{"title":"A Photofunctional Trithiocarbonate RAFT Agent Enabling Ultrafast and Fast Synthesis of Well-defined Telechelic Polymeric Photoinitiators","authors":"Zafer Uyar, Ulku Arslan, Mustafa Degirmenci","doi":"10.1016/j.polymer.2025.128293","DOIUrl":null,"url":null,"abstract":"A versatile and highly active photofunctional RAFT agent based on a trithiocarbonate core, capable of both controlling RAFT polymerization and initiating photopolymerization, was synthesized. The RAFT agent was derived from a bis(dimethylacetic acid) RAFT agent precursor by introducing two photoactive benzoin molecules into its carboxyl groups. This newly developed agent was successfully employed in the RAFT polymerization of acrylonitrile (AN), acrylamide (AM), styrene (St), and methyl methacrylate (MMA) monomers, producing telechelic polymeric photoinitiators with well-defined structures. Notably, the RAFT agent exhibited ultrafast polymerization rates with AN and AM, completing within minutes. While styrene (St) and MMA polymerizations were also rapid, they proceeded at a slower rate compared to AN and AM. Time-dependent <sup>1</sup>H NMR analysis of styrene polymerization showed an initial ultrafast reaction phase followed by a significant slowdown, suggesting the formation of dormant species. The resulting telechelic polymeric photoinitiators were further utilized for photoinduced free radical-promoted cationic polymerization (FRPCP) of cyclohexene oxide (CHO) and butyl vinyl ether (BVE), leading to the formation of ABA-type block copolymers. Comprehensive spectroscopic and analytical techniques confirmed the molecular structures of all synthesized polymers, demonstrating the effectiveness of the RAFT agent in facilitating complex polymer architectures.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"17 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.2025.128293","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
A versatile and highly active photofunctional RAFT agent based on a trithiocarbonate core, capable of both controlling RAFT polymerization and initiating photopolymerization, was synthesized. The RAFT agent was derived from a bis(dimethylacetic acid) RAFT agent precursor by introducing two photoactive benzoin molecules into its carboxyl groups. This newly developed agent was successfully employed in the RAFT polymerization of acrylonitrile (AN), acrylamide (AM), styrene (St), and methyl methacrylate (MMA) monomers, producing telechelic polymeric photoinitiators with well-defined structures. Notably, the RAFT agent exhibited ultrafast polymerization rates with AN and AM, completing within minutes. While styrene (St) and MMA polymerizations were also rapid, they proceeded at a slower rate compared to AN and AM. Time-dependent 1H NMR analysis of styrene polymerization showed an initial ultrafast reaction phase followed by a significant slowdown, suggesting the formation of dormant species. The resulting telechelic polymeric photoinitiators were further utilized for photoinduced free radical-promoted cationic polymerization (FRPCP) of cyclohexene oxide (CHO) and butyl vinyl ether (BVE), leading to the formation of ABA-type block copolymers. Comprehensive spectroscopic and analytical techniques confirmed the molecular structures of all synthesized polymers, demonstrating the effectiveness of the RAFT agent in facilitating complex polymer architectures.
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.