{"title":"Design of sec-Benzyl Vinyl Ethers toward the Synthesis of Alternating Copolymers Composed of Vinyl Alcohol and Vinyl Ether Units","authors":"Hiroyuki Kubota, and , Makoto Ouchi*, ","doi":"10.1021/acsmacrolett.4c00118","DOIUrl":null,"url":null,"abstract":"<p >In this work, we designed benzyl vinyl ethers carrying alkyl substituents at the benzyl position (i.e., <i>sec</i>-BnVEs) as bulky, reactive, and transformable monomers to realize the alternating cationic copolymerization with an alkyl vinyl ether (VE). In particular, the isopropyl substitution caused not only the bulkiness to suppress the successive propagation but also an enhancement of the vinyl group reactivity to promote crossover propagation with a less bulky VE comonomer. The isopropyl-substituted BnVE (<i>i</i>Pr-BnVE) underwent living cationic alternating copolymerization with <i>n</i>-butyl VE (<i>n</i>BVE), and the alternating propagation was strongly suggested by the reactivity ratios. The subsequent deprotection of the <i>sec</i>-benzyl pendant afforded the vinyl alcohol (VA)–<i>n</i>BVE alternating copolymer, and the corresponding statistical copolymer was also synthesized by using the nonsubstituted monomer (BnVE) instead of <i>i</i>Pr-BnVE. The alternating copolymer exhibited a higher glass transition temperature, which likely stems from the uniform and efficient hydrogen-bonding formation due to the periodic sequence.</p>","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Macro Letters","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsmacrolett.4c00118","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
In this work, we designed benzyl vinyl ethers carrying alkyl substituents at the benzyl position (i.e., sec-BnVEs) as bulky, reactive, and transformable monomers to realize the alternating cationic copolymerization with an alkyl vinyl ether (VE). In particular, the isopropyl substitution caused not only the bulkiness to suppress the successive propagation but also an enhancement of the vinyl group reactivity to promote crossover propagation with a less bulky VE comonomer. The isopropyl-substituted BnVE (iPr-BnVE) underwent living cationic alternating copolymerization with n-butyl VE (nBVE), and the alternating propagation was strongly suggested by the reactivity ratios. The subsequent deprotection of the sec-benzyl pendant afforded the vinyl alcohol (VA)–nBVE alternating copolymer, and the corresponding statistical copolymer was also synthesized by using the nonsubstituted monomer (BnVE) instead of iPr-BnVE. The alternating copolymer exhibited a higher glass transition temperature, which likely stems from the uniform and efficient hydrogen-bonding formation due to the periodic sequence.
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.