Selective Block Copolymerization of Lactide and Methyl Methacrylate with Cationic Indium Catalysts: Exploring the Influence of Noncovalent Ligand Interactions

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-04-22 DOI:10.1021/acscatal.5c00092

Jason Wai-Lok Poon, Yutao Kuang, Nafiseh Moradinik, Chatura Goonesinghe, Salik Hasan Rushdy, Joseph Chang, Takeo Iwase, Maria Ezhova, Savvas G. Hatzikiriakos, Jolene P. Reid, Parisa Mehrkhodavandi

{"title":"Selective Block Copolymerization of Lactide and Methyl Methacrylate with Cationic Indium Catalysts: Exploring the Influence of Noncovalent Ligand Interactions","authors":"Jason Wai-Lok Poon, Yutao Kuang, Nafiseh Moradinik, Chatura Goonesinghe, Salik Hasan Rushdy, Joseph Chang, Takeo Iwase, Maria Ezhova, Savvas G. Hatzikiriakos, Jolene P. Reid, Parisa Mehrkhodavandi","doi":"10.1021/acscatal.5c00092","DOIUrl":null,"url":null,"abstract":"Synthesizing a pure, high molecular weight block copolymer of methyl methacrylate (MMA) and lactide (LA) using a one-pot, sequential addition approach is challenging, as these two monomers are generally polymerized via orthogonal mechanisms. In this work, we report the synthesis of PMMA-<i>b</i>-PLA using a cationic indium complex featuring a hemilabile arm. Extensive efforts were made to confirm block copolymer formation, differentiate it from homopolymer blends, and quantify homopolymer impurities. The copolymers were characterized by Size Exclusion Chromatography, Diffusion Ordered NMR Spectroscopy, Differential Scanning Calorimetry, Thermogravimetric Analysis, and fractional precipitation. Block copolymers with tunable molecular weights were synthesized and rheologically characterized, exhibiting enhanced rheo-mechanical properties over PLA and tunable morphologies based on MMA-to-<i>rac</i>-LA ratios. Computational studies revealed that noncovalent interactions between aromatic substituents in the ligand backbone of the cationic indium complex facilitate MMA polymerization, highlighting a unique strategy for tuning polymerization reactivity through ligand design.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"63 1","pages":""},"PeriodicalIF":11.3000,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.5c00092","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

Abstract

Synthesizing a pure, high molecular weight block copolymer of methyl methacrylate (MMA) and lactide (LA) using a one-pot, sequential addition approach is challenging, as these two monomers are generally polymerized via orthogonal mechanisms. In this work, we report the synthesis of PMMA-b-PLA using a cationic indium complex featuring a hemilabile arm. Extensive efforts were made to confirm block copolymer formation, differentiate it from homopolymer blends, and quantify homopolymer impurities. The copolymers were characterized by Size Exclusion Chromatography, Diffusion Ordered NMR Spectroscopy, Differential Scanning Calorimetry, Thermogravimetric Analysis, and fractional precipitation. Block copolymers with tunable molecular weights were synthesized and rheologically characterized, exhibiting enhanced rheo-mechanical properties over PLA and tunable morphologies based on MMA-to-rac-LA ratios. Computational studies revealed that noncovalent interactions between aromatic substituents in the ligand backbone of the cationic indium complex facilitate MMA polymerization, highlighting a unique strategy for tuning polymerization reactivity through ligand design.

Abstract Image

查看原文本刊更多论文

求助全文

约1分钟内获得全文求助全文

来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.