Modular Synthesis of Mid-Chain-Functionalized Polymers by Photoinduced Diene- and Styrene-Assisted Radical Coupling Reaction of Polymer-End Radicals

• Published in: Macromolecules Vol. 47; no. 2; pp. 582 - 588
• Main Authors: Nakamura, Yasuyuki, Arima, Takahiro, Yamago, Shigeru
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 28.01.2014
• Subjects: Applied sciences; Exact sciences and technology; Grafting and modifications; Physicochemistry of polymers; Polymers and radiations; Ring opening polymerization; Organic telluride; End group; Lactic acid copolymer; Chain elongation; Methyl methacrylate polymer; Lactone; Photochemical reaction; Dienic compound; Methyl methacrylate copolymer; Thermal stability; Star copolymer; Monodispersed polymer; Initiator polymer; Preparation; Styrene; Reaction mechanism; Sampling; Chemical reactivity; Block copolymer; Isoprene
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma402354m

Photoirradiation of structurally well-defined “living” polymers prepared by organotellurium-mediated living radical polymerization in the presence of dienes or styrenes induced selective polymer-end coupling reaction with the concomitant insertion of the dienes or styrenes with >90% coupling efficiency. The number of inserted dienes or styrenes could be highly controlled to two molecules when acrylic polymers were used. Therefore, various mid-chain-functionalized polymers with well-controlled molecular and macromolecular structure in terms of their molecular weight, molecular weight distribution, functionality, and position were successfully synthesized by employing functionalized dienes or styrenes. The method was applied to the facile synthesis of mid-chain-functionalized telechelic polymers and a 4-miktoarm star polymer with a well-controlled structure.