Seigo Watanabe, Yoshino Tsunekawa, Teru Takayama and Kenichi Oyaizu*,
{"title":"高折射率甲硫基取代聚苯硫醚的多种侧链转变","authors":"Seigo Watanabe, Yoshino Tsunekawa, Teru Takayama and Kenichi Oyaizu*, ","doi":"10.1021/acs.macromol.4c00054","DOIUrl":null,"url":null,"abstract":"<p >Sulfur-containing polymers are useful in a wide range of optoelectronic applications, although their transparency and refractive indices are challenging to control precisely. Herein, we present a facile strategy for systematically modulating the optical properties of poly(2-methylthio-1,5-phenylene sulfide) (<b>SMePPS</b>) via post-polymerization modification. Initially, the selective side-chain oxidation of <b>SMePPS</b> yielded methyl sulfoxide-containing poly(phenylene sulfide) (PPS), exhibiting higher Abbe numbers, higher transparency, and ultrahigh refractive indices (<i>n</i><sub>D</sub> = 1.75–1.80). Demethylation of <b>SMePPS</b> also yielded thiol-substituted PPS (<b>SHPPS</b>) with an even higher refractive index (<i>n</i><sub>D</sub> = 1.84), owing to the intermolecular hydrogen bonding and the trace cross-linking effect. Furthermore, the film formability/stability of <b>SHPPS</b> was enhanced through copolymerization with methoxy-substituted PPS without comprising the refractive index properties. This facile post-polymerization modification strategy can achieve desirable tuning of optical properties in various sulfur-containing polymers.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"57 6","pages":"2897–2904"},"PeriodicalIF":5.2000,"publicationDate":"2024-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Diverse Side-Chain Transformation of High Refractive Index Methylthio-Substituted Poly(phenylene sulfide)s\",\"authors\":\"Seigo Watanabe, Yoshino Tsunekawa, Teru Takayama and Kenichi Oyaizu*, \",\"doi\":\"10.1021/acs.macromol.4c00054\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Sulfur-containing polymers are useful in a wide range of optoelectronic applications, although their transparency and refractive indices are challenging to control precisely. Herein, we present a facile strategy for systematically modulating the optical properties of poly(2-methylthio-1,5-phenylene sulfide) (<b>SMePPS</b>) via post-polymerization modification. Initially, the selective side-chain oxidation of <b>SMePPS</b> yielded methyl sulfoxide-containing poly(phenylene sulfide) (PPS), exhibiting higher Abbe numbers, higher transparency, and ultrahigh refractive indices (<i>n</i><sub>D</sub> = 1.75–1.80). Demethylation of <b>SMePPS</b> also yielded thiol-substituted PPS (<b>SHPPS</b>) with an even higher refractive index (<i>n</i><sub>D</sub> = 1.84), owing to the intermolecular hydrogen bonding and the trace cross-linking effect. Furthermore, the film formability/stability of <b>SHPPS</b> was enhanced through copolymerization with methoxy-substituted PPS without comprising the refractive index properties. This facile post-polymerization modification strategy can achieve desirable tuning of optical properties in various sulfur-containing polymers.</p>\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":\"57 6\",\"pages\":\"2897–2904\"},\"PeriodicalIF\":5.2000,\"publicationDate\":\"2024-03-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.macromol.4c00054\",\"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.4c00054","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Diverse Side-Chain Transformation of High Refractive Index Methylthio-Substituted Poly(phenylene sulfide)s
Sulfur-containing polymers are useful in a wide range of optoelectronic applications, although their transparency and refractive indices are challenging to control precisely. Herein, we present a facile strategy for systematically modulating the optical properties of poly(2-methylthio-1,5-phenylene sulfide) (SMePPS) via post-polymerization modification. Initially, the selective side-chain oxidation of SMePPS yielded methyl sulfoxide-containing poly(phenylene sulfide) (PPS), exhibiting higher Abbe numbers, higher transparency, and ultrahigh refractive indices (nD = 1.75–1.80). Demethylation of SMePPS also yielded thiol-substituted PPS (SHPPS) with an even higher refractive index (nD = 1.84), owing to the intermolecular hydrogen bonding and the trace cross-linking effect. Furthermore, the film formability/stability of SHPPS was enhanced through copolymerization with methoxy-substituted PPS without comprising the refractive index properties. This facile post-polymerization modification strategy can achieve desirable tuning of optical properties in various sulfur-containing polymers.
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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