Ryota Tsutsui, Akiyuki Ryoki, Hiroaki Uchiyama and Hiroto Kudo*,
{"title":"由硫烷和氨基甲酸硫酯控制插入反应构建的定义良好的线性和星形多硫化物的合成及其结构/物理性质","authors":"Ryota Tsutsui, Akiyuki Ryoki, Hiroaki Uchiyama and Hiroto Kudo*, ","doi":"10.1021/acs.macromol.5c00653","DOIUrl":null,"url":null,"abstract":"<p >Well-defined linear polysulfides and star-shaped polysulfides were synthesized and characterized. Controlled insertion reaction of phenoxypropylene sulfide (PPS) and S-(4-methoxyphenyl)carbamic acid thioester (PCPOMe) in the presence of tetrabutylammonium chloride (TBAC) in 1-methyl-2-pyrrolidone (NMP) at 60 °C for 20 h afforded corresponding well-defined linear polysulfides poly[PC-(PPS)<sub><i>n</i></sub>-POMe] (<i>n</i> = 10–50) in satisfactory yields. Core-gel type star-shaped polysulfides, <i>star-</i>{poly[PC-(PPS)<sub><i>n</i></sub>-POMe]-PBT(3.0)<sub>core</sub>}, were obtained by the reaction of poly[PC-(PPS)<sub><i>n</i></sub>-POMe] (<i>n</i> = 10, 20, and 30) and 2,2-bis(phenoxypropylene sulfide)propane (PBT). The thermal stability, refractive index, and hydrophobicity of <i>star-</i>{poly[PC-(PPS)<sub><i>n</i></sub>-POMe]-PBT(3.0)<sub>core</sub>} were greater than those of corresponding-arm poly[PC-(PPS)<sub><i>n</i></sub>-POMe]. Small-angle X-ray scattering (SAXS) structure analysis using Berry and Kratky plots showed that the synthesized <i>star-</i>{poly[PC-(PPS)<sub><i>n</i></sub>-POMe]-PBT(3.0)<sub>core</sub>} has 9–16 arms and a radius of gyration (<i>R</i><sub>g</sub>) of 3.3–4.2 nm. Fitting the Kratky plot with a core-gel wormlike star model indicated that the <i>star-</i>{poly[PC-(PPS)<sub><i>n</i></sub>-POMe]-PBT(3.0)<sub>core</sub>} has a maximum core radius of 1.6–2.7 nm.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 15","pages":"8173–8184"},"PeriodicalIF":5.2000,"publicationDate":"2025-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis and Structural/Physical Properties of Well-Defined Linear and Star-Shaped Polysulfides Constructed by Controlled Insertion Reaction of Thiirane and Carbamic Acid Thioester\",\"authors\":\"Ryota Tsutsui, Akiyuki Ryoki, Hiroaki Uchiyama and Hiroto Kudo*, \",\"doi\":\"10.1021/acs.macromol.5c00653\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Well-defined linear polysulfides and star-shaped polysulfides were synthesized and characterized. Controlled insertion reaction of phenoxypropylene sulfide (PPS) and S-(4-methoxyphenyl)carbamic acid thioester (PCPOMe) in the presence of tetrabutylammonium chloride (TBAC) in 1-methyl-2-pyrrolidone (NMP) at 60 °C for 20 h afforded corresponding well-defined linear polysulfides poly[PC-(PPS)<sub><i>n</i></sub>-POMe] (<i>n</i> = 10–50) in satisfactory yields. Core-gel type star-shaped polysulfides, <i>star-</i>{poly[PC-(PPS)<sub><i>n</i></sub>-POMe]-PBT(3.0)<sub>core</sub>}, were obtained by the reaction of poly[PC-(PPS)<sub><i>n</i></sub>-POMe] (<i>n</i> = 10, 20, and 30) and 2,2-bis(phenoxypropylene sulfide)propane (PBT). The thermal stability, refractive index, and hydrophobicity of <i>star-</i>{poly[PC-(PPS)<sub><i>n</i></sub>-POMe]-PBT(3.0)<sub>core</sub>} were greater than those of corresponding-arm poly[PC-(PPS)<sub><i>n</i></sub>-POMe]. Small-angle X-ray scattering (SAXS) structure analysis using Berry and Kratky plots showed that the synthesized <i>star-</i>{poly[PC-(PPS)<sub><i>n</i></sub>-POMe]-PBT(3.0)<sub>core</sub>} has 9–16 arms and a radius of gyration (<i>R</i><sub>g</sub>) of 3.3–4.2 nm. Fitting the Kratky plot with a core-gel wormlike star model indicated that the <i>star-</i>{poly[PC-(PPS)<sub><i>n</i></sub>-POMe]-PBT(3.0)<sub>core</sub>} has a maximum core radius of 1.6–2.7 nm.</p>\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":\"58 15\",\"pages\":\"8173–8184\"},\"PeriodicalIF\":5.2000,\"publicationDate\":\"2025-06-22\",\"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.5c00653\",\"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.5c00653","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Synthesis and Structural/Physical Properties of Well-Defined Linear and Star-Shaped Polysulfides Constructed by Controlled Insertion Reaction of Thiirane and Carbamic Acid Thioester
Well-defined linear polysulfides and star-shaped polysulfides were synthesized and characterized. Controlled insertion reaction of phenoxypropylene sulfide (PPS) and S-(4-methoxyphenyl)carbamic acid thioester (PCPOMe) in the presence of tetrabutylammonium chloride (TBAC) in 1-methyl-2-pyrrolidone (NMP) at 60 °C for 20 h afforded corresponding well-defined linear polysulfides poly[PC-(PPS)n-POMe] (n = 10–50) in satisfactory yields. Core-gel type star-shaped polysulfides, star-{poly[PC-(PPS)n-POMe]-PBT(3.0)core}, were obtained by the reaction of poly[PC-(PPS)n-POMe] (n = 10, 20, and 30) and 2,2-bis(phenoxypropylene sulfide)propane (PBT). The thermal stability, refractive index, and hydrophobicity of star-{poly[PC-(PPS)n-POMe]-PBT(3.0)core} were greater than those of corresponding-arm poly[PC-(PPS)n-POMe]. Small-angle X-ray scattering (SAXS) structure analysis using Berry and Kratky plots showed that the synthesized star-{poly[PC-(PPS)n-POMe]-PBT(3.0)core} has 9–16 arms and a radius of gyration (Rg) of 3.3–4.2 nm. Fitting the Kratky plot with a core-gel wormlike star model indicated that the star-{poly[PC-(PPS)n-POMe]-PBT(3.0)core} has a maximum core radius of 1.6–2.7 nm.
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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