{"title":"环酯开环聚合中有效的锡(II)-大引发剂的研制及其在超高分子量聚酯生产中的应用","authors":"Wanich Limwanich, Sawarot Phetsuk, Manita Dumklang, Nathaporn Cheechana, Puttinan Meepowpan, Winita Punyodom","doi":"10.1007/s00289-024-05563-9","DOIUrl":null,"url":null,"abstract":"<div><p>Development of the effective tin(II)-macroinitiators (SnLL and SnCL) was successfully carried out via the ring-opening polymerization (ROP) of <span>l</span>-lactide (LL) and <i>ε-</i>caprolactone (<i>ε</i>-CL) with 4.0 and 8.0 mol% of liquid tin(II) <i>n</i>-butoxide (Sn(O<i>n</i>Bu)<sub>2</sub>) initiator (SnLL4, SnLL8, SnCL4, and SnCL8) at a temperature of 130 °C. The synthesized tin(II)-macroinitiators were completely characterized by various techniques. The performance of the solid SnCL macroinitiators in the ROP of <i>ε</i>-CL was reported for the first time by using the non-isothermal differential scanning calorimetry (DSC) technique. Non-isothermal kinetics results revealed that the rate of <i>ε</i>-CL polymerization depended on the amount of Sn–O active center presented in macroinitiators. The activation energy (<i>E</i><sub><i>a</i></sub>) of the ROP of <i>ε</i>-CL with the prepared SnCL8 was lower than SnCL4. Our synthesized SnLL4 was better than other tin(II)-macroinitiators for small scale production of an ultra-high molecular weight poly(<i>ε</i>-caprolactone) (PCL) with number average molecular weight (<i>M</i><sub>n</sub>) up to 6.3 × 10<sup>5</sup> g/mol and also showed a higher effectiveness than the conventional initiating system of tin(II) octoate (Sn(Oct)<sub>2</sub>) and Sn(Oct)<sub>2</sub>/<i>n</i>-butanol (<i>n</i>BuOH) under a similar synthesis temperature and time. The mechanism of the ROP of <i>ε</i>-CL with our macroinitiators was also studied and proposed through the classic coordination–insertion mechanism. The tin(II)-macroinitiators could be considered as the powerful initiator for the manufacturing of the biodegradable polymers applied for the ecofriendly materials that could support the sustainable management of the plastic waste in the future.</p><h3>Graphical abstract</h3>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":737,"journal":{"name":"Polymer Bulletin","volume":"82 4","pages":"1085 - 1105"},"PeriodicalIF":3.1000,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Development of the effective tin(II)-macroinitiators from the ring-opening polymerization of cyclic esters for utilizing in the production of the ultra-high molecular weight polyester\",\"authors\":\"Wanich Limwanich, Sawarot Phetsuk, Manita Dumklang, Nathaporn Cheechana, Puttinan Meepowpan, Winita Punyodom\",\"doi\":\"10.1007/s00289-024-05563-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Development of the effective tin(II)-macroinitiators (SnLL and SnCL) was successfully carried out via the ring-opening polymerization (ROP) of <span>l</span>-lactide (LL) and <i>ε-</i>caprolactone (<i>ε</i>-CL) with 4.0 and 8.0 mol% of liquid tin(II) <i>n</i>-butoxide (Sn(O<i>n</i>Bu)<sub>2</sub>) initiator (SnLL4, SnLL8, SnCL4, and SnCL8) at a temperature of 130 °C. The synthesized tin(II)-macroinitiators were completely characterized by various techniques. The performance of the solid SnCL macroinitiators in the ROP of <i>ε</i>-CL was reported for the first time by using the non-isothermal differential scanning calorimetry (DSC) technique. Non-isothermal kinetics results revealed that the rate of <i>ε</i>-CL polymerization depended on the amount of Sn–O active center presented in macroinitiators. The activation energy (<i>E</i><sub><i>a</i></sub>) of the ROP of <i>ε</i>-CL with the prepared SnCL8 was lower than SnCL4. Our synthesized SnLL4 was better than other tin(II)-macroinitiators for small scale production of an ultra-high molecular weight poly(<i>ε</i>-caprolactone) (PCL) with number average molecular weight (<i>M</i><sub>n</sub>) up to 6.3 × 10<sup>5</sup> g/mol and also showed a higher effectiveness than the conventional initiating system of tin(II) octoate (Sn(Oct)<sub>2</sub>) and Sn(Oct)<sub>2</sub>/<i>n</i>-butanol (<i>n</i>BuOH) under a similar synthesis temperature and time. The mechanism of the ROP of <i>ε</i>-CL with our macroinitiators was also studied and proposed through the classic coordination–insertion mechanism. The tin(II)-macroinitiators could be considered as the powerful initiator for the manufacturing of the biodegradable polymers applied for the ecofriendly materials that could support the sustainable management of the plastic waste in the future.