{"title":"通过 Ylide 功能化膦基受挫路易斯对精确获取超高分子量聚合物","authors":"Yun Bai, Shiquan Li, Jianghua He, Changfei He, Yibao Li, Zhonggao Zhou, Yiwang Chen, Yuetao Zhang","doi":"10.1021/acs.macromol.4c01801","DOIUrl":null,"url":null,"abstract":"Lewis pair polymerization (LPP) is an advanced polymerization technique known for its ability to synthesize ultrahigh-molecular-weight (UHMW) polymers under mild conditions with remarkable efficiency and precise control. In this study, a strong electron-donor ylide-functionalized phosphine, (1-(diethylphosphanyl)ethylidene)triphenyl-λ<sup>5</sup>-phosphane (<b>YFP2</b>), is introduced as a Lewis base (LB). It is combined with a sterically hindered moderately acidic Lewis acid (LA), (4-Me-2,6-<i><sup>t</sup></i>Bu<sub>2</sub>-C<sub>6</sub>H<sub>2</sub>O)Al<i><sup>i</sup></i>Bu<sub>2</sub> ((BHT)Al<i><sup>i</sup></i>Bu<sub>2</sub>), to prepare a frustrated Lewis pair (FLP) catalyst for the living methacrylates polymerization. The living character of this polymerization has been confirmed through various key observations: successful chain-extension experiments, a linear increase in the number-average molecular weight (<i>M</i><sub>n</sub>) of the polymer corresponding to monomer conversion and the ratio of monomer to initiator, and the development of distinct di- and triblock copolymers using different comonomer addition sequences. Importantly, this FLP catalyst system has successfully synthesized UHMW poly(methyl methacrylate) (PMMA) with <i>M</i><sub>n</sub> values reaching up to 2935 kg/mol and narrow molecular weight distribution (<i>Đ</i>) at room temperature (RT). This achievement establishes a new record for the highest reported <i>M</i><sub>n</sub> for PMMA using a living/controlled LPP system.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"292 1","pages":""},"PeriodicalIF":5.1000,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Precise Access to Ultrahigh-Molecular-Weight Polymers by Ylide-Functionalized Phosphine-Based Frustrated Lewis Pairs\",\"authors\":\"Yun Bai, Shiquan Li, Jianghua He, Changfei He, Yibao Li, Zhonggao Zhou, Yiwang Chen, Yuetao Zhang\",\"doi\":\"10.1021/acs.macromol.4c01801\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Lewis pair polymerization (LPP) is an advanced polymerization technique known for its ability to synthesize ultrahigh-molecular-weight (UHMW) polymers under mild conditions with remarkable efficiency and precise control. In this study, a strong electron-donor ylide-functionalized phosphine, (1-(diethylphosphanyl)ethylidene)triphenyl-λ<sup>5</sup>-phosphane (<b>YFP2</b>), is introduced as a Lewis base (LB). It is combined with a sterically hindered moderately acidic Lewis acid (LA), (4-Me-2,6-<i><sup>t</sup></i>Bu<sub>2</sub>-C<sub>6</sub>H<sub>2</sub>O)Al<i><sup>i</sup></i>Bu<sub>2</sub> ((BHT)Al<i><sup>i</sup></i>Bu<sub>2</sub>), to prepare a frustrated Lewis pair (FLP) catalyst for the living methacrylates polymerization. The living character of this polymerization has been confirmed through various key observations: successful chain-extension experiments, a linear increase in the number-average molecular weight (<i>M</i><sub>n</sub>) of the polymer corresponding to monomer conversion and the ratio of monomer to initiator, and the development of distinct di- and triblock copolymers using different comonomer addition sequences. Importantly, this FLP catalyst system has successfully synthesized UHMW poly(methyl methacrylate) (PMMA) with <i>M</i><sub>n</sub> values reaching up to 2935 kg/mol and narrow molecular weight distribution (<i>Đ</i>) at room temperature (RT). This achievement establishes a new record for the highest reported <i>M</i><sub>n</sub> for PMMA using a living/controlled LPP system.\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":\"292 1\",\"pages\":\"\"},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2024-11-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.macromol.4c01801\",\"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://doi.org/10.1021/acs.macromol.4c01801","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Precise Access to Ultrahigh-Molecular-Weight Polymers by Ylide-Functionalized Phosphine-Based Frustrated Lewis Pairs
Lewis pair polymerization (LPP) is an advanced polymerization technique known for its ability to synthesize ultrahigh-molecular-weight (UHMW) polymers under mild conditions with remarkable efficiency and precise control. In this study, a strong electron-donor ylide-functionalized phosphine, (1-(diethylphosphanyl)ethylidene)triphenyl-λ5-phosphane (YFP2), is introduced as a Lewis base (LB). It is combined with a sterically hindered moderately acidic Lewis acid (LA), (4-Me-2,6-tBu2-C6H2O)AliBu2 ((BHT)AliBu2), to prepare a frustrated Lewis pair (FLP) catalyst for the living methacrylates polymerization. The living character of this polymerization has been confirmed through various key observations: successful chain-extension experiments, a linear increase in the number-average molecular weight (Mn) of the polymer corresponding to monomer conversion and the ratio of monomer to initiator, and the development of distinct di- and triblock copolymers using different comonomer addition sequences. Importantly, this FLP catalyst system has successfully synthesized UHMW poly(methyl methacrylate) (PMMA) with Mn values reaching up to 2935 kg/mol and narrow molecular weight distribution (Đ) at room temperature (RT). This achievement establishes a new record for the highest reported Mn for PMMA using a living/controlled LPP system.
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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