{"title":"ε-己内酯深共晶溶剂无溶剂低温开环聚合及其解聚循环","authors":"Puracheth Rithchumpon , Wanich Limwanich , Kraikrit Utama , Nathaporn Cheechana , Natthapol Akkravijitrkul , Padchanee Sangthong , Winita Punyodom , Puttinan Meepowpan","doi":"10.1016/j.jcat.2025.116400","DOIUrl":null,"url":null,"abstract":"<div><div>The catalytic performance of deep eutectic solvents (DESs) between choline chloride (ChCl) and organic acids was investigated for the ring-opening polymerization (ROP) of <em>ε</em>-caprolactone (CL). These organic acids act as hydrogen bond donors (HBDs), while choline chloride serves as the hydrogen bond acceptor (HBA). Among fifteen acids, (–)-camphorsulfonic acid (CSA), diphenyl phosphate (DPP), 2,5-dimethylbenzenesulfonic acid (DSA), and <em>p</em>-toluenesulfonic acid (PTSA) with ChCl at 100:1:1 M ratio could effectively poly(<em>ε</em>-caprolactone) (PCL) with the molecular weight ranging from 8,000 to 10,000 g/mol and a low dispersity (<em>Ð</em>) (1.2–1.5). The ROP kinetics was powerfully investigated differential scanning calorimetry (DSC) technique. PTSA in combination with ChCl exhibited the fastest reaction and the lowest activation energy (<em>E<sub>a</sub></em>). Additionally, the depolymerization processes of PCL back to its CL monomer was studied by thermogravimetric analysis (TGA). Notably, phosphotungstic acid (PTA) demonstrated the highest depolymerization activity achieving a 100 % yield of CL at 160 °C for 1 h under vacuum distillation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116400"},"PeriodicalIF":6.5000,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Solventless and low-temperature ring-opening polymerization using deep eutectic solvents of ε-caprolactone and their depolymerization cycles for biodegradable polyesters\",\"authors\":\"Puracheth Rithchumpon , Wanich Limwanich , Kraikrit Utama , Nathaporn Cheechana , Natthapol Akkravijitrkul , Padchanee Sangthong , Winita Punyodom , Puttinan Meepowpan\",\"doi\":\"10.1016/j.jcat.2025.116400\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The catalytic performance of deep eutectic solvents (DESs) between choline chloride (ChCl) and organic acids was investigated for the ring-opening polymerization (ROP) of <em>ε</em>-caprolactone (CL). These organic acids act as hydrogen bond donors (HBDs), while choline chloride serves as the hydrogen bond acceptor (HBA). Among fifteen acids, (–)-camphorsulfonic acid (CSA), diphenyl phosphate (DPP), 2,5-dimethylbenzenesulfonic acid (DSA), and <em>p</em>-toluenesulfonic acid (PTSA) with ChCl at 100:1:1 M ratio could effectively poly(<em>ε</em>-caprolactone) (PCL) with the molecular weight ranging from 8,000 to 10,000 g/mol and a low dispersity (<em>Ð</em>) (1.2–1.5). The ROP kinetics was powerfully investigated differential scanning calorimetry (DSC) technique. PTSA in combination with ChCl exhibited the fastest reaction and the lowest activation energy (<em>E<sub>a</sub></em>). Additionally, the depolymerization processes of PCL back to its CL monomer was studied by thermogravimetric analysis (TGA). Notably, phosphotungstic acid (PTA) demonstrated the highest depolymerization activity achieving a 100 % yield of CL at 160 °C for 1 h under vacuum distillation.</div></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":\"451 \",\"pages\":\"Article 116400\"},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2025-08-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S002195172500466X\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S002195172500466X","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Solventless and low-temperature ring-opening polymerization using deep eutectic solvents of ε-caprolactone and their depolymerization cycles for biodegradable polyesters
The catalytic performance of deep eutectic solvents (DESs) between choline chloride (ChCl) and organic acids was investigated for the ring-opening polymerization (ROP) of ε-caprolactone (CL). These organic acids act as hydrogen bond donors (HBDs), while choline chloride serves as the hydrogen bond acceptor (HBA). Among fifteen acids, (–)-camphorsulfonic acid (CSA), diphenyl phosphate (DPP), 2,5-dimethylbenzenesulfonic acid (DSA), and p-toluenesulfonic acid (PTSA) with ChCl at 100:1:1 M ratio could effectively poly(ε-caprolactone) (PCL) with the molecular weight ranging from 8,000 to 10,000 g/mol and a low dispersity (Ð) (1.2–1.5). The ROP kinetics was powerfully investigated differential scanning calorimetry (DSC) technique. PTSA in combination with ChCl exhibited the fastest reaction and the lowest activation energy (Ea). Additionally, the depolymerization processes of PCL back to its CL monomer was studied by thermogravimetric analysis (TGA). Notably, phosphotungstic acid (PTA) demonstrated the highest depolymerization activity achieving a 100 % yield of CL at 160 °C for 1 h under vacuum distillation.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.