Progress and Perspectives Beyond Traditional RAFT Polymerization

Abstract

The development of advanced materials based on well-defined polymeric architectures is proving to be a highly prosperous research direction across both industry and academia. Controlled radical polymerization techniques are receiving unprecedented attention, with reversible-deactivation chain growth procedures now routinely leveraged to prepare exquisitely precise polymer products. Reversible addition-fragmentation chain transfer (RAFT) polymerization is a powerful protocol within this domain, where the unique chemistry of thiocarbonylthio (TCT) compounds can be harnessed to control radical chain growth of vinyl polymers. With the intense recent focus on RAFT, new strategies for initiation and external control have emerged that are paving the way for preparing well-defined polymers for demanding applications. In this work, the cutting-edge innovations in RAFT that are opening up this technique to a broader suite of materials researchers are explored. Emerging strategies for activating TCTs are surveyed, which are providing access into traditionally challenging environments for reversible-deactivation radical polymerization. The latest advances and future perspectives in applying RAFT-derived polymers are also shared, with the goal to convey the rich potential of RAFT for an ever-expanding range of high-performance applications.

Biobased Polymers via Radical Homopolymerization and Copolymerization of a Series of Terpenoid-Derived Conjugated Dienes with exo-Methylene and 6-Membered Ring

“…Radical polymerization is one of the most effective and widely used techniques to produce a wide variety of polymeric materials from various vinyl monomers due to the high reactivity of radical species and its robustness toward polar functional groups in the monomer substituents as well as aqueous compounds in the reaction mixture [ 1 ]. In addition, recent progress in controlled/living or reversible deactivation radical polymerization (RDRP) has dramatically expanded the scope of radical polymerization to synthesize precision polymers with various well-defined structures that can be used as high-performance materials [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 ].…”

Initiation of RAFT Polymerization: Electrochemically Initiated RAFT Polymerization in Emulsion (Emulsion eRAFT), and Direct PhotoRAFT Polymerization of Liquid Crystalline Monomers

“…[8] More recent studies have made use of visible irradiation and report fewer, but still not completely defined, byproducts. [10][11][12][13] The recent upsurge in interest in direct photoinitiated RAFT and photoinduced energy or electron transfer (PET)-RAFT [14,15] can largely be linked to the desire to obtain polymers free from initiator-derived by-products (a particular concern in RAFT single-unit monomer insertion (RAFT-SUMI)) [16,17] and in the synthesis of sequence-defined polymers [18,19] and the need for spatial and temporal control over the RAFT process, which is critically important in flow and high-throughput polymer synthesis. [20,21] Electrochemically initiated RAFT polymerization, dubbed eRAFT, has recently attracted attention for similar reasons.…”

Nanoengineering with RAFT polymers: from nanocomposite design to applications

“…23 Since the invention of RAFT polymerization, extensive research efforts were initiated towards developing versatile RAFT agents which are suitable for a great number of monomer sand reaction conditions, including aerobic, biological, or continuous-flow conditions. 23,55,56 Boosted by growing industry demands, the range of reported RAFT agents as well as their commercial availability is rapidly expanding. 23,57,58 Development of the initiation process for RAFT polymerization also has been developed rapidly, amongst others via light, enzymes, electric fields, or ultra-sonication.…”