{"title":"Green Light-Controlled Switchable Photoiniferter Polymerization","authors":"Meng Zhang, Steven P. Armes, Zesheng An","doi":"10.1021/acs.macromol.4c02489","DOIUrl":null,"url":null,"abstract":"Isoquinoline-based acid/base switchable RAFT agents (SRAs) were synthesized and used as new photoiniferters for visible light-controlled polymerization. In contrast to commercially available pyridyl-substituted SRAs, isoquinoline-based SRAs absorb green light more strongly, exhibit higher p<i>K</i><sub>a</sub> values, and offer higher rates of photolysis. Photoiniferter polymerization was conducted in the presence of either blue or green light at 25 °C. A faster rate of polymerization was observed for syntheses conducted using isoquinoline-based SRAs than using pyridyl-substituted SRAs. Polymers with controlled molecular weights and tunable dispersities were prepared in the presence of varying amounts of 4-toluenesulfonic acid. Four pseudoblock poly(methyl acrylate)s of tunable dispersity were prepared via chain extension experiments. Well-defined diblock copolymers consisting of a more activated monomer (methyl acrylate) and a less activated monomer (<i>N</i>-vinylpyrrolidone) can be prepared with relatively low dispersities.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"123 1","pages":""},"PeriodicalIF":5.1000,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c02489","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
Abstract
Isoquinoline-based acid/base switchable RAFT agents (SRAs) were synthesized and used as new photoiniferters for visible light-controlled polymerization. In contrast to commercially available pyridyl-substituted SRAs, isoquinoline-based SRAs absorb green light more strongly, exhibit higher pKa values, and offer higher rates of photolysis. Photoiniferter polymerization was conducted in the presence of either blue or green light at 25 °C. A faster rate of polymerization was observed for syntheses conducted using isoquinoline-based SRAs than using pyridyl-substituted SRAs. Polymers with controlled molecular weights and tunable dispersities were prepared in the presence of varying amounts of 4-toluenesulfonic acid. Four pseudoblock poly(methyl acrylate)s of tunable dispersity were prepared via chain extension experiments. Well-defined diblock copolymers consisting of a more activated monomer (methyl acrylate) and a less activated monomer (N-vinylpyrrolidone) can be prepared with relatively low dispersities.
期刊介绍：
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.
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