{"title":"Amino-Triphenolate Cerium (Ⅳ) Complexes for High Molecular Weight PLLA Synthesis and Highly Stereoselective ROP of rac-LA","authors":"Jianxin Sun, Xin Zhao, Luya Cao, Hongzhang Cao, Ji Xian, Xiaobo Pan, Jincai Wu","doi":"10.1016/j.polymer.2025.128291","DOIUrl":null,"url":null,"abstract":"In the industrial production of biodegradable, bio-based, and recyclable polylactic acid (PLA), Sn(Oct)<sub>2</sub> is the most commonly used catalyst for the ring-opening polymerization (ROP) of <em>L</em>-lactide (<em>L</em>-LA). However, its toxicity presents significant limitations, particularly in biomedical applications. Identifying a non-toxic alternative to Sn(Oct)<sub>2</sub> under melting conditions remains a challenge. In this study, we report cerium(IV) complexes with aminotriphenol ligands that exhibit excellent catalytic performances for the ROP of <em>L</em>-LA under both mild and melting conditions. Ultra-high molecular weight PLA (up to 224.00 kg/mol) was obtained at 140°C and high catalytic activity was observed even at low catalyst loading. This is the first report of cerium(IV) complexes exhibiting such high activity, suggesting that they could serve as a viable substitute for Sn(Oct)<sub>2</sub>. Additionally, high heteroselectivity for <em>rac</em>-LA was observed in both solution (<em>P</em><sub><em>r</em></sub> = 0.98) and melting conditions (<em>P</em><sub><em>r</em></sub> = 0.86).","PeriodicalId":405,"journal":{"name":"Polymer","volume":"11 1","pages":""},"PeriodicalIF":4.1000,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1016/j.polymer.2025.128291","RegionNum":2,"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
Abstract
In the industrial production of biodegradable, bio-based, and recyclable polylactic acid (PLA), Sn(Oct)2 is the most commonly used catalyst for the ring-opening polymerization (ROP) of L-lactide (L-LA). However, its toxicity presents significant limitations, particularly in biomedical applications. Identifying a non-toxic alternative to Sn(Oct)2 under melting conditions remains a challenge. In this study, we report cerium(IV) complexes with aminotriphenol ligands that exhibit excellent catalytic performances for the ROP of L-LA under both mild and melting conditions. Ultra-high molecular weight PLA (up to 224.00 kg/mol) was obtained at 140°C and high catalytic activity was observed even at low catalyst loading. This is the first report of cerium(IV) complexes exhibiting such high activity, suggesting that they could serve as a viable substitute for Sn(Oct)2. Additionally, high heteroselectivity for rac-LA was observed in both solution (Pr = 0.98) and melting conditions (Pr = 0.86).
期刊介绍:
Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics.
The main scope is covered but not limited to the following core areas:
Polymer Materials
Nanocomposites and hybrid nanomaterials
Polymer blends, films, fibres, networks and porous materials
Physical Characterization
Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films
Polymer Engineering
Advanced multiscale processing methods
Polymer Synthesis, Modification and Self-assembly
Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization
Technological Applications
Polymers for energy generation and storage
Polymer membranes for separation technology
Polymers for opto- and microelectronics.