>(O<sub>2</sub><sup>2–</sup>)]<sup>2+</sup><b>(1)</b> to form the required activator, which was demonstrated by simple benchtop oxygen/nitrogen purging experiments. The binding mode of oxygen in <b>(1)</b> (μ(η<sup>2</sup>-η<sup>2</sup>) peroxo dicopper(II)) was investigated using UV Visible-NIR, FT-Raman and X-ray photoelectron (XPS) spectroscopic techniques. DFT studies and electrochemical measurements further support the catalytic role of <b>(1)</b> in open-air photo ATRP. With the synergistic involvement of Cu (II)Br<sub>2</sub>, PMDETA ligand and the intensity of light (365 nm, 4.2 mW cm<sup>–2</sup>), a well-controlled rapid polymerization of MMA under open-air condition was achieved (1.25< <i>Đ</i> < 1.47, 94% conversion in 200 min). The bromo chain end fidelity was exemplified by chain extension experiment, block copolymerization and MALDI-ToF analysis. Other monomers such as methyl acrylate, glycidyl methacrylate, and benzyl methacrylate were also polymerized under open-air condition with reasonable control over molecular weight and <i>Đ</i>. An open-air photo polymerization methodology would be fruitful for applications like photocurable printing, dental, optoelectronics, stereolithography, and protective coatings where simple but rapid photopolymerizations are desirable.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 45","pages":"44916–44930 44916–44930"},"PeriodicalIF":3.7000,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsomega.4c02773","citationCount":"0","resultStr":"{\"title\":\"Evaluation of the Role of [{Cu(PMDETA)}2(O22–)]2+ in Open-Air Photo ATRP of Methyl Methacrylate\",\"authors\":\"Arumugam Ramu, and , Kannapiran Rajendrakumar*, \",\"doi\":\"10.1021/acsomega.4c0277310.1021/acsomega.4c02773\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Herein, we report an open-air, photo accelerated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) without employing any deoxygenating agent. Under open-air photo ATRP conditions, oxygen reversibly binds with [{Cu (PMDETA)}<sub>2</sub>(O<sub>2</sub><sup>2–</sup>)]<sup>2+</sup><b>(1)</b> to form the required activator, which was demonstrated by simple benchtop oxygen/nitrogen purging experiments. The binding mode of oxygen in <b>(1)</b> (μ(η<sup>2</sup>-η<sup>2</sup>) peroxo dicopper(II)) was investigated using UV Visible-NIR, FT-Raman and X-ray photoelectron (XPS) spectroscopic techniques. DFT studies and electrochemical measurements further support the catalytic role of <b>(1)</b> in open-air photo ATRP. With the synergistic involvement of Cu (II)Br<sub>2</sub>, PMDETA ligand and the intensity of light (365 nm, 4.2 mW cm<sup>–2</sup>), a well-controlled rapid polymerization of MMA under open-air condition was achieved (1.25< <i>Đ</i> < 1.47, 94% conversion in 200 min). The bromo chain end fidelity was exemplified by chain extension experiment, block copolymerization and MALDI-ToF analysis. Other monomers such as methyl acrylate, glycidyl methacrylate, and benzyl methacrylate were also polymerized under open-air condition with reasonable control over molecular weight and <i>Đ</i>. An open-air photo polymerization methodology would be fruitful for applications like photocurable printing, dental, optoelectronics, stereolithography, and protective coatings where simple but rapid photopolymerizations are desirable.</p>\",\"PeriodicalId\":22,\"journal\":{\"name\":\"ACS Omega\",\"volume\":\"9 45\",\"pages\":\"44916–44930 44916–44930\"},\"PeriodicalIF\":3.7000,\"publicationDate\":\"2024-10-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acsomega.4c02773\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Omega\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsomega.4c02773\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Omega","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsomega.4c02773","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Evaluation of the Role of [{Cu(PMDETA)}2(O22–)]2+ in Open-Air Photo ATRP of Methyl Methacrylate
Herein, we report an open-air, photo accelerated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) without employing any deoxygenating agent. Under open-air photo ATRP conditions, oxygen reversibly binds with [{Cu (PMDETA)}2(O22–)]2+(1) to form the required activator, which was demonstrated by simple benchtop oxygen/nitrogen purging experiments. The binding mode of oxygen in (1) (μ(η2-η2) peroxo dicopper(II)) was investigated using UV Visible-NIR, FT-Raman and X-ray photoelectron (XPS) spectroscopic techniques. DFT studies and electrochemical measurements further support the catalytic role of (1) in open-air photo ATRP. With the synergistic involvement of Cu (II)Br2, PMDETA ligand and the intensity of light (365 nm, 4.2 mW cm–2), a well-controlled rapid polymerization of MMA under open-air condition was achieved (1.25< Đ < 1.47, 94% conversion in 200 min). The bromo chain end fidelity was exemplified by chain extension experiment, block copolymerization and MALDI-ToF analysis. Other monomers such as methyl acrylate, glycidyl methacrylate, and benzyl methacrylate were also polymerized under open-air condition with reasonable control over molecular weight and Đ. An open-air photo polymerization methodology would be fruitful for applications like photocurable printing, dental, optoelectronics, stereolithography, and protective coatings where simple but rapid photopolymerizations are desirable.
ACS OmegaChemical Engineering-General Chemical Engineering
CiteScore
6.60
自引率
4.90%
发文量
3945
审稿时长
2.4 months
期刊介绍:
ACS Omega is an open-access global publication for scientific articles that describe new findings in chemistry and interfacing areas of science, without any perceived evaluation of immediate impact.