{"title":"Polymer Chain Modification via HAT Chemistry and Its Application in Graft Copolymer Synthesis","authors":"Manish Kumar, Maxime Michelas, Cyrille Boyer","doi":"10.1021/acsmacrolett.5c00068","DOIUrl":null,"url":null,"abstract":"Hydrogen atom transfer (HAT) chemistry has emerged as a powerful tool for selective molecular functionalization, with significant applications in the pharmaceutical and agricultural industries. More recently, HAT has been explored in polymer chemistry as a versatile strategy for introducing targeted functional groups onto polymer chains, enabling precise control over properties such as solubility and mechanical strength. This study investigates the use of HAT to synthesize reversible addition–fragmentation chain transfer (RAFT) agents (or chain transfer agents, CTAs) by modifying various substrates, including toluene, ethyl acetate, and dioxane, in the presence of bis(dodecylsulfanylthiocarbonyl) disulfide or bis(3,5-dimethyl-1<i>H</i>-pyrazol-1-ylthiocarbonyl) disulfide. The resulting CTAs were evaluated in both thermal and photoinduced electron transfer (PET)-RAFT polymerization for controlled polymerization of various monomers. This approach was then extended to functionalize polycaprolactone (PCL) and polyvinyl acetate (PVAc), enabling the synthesis of graft copolymers with various vinyl monomers. To promote HAT, a range of photocatalysts, including iron(III) chloride (FeCl<sub>3</sub>), were investigated, offering advantages over conventional thermal HAT systems. Photocatalysis enables mild and efficient radical generation under light irradiation, providing a cost-effective and environmentally friendly alternative to expensive or toxic metal catalysts.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"216 1","pages":""},"PeriodicalIF":5.1000,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Macro Letters","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acsmacrolett.5c00068","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
Abstract
Hydrogen atom transfer (HAT) chemistry has emerged as a powerful tool for selective molecular functionalization, with significant applications in the pharmaceutical and agricultural industries. More recently, HAT has been explored in polymer chemistry as a versatile strategy for introducing targeted functional groups onto polymer chains, enabling precise control over properties such as solubility and mechanical strength. This study investigates the use of HAT to synthesize reversible addition–fragmentation chain transfer (RAFT) agents (or chain transfer agents, CTAs) by modifying various substrates, including toluene, ethyl acetate, and dioxane, in the presence of bis(dodecylsulfanylthiocarbonyl) disulfide or bis(3,5-dimethyl-1H-pyrazol-1-ylthiocarbonyl) disulfide. The resulting CTAs were evaluated in both thermal and photoinduced electron transfer (PET)-RAFT polymerization for controlled polymerization of various monomers. This approach was then extended to functionalize polycaprolactone (PCL) and polyvinyl acetate (PVAc), enabling the synthesis of graft copolymers with various vinyl monomers. To promote HAT, a range of photocatalysts, including iron(III) chloride (FeCl3), were investigated, offering advantages over conventional thermal HAT systems. Photocatalysis enables mild and efficient radical generation under light irradiation, providing a cost-effective and environmentally friendly alternative to expensive or toxic metal catalysts.
期刊介绍:
ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science.
With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.