文献类型：期刊文献

英文题名：Photoinduced inverse vulcanization

作者：Jia, Jinhong[1];Liu, Jingjiang[1];Wang, Zhi-Qiang[2];Liu, Tao[3,4];Yan, Peiyao[4];Gong, Xue-Qing[2];Zhao, Chengxi[2,3,4];Chen, Linjiang[2,3,4,5];Miao, Congcong[1];Zhao, Wei[3,4];Cai, Shanshan (Diana)[4];Wang, Xi-Cun[1];Cooper, Andrew, I[2,3,4];Wu, Xiaofeng[1,2,3,4];Hasell, Tom[1,4];Quan, Zheng-Jun[1]

机构：[1]Northwest Normal Univ, Coll Chem & Chem Engn, Gansu Int Sci & Technol Cooperat Base Water Reten, Lanzhou, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Res Ctr, Sch Chem & Mol Engn, Key Lab Adv Mat & Joint Int Res Lab Precis Chem &, Shanghai, Peoples R China;[3]Univ Liverpool, Leverhulme Res Ctr Funct Mat Design, Mat Innovat Factory, Liverpool, Merseyside, England;[4]Univ Liverpool, Dept Chem, Liverpool, Merseyside, England;[5]Univ Birmingham, Sch Chem, Birmingham, W Midlands, England

年份：2022

卷号：14

期号：11

起止页码：1249

外文期刊名：NATURE CHEMISTRY

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000874408300007)】；

基金：The authors acknowledge funding from the National Nature Science Foundation of China (numbers 22061038, 21825301), the Key Talent Projects of Gansu Province [2019]39, the Nature Science Foundation of Gansu Province (number 20YF3GA032), the National Key R&D Program of China (number 2018YFA0208602), the Shanghai Municipal Science and Technology Major Project (number 2018SHZDX03), the Programme of Introducing Talents of Discipline to Universities (number B16017), the Shanghai Science and Technology Committee (number 175207750100) and the China Postdoctoral Science Foundation (number 2020M673640XB, 2020M671020), the Natural Science Foundation of Gansu Province (20YF3GA023) and Engineering and Physical Sciences Research Council (EPSRC) (EP/v026887/1). P.Y., C.Z. and S.C. thank the China Scholarship Council (CSC) for awarding their PhD scholarships. T.H. was supported by a Royal Society University Research Fellowship. L.C., W.Z., A.I.C. and X.W. acknowledge the Leverhulme Trust via the Leverhulme Research Centre for Functional Materials Design for funding. We thank the Materials Innovation Factory (MIF) team members for their support in operating instruments. We also thank X. Zhu for his contribution to discussion and design of the figures, and D. Lester for GPC measurement.

语种：英文

摘要：The inverse vulcanization (IV) of elemental sulfur to generate sulfur-rich functional polymers has attracted much recent attention. However, the harsh reaction conditions required, even with metal catalysts, constrains the range of feasible crosslinkers. We report here a photoinduced IV that enables reaction at ambient temperatures, greatly broadening the scope for both substrates and products. These conditions enable volatile and gaseous alkenes and alkynes to be used in IV, leading to sustainable alternatives for environmentally harmful plastics that were hitherto inaccessible. Density functional theory calculations reveal different energy barriers for thermal, catalytic and photoinduced IV processes. This protocol circumvents the long curing times that are common in IV, generates no H2S by-products, and produces high-molecular-weight polymers (up to 460,000 g mol(-1)) with almost 100% atom economy. This photoinduced IV strategy advances both the fundamental chemistry of IV and its potential industrial application to generate materials from waste feedstocks.