Hamin Kim, Raita Goseki, Chihiro Homma and Takashi Ishizone*,
{"title":"间乙烯基-1,1-二苯乙烯的自交替聚合和邻乙烯基-1,1-二苯乙烯的环聚合","authors":"Hamin Kim, Raita Goseki, Chihiro Homma and Takashi Ishizone*, ","doi":"10.1021/acs.macromol.5c0025710.1021/acs.macromol.5c00257","DOIUrl":null,"url":null,"abstract":"<p >4-Vinyl-1,1-diphenylethylene (<i><b>p</b></i><b>-VDPE</b>)─an AB-type difunctional monomer containing two reactive C═C bonds─undergoes anionic polymerization via intermolecular crossover propagation on styrene and 1,1-diphenylethylene frameworks in an alternating manner. In this study, the anionic polymerization behavior of the positional isomers of <i><b>p</b></i><b>-VDPE</b>, 3-vinyl-1,1-diphenylethylene (<i><b>m</b></i><b>-VDPE</b>), and 2-vinyl-1,1-diphenylethylene (<i><b>o</b></i><b>-VDPE</b>) was investigated under various conditions in tetrahydrofuran. Their anionic polymerization produced soluble polymers with predictable molecular weights and relatively narrow molecular weight distributions (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> = 1.14–1.44). The polymer of <i><b>m</b></i><b>-VDPE</b> possessed a unique polymeric structure corresponding to the (AB)<sub>n</sub>-type sequence, indicating that the anionic self-alternating polymerization of <i><b>m</b></i>-<b>VDPE</b> proceeded similarly to that of <i><b>p</b></i><b>-VDPE</b>. In contrast, the polymer of <i><b>o</b></i><b>-VDPE</b> had an annular Indane-type main chain with a cyclization efficiency of 68–82%, suggesting that <i><b>o</b></i><b>-VDPE</b> undergoes cyclopolymerization involving an intramolecular cyclization reaction. Thus, the substitution position of the vinyl group in <b>VDPE</b> framework strongly affects the polymerization behavior of the AB-type difunctional monomer.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 9","pages":"4758–4768 4758–4768"},"PeriodicalIF":5.2000,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.macromol.5c00257","citationCount":"0","resultStr":"{\"title\":\"Self-Alternating Polymerization of m-Vinyl-1,1-diphenylethylene and Cyclopolymerization of o-Vinyl-1,1-diphenylethylene\",\"authors\":\"Hamin Kim, Raita Goseki, Chihiro Homma and Takashi Ishizone*, \",\"doi\":\"10.1021/acs.macromol.5c0025710.1021/acs.macromol.5c00257\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >4-Vinyl-1,1-diphenylethylene (<i><b>p</b></i><b>-VDPE</b>)─an AB-type difunctional monomer containing two reactive C═C bonds─undergoes anionic polymerization via intermolecular crossover propagation on styrene and 1,1-diphenylethylene frameworks in an alternating manner. In this study, the anionic polymerization behavior of the positional isomers of <i><b>p</b></i><b>-VDPE</b>, 3-vinyl-1,1-diphenylethylene (<i><b>m</b></i><b>-VDPE</b>), and 2-vinyl-1,1-diphenylethylene (<i><b>o</b></i><b>-VDPE</b>) was investigated under various conditions in tetrahydrofuran. Their anionic polymerization produced soluble polymers with predictable molecular weights and relatively narrow molecular weight distributions (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> = 1.14–1.44). The polymer of <i><b>m</b></i><b>-VDPE</b> possessed a unique polymeric structure corresponding to the (AB)<sub>n</sub>-type sequence, indicating that the anionic self-alternating polymerization of <i><b>m</b></i>-<b>VDPE</b> proceeded similarly to that of <i><b>p</b></i><b>-VDPE</b>. In contrast, the polymer of <i><b>o</b></i><b>-VDPE</b> had an annular Indane-type main chain with a cyclization efficiency of 68–82%, suggesting that <i><b>o</b></i><b>-VDPE</b> undergoes cyclopolymerization involving an intramolecular cyclization reaction. Thus, the substitution position of the vinyl group in <b>VDPE</b> framework strongly affects the polymerization behavior of the AB-type difunctional monomer.</p>\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":\"58 9\",\"pages\":\"4758–4768 4758–4768\"},\"PeriodicalIF\":5.2000,\"publicationDate\":\"2025-04-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.macromol.5c00257\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.macromol.5c00257\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.macromol.5c00257","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Self-Alternating Polymerization of m-Vinyl-1,1-diphenylethylene and Cyclopolymerization of o-Vinyl-1,1-diphenylethylene
4-Vinyl-1,1-diphenylethylene (p-VDPE)─an AB-type difunctional monomer containing two reactive C═C bonds─undergoes anionic polymerization via intermolecular crossover propagation on styrene and 1,1-diphenylethylene frameworks in an alternating manner. In this study, the anionic polymerization behavior of the positional isomers of p-VDPE, 3-vinyl-1,1-diphenylethylene (m-VDPE), and 2-vinyl-1,1-diphenylethylene (o-VDPE) was investigated under various conditions in tetrahydrofuran. Their anionic polymerization produced soluble polymers with predictable molecular weights and relatively narrow molecular weight distributions (Mw/Mn = 1.14–1.44). The polymer of m-VDPE possessed a unique polymeric structure corresponding to the (AB)n-type sequence, indicating that the anionic self-alternating polymerization of m-VDPE proceeded similarly to that of p-VDPE. In contrast, the polymer of o-VDPE had an annular Indane-type main chain with a cyclization efficiency of 68–82%, suggesting that o-VDPE undergoes cyclopolymerization involving an intramolecular cyclization reaction. Thus, the substitution position of the vinyl group in VDPE framework strongly affects the polymerization behavior of the AB-type difunctional monomer.
期刊介绍：
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.
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