This Perspective summarizes the features and limitations of reversible addition–fragmentation chain transfer (RAFT) polymerization, highlighting its strengths and weaknesses, as our understanding of the process, from both a mechanistic and an application point of view, has matured over the past 20 years. It is aimed at both experts in the field and newcomers, including undergraduate and postgraduate students, as well as nonexperts in polymerization who are interested in developing their own polymeric structures by exploiting the simple setup of a RAFT polymerization.
RAFT is a reversible deactivation radical polymerization (RDRP), also known as living or controlled radical polymerization—a process that mimics closely the feature of living polymerization while benefiting from the versatility of a radical process. RDRP enables the synthesis of polymeric architectures exhibiting predictable molecular weight, low molar mass dispersity (D), high end-group fidelity, and capacity for continued chain growth. The past 20 years have witnessed a rapidly growing interest in RAFT polymerization, initially focusing on the elucidation of the mechanism, then the demonstration of the myriad of polymeric architectures and functional materials that can be obtained from the process, and recently more application-driven reports. Today, with more than 8000 publications, the RAFT process is a widely recognized polymerization technique, and it has been adopted by the wider scientific community, beyond polymer synthesis laboratories, as a tool to generate materials with a broad range of applications from materials science to medicine.
Over 300 reviews have been published on RAFT polymerization, covering mechanistic understanding, polymer synthesis, and the numerous applications of materials obtained by RAFT. With such a vast amount of literature, the RAFT process may appear a daunting topic to newcomers and nonexperts. This Perspective aims at summarizing the system and is designed as both an overview and a tutorial on the RAFT process in order to facilitate its adoption by the wider scientific community. For a detailed account of specific features of RAFT, the reader is referred to the more specialized reviews on the range of materials obtainable by RAFT, in terms of architectures (block, star, branched, hyper-branched, network, stimuli-responsive, and surface-grafted copolymers), nanoparticles and nanocomposites, green and sustainable materials, and bioapplications.
The RAFT mechanism is depicted in Scheme 1. Following activation (step I), the radical species add to the RAFT agent (chain transfer agent, CTA) to enter equilibrium between active and dormant species (steps III and V). The chain transfers steps that form the basis of the RAFT mechanism are degenerate as they involve a reversible transfer of the functional chain end-group (typically a thiocarbonylthio group, Z-C(=S)S-R) between the dormant chains (macroRAFT agent or macroCTA) and the propagating radicals. In an effective process, theThis Perspective summarizes the features and limitations of reversible addition–fragmentation chain transfer (RAFT) polymerization, highlighting its strengths and weaknesses, as our understanding of the process, from both a mechanistic and an application point of view, has matured over the past 20 years. It is aimed at both experts in the field and newcomers, including undergraduate and postgraduate students, as well as nonexperts in polymerization who are interested in developing their own polymeric structures by exploiting the simple setup of a RAFT polymerization.
RAFT is a reversible deactivation radical polymerization (RDRP), also known as living or controlled radical polymerization—a process that mimics closely the feature of living polymerization while benefiting from the versatility of a radical process. RDRP enables the synthesis of polymeric architectures exhibiting predictable molecular weight, low molar mass dispersity (D), high end-group fidelity, and capacity for continued chain growth. The past 20 years have witnessed a rapidly growing interest in RAFT polymerization, initially focusing on the elucidation of the mechanism, then the demonstration of the myriad of polymeric architectures and functional materials that can be obtained from the process, and recently more application-driven reports. Today, with more than 8000 publications, the RAFT process is a widely recognized polymerization technique, and it has been adopted by the wider scientific community, beyond polymer synthesis laboratories, as a tool to generate materials with a broad range of applications from materials science to medicine.
Over 300 reviews have been published on RAFT polymerization, covering mechanistic understanding, polymer synthesis, and the numerous applications of materials obtained by RAFT. With such a vast amount of literature, the RAFT process may appear a daunting topic to newcomers and nonexperts. This Perspective aims at summarizing the system and is designed as both an overview and a tutorial on the RAFT process in order to facilitate its adoption by the wider scientific