Zhenqing Zhang , Xiaoyu Guo , Xinhui Kou , Na Zhao , Zhibo Li
{"title":"1,8-双(六甲基三氨基磷烯基)萘的质子海绵双磷烯催化的 rac-内酰胺立体选择性开环聚合反应","authors":"Zhenqing Zhang , Xiaoyu Guo , Xinhui Kou , Na Zhao , Zhibo Li","doi":"10.1039/d4py00242c","DOIUrl":null,"url":null,"abstract":"<div><p>Synthesis of highly isotactic polylactide (PLA) <em>via</em> organocatalyzed stereoselective ring-opening polymerization (ROP) of racemic lactide (<em>rac</em>-LA) is a key strategy to improve the physico-chemical properties of PLA. In this context, the proton sponge bisphosphazene 1,8-bis(hexamethyltriaminophosphazenyl)naphthalene (HMPN) was synthesized and applied to catalyze the stereoselective ROP of <em>rac</em>-LA. Semicrystalline PLA with a <em>P</em><sub>m</sub> of 0.75 was conveniently prepared at room temperature. PLAs with higher tacticity (<em>P</em><sub>m</sub> up to 0.93) and higher melting temperature (<em>T</em><sub>m</sub> up to 189 °C) were obtained at lowered temperature. Binary catalysts composed of HMPN and ureas exhibited both high activity (99% monomer conversion within 5 minutes) and high stereoselectivity (<em>P</em><sub>m</sub> up to 0.83) at room temperature. <em>In situ</em> NMR study of HMPN, urea, and BnOH demonstrated the weak interactions between HMPN and BnOH, verifying the kinetic inactivity to deprotonation of HMPN. Kinetic studies verified the controlled manner and chain end control mechanism for the HMPN/U-2 catalyzed ROP of <em>rac</em>-LA.</p></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 21","pages":"Pages 2212-2219"},"PeriodicalIF":3.9000,"publicationDate":"2024-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Stereoselective ring-opening polymerization of rac-lactide catalyzed by the proton sponge bisphosphazene 1,8-bis(hexamethyltriaminophosphazenyl)naphthalene†\",\"authors\":\"Zhenqing Zhang , Xiaoyu Guo , Xinhui Kou , Na Zhao , Zhibo Li\",\"doi\":\"10.1039/d4py00242c\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Synthesis of highly isotactic polylactide (PLA) <em>via</em> organocatalyzed stereoselective ring-opening polymerization (ROP) of racemic lactide (<em>rac</em>-LA) is a key strategy to improve the physico-chemical properties of PLA. In this context, the proton sponge bisphosphazene 1,8-bis(hexamethyltriaminophosphazenyl)naphthalene (HMPN) was synthesized and applied to catalyze the stereoselective ROP of <em>rac</em>-LA. Semicrystalline PLA with a <em>P</em><sub>m</sub> of 0.75 was conveniently prepared at room temperature. PLAs with higher tacticity (<em>P</em><sub>m</sub> up to 0.93) and higher melting temperature (<em>T</em><sub>m</sub> up to 189 °C) were obtained at lowered temperature. Binary catalysts composed of HMPN and ureas exhibited both high activity (99% monomer conversion within 5 minutes) and high stereoselectivity (<em>P</em><sub>m</sub> up to 0.83) at room temperature. <em>In situ</em> NMR study of HMPN, urea, and BnOH demonstrated the weak interactions between HMPN and BnOH, verifying the kinetic inactivity to deprotonation of HMPN. Kinetic studies verified the controlled manner and chain end control mechanism for the HMPN/U-2 catalyzed ROP of <em>rac</em>-LA.</p></div>\",\"PeriodicalId\":100,\"journal\":{\"name\":\"Polymer Chemistry\",\"volume\":\"15 21\",\"pages\":\"Pages 2212-2219\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2024-05-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S1759995424001827\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S1759995424001827","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Stereoselective ring-opening polymerization of rac-lactide catalyzed by the proton sponge bisphosphazene 1,8-bis(hexamethyltriaminophosphazenyl)naphthalene†
Synthesis of highly isotactic polylactide (PLA) via organocatalyzed stereoselective ring-opening polymerization (ROP) of racemic lactide (rac-LA) is a key strategy to improve the physico-chemical properties of PLA. In this context, the proton sponge bisphosphazene 1,8-bis(hexamethyltriaminophosphazenyl)naphthalene (HMPN) was synthesized and applied to catalyze the stereoselective ROP of rac-LA. Semicrystalline PLA with a Pm of 0.75 was conveniently prepared at room temperature. PLAs with higher tacticity (Pm up to 0.93) and higher melting temperature (Tm up to 189 °C) were obtained at lowered temperature. Binary catalysts composed of HMPN and ureas exhibited both high activity (99% monomer conversion within 5 minutes) and high stereoselectivity (Pm up to 0.83) at room temperature. In situ NMR study of HMPN, urea, and BnOH demonstrated the weak interactions between HMPN and BnOH, verifying the kinetic inactivity to deprotonation of HMPN. Kinetic studies verified the controlled manner and chain end control mechanism for the HMPN/U-2 catalyzed ROP of rac-LA.
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