</p><h3>Graphical abstract</h3>\\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":737,\"journal\":{\"name\":\"Polymer Bulletin\",\"volume\":\"82 4\",\"pages\":\"1085 - 1105\"},\"PeriodicalIF\":3.1000,\"publicationDate\":\"2024-11-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Bulletin\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s00289-024-05563-9\",\"RegionNum\":3,\"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 Bulletin","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s00289-024-05563-9","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Development of the effective tin(II)-macroinitiators from the ring-opening polymerization of cyclic esters for utilizing in the production of the ultra-high molecular weight polyester
Development of the effective tin(II)-macroinitiators (SnLL and SnCL) was successfully carried out via the ring-opening polymerization (ROP) of l-lactide (LL) and ε-caprolactone (ε-CL) with 4.0 and 8.0 mol% of liquid tin(II) n-butoxide (Sn(OnBu)2) initiator (SnLL4, SnLL8, SnCL4, and SnCL8) at a temperature of 130 °C. The synthesized tin(II)-macroinitiators were completely characterized by various techniques. The performance of the solid SnCL macroinitiators in the ROP of ε-CL was reported for the first time by using the non-isothermal differential scanning calorimetry (DSC) technique. Non-isothermal kinetics results revealed that the rate of ε-CL polymerization depended on the amount of Sn–O active center presented in macroinitiators. The activation energy (Ea) of the ROP of ε-CL with the prepared SnCL8 was lower than SnCL4. Our synthesized SnLL4 was better than other tin(II)-macroinitiators for small scale production of an ultra-high molecular weight poly(ε-caprolactone) (PCL) with number average molecular weight (Mn) up to 6.3 × 105 g/mol and also showed a higher effectiveness than the conventional initiating system of tin(II) octoate (Sn(Oct)2) and Sn(Oct)2/n-butanol (nBuOH) under a similar synthesis temperature and time. The mechanism of the ROP of ε-CL with our macroinitiators was also studied and proposed through the classic coordination–insertion mechanism. The tin(II)-macroinitiators could be considered as the powerful initiator for the manufacturing of the biodegradable polymers applied for the ecofriendly materials that could support the sustainable management of the plastic waste in the future.
期刊介绍：
"Polymer Bulletin" is a comprehensive academic journal on polymer science founded in 1988. It was founded under the initiative of the late Mr. Wang Baoren, a famous Chinese chemist and educator. This journal is co-sponsored by the Chinese Chemical Society, the Institute of Chemistry, and the Chinese Academy of Sciences and is supervised by the China Association for Science and Technology. It is a core journal and is publicly distributed at home and abroad.
"Polymer Bulletin" is a monthly magazine with multiple columns, including a project application guide, outlook, review, research papers, highlight reviews, polymer education and teaching, information sharing, interviews, polymer science popularization, etc. The journal is included in the CSCD Chinese Science Citation Database. It serves as the source journal for Chinese scientific and technological paper statistics and the source journal of Peking University's "Overview of Chinese Core Journals."
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