Montira Sriyai, Tawan Chaiwon, Robert Molloy, Patnarin Worajittiphon, Puttinan Meepowpan, Winita Punyodom
求助PDF
{"title":"l-丙交酯与有效液态锡(II)正丁醇引发剂的体积开环聚合:生物医学应用的比较动力学研究","authors":"Montira Sriyai, Tawan Chaiwon, Robert Molloy, Patnarin Worajittiphon, Puttinan Meepowpan, Winita Punyodom","doi":"10.1002/pi.70003","DOIUrl":null,"url":null,"abstract":"<p>In this study, liquid tin(II) <i>n</i>-butoxide (Sn(O<i>n</i>Bu)<sub>2</sub>) is employed as an initiator in the bulk ring-opening polymerization of <span>l</span>-lactide. Its effectiveness is compared with the conventional tin(II) octoate/<i>n</i>-butanol (Sn(Oct)<sub>2</sub>/<i>n</i>-BuOH) initiating system by analyzing kinetics parameters derived from monomer conversion data obtained through gravimetry, <sup>1</sup>H NMR spectroscopy and Fourier transform infrared (FTIR) spectroscopy. Gravimetry kinetics studies of <span>l</span>-lactide ring-opening polymerization in bulk at 120 °C for 24 h reveal that both Sn(O<i>n</i>Bu)<sub>2</sub> and Sn(Oct)<sub>2</sub>/<i>n</i>-BuOH achieve high conversions (>90%), with first-order rate constants of 0.0432 and 0.0157 min<sup>−1</sup>, respectively. These results indicate that the highly soluble liquid Sn(O<i>n</i>Bu)<sub>2</sub> leads to a faster polymerization rate and higher molecular weight (<i>M</i><sub>n</sub> = 1.45 × 10<sup>4</sup> g mol<sup>−1</sup>) than Sn(Oct)<sub>2</sub>/<i>n</i>-BuOH (<i>M</i><sub>n</sub> = 6.03 × 10<sup>3</sup> g mol<sup>−1</sup>). However, kinetics studies using <sup>1</sup>H NMR and FTIR suggest that liquid Sn(O<i>n</i>Bu)<sub>2</sub> and Sn(Oct)<sub>2</sub>/<i>n</i>-BuOH exhibit similar effectiveness in terms of monomer conversion. Finally, the high efficiency of liquid Sn(O<i>n</i>Bu)<sub>2</sub> is demonstrated in the first-time synthesis of medical-grade poly(<span>l</span>-lactide) at a large scale (500 g). This advancement paves the way for biomedical applications, such as absorbable surgical sutures, demonstrating performance comparable to commercial medical-grade poly(<span>l</span>-lactide) products. © 2025 Society of Chemical Industry.</p>","PeriodicalId":20404,"journal":{"name":"Polymer International","volume":"74 11","pages":"990-1002"},"PeriodicalIF":3.6000,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Bulk ring-opening polymerization of l-lactide with an effective liquid tin(II) n-butoxide initiator for biomedical applications: a comparative kinetics study\",\"authors\":\"Montira Sriyai, Tawan Chaiwon, Robert Molloy, Patnarin Worajittiphon, Puttinan Meepowpan, Winita Punyodom\",\"doi\":\"10.1002/pi.70003\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>In this study, liquid tin(II) <i>n</i>-butoxide (Sn(O<i>n</i>Bu)<sub>2</sub>) is employed as an initiator in the bulk ring-opening polymerization of <span>l</span>-lactide. Its effectiveness is compared with the conventional tin(II) octoate/<i>n</i>-butanol (Sn(Oct)<sub>2</sub>/<i>n</i>-BuOH) initiating system by analyzing kinetics parameters derived from monomer conversion data obtained through gravimetry, <sup>1</sup>H NMR spectroscopy and Fourier transform infrared (FTIR) spectroscopy. Gravimetry kinetics studies of <span>l</span>-lactide ring-opening polymerization in bulk at 120 °C for 24 h reveal that both Sn(O<i>n</i>Bu)<sub>2</sub> and Sn(Oct)<sub>2</sub>/<i>n</i>-BuOH achieve high conversions (>90%), with first-order rate constants of 0.0432 and 0.0157 min<sup>−1</sup>, respectively. These results indicate that the highly soluble liquid Sn(O<i>n</i>Bu)<sub>2</sub> leads to a faster polymerization rate and higher molecular weight (<i>M</i><sub>n</sub> = 1.45 × 10<sup>4</sup> g mol<sup>−1</sup>) than Sn(Oct)<sub>2</sub>/<i>n</i>-BuOH (<i>M</i><sub>n</sub> = 6.03 × 10<sup>3</sup> g mol<sup>−1</sup>). However, kinetics studies using <sup>1</sup>H NMR and FTIR suggest that liquid Sn(O<i>n</i>Bu)<sub>2</sub> and Sn(Oct)<sub>2</sub>/<i>n</i>-BuOH exhibit similar effectiveness in terms of monomer conversion. Finally, the high efficiency of liquid Sn(O<i>n</i>Bu)<sub>2</sub> is demonstrated in the first-time synthesis of medical-grade poly(<span>l</span>-lactide) at a large scale (500 g). This advancement paves the way for biomedical applications, such as absorbable surgical sutures, demonstrating performance comparable to commercial medical-grade poly(<span>l</span>-lactide) products. © 2025 Society of Chemical Industry.</p>\",\"PeriodicalId\":20404,\"journal\":{\"name\":\"Polymer International\",\"volume\":\"74 11\",\"pages\":\"990-1002\"},\"PeriodicalIF\":3.6000,\"publicationDate\":\"2025-07-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer International\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://scijournals.onlinelibrary.wiley.com/doi/10.1002/pi.70003\",\"RegionNum\":4,\"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 International","FirstCategoryId":"92","ListUrlMain":"https://scijournals.onlinelibrary.wiley.com/doi/10.1002/pi.70003","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
引用
批量引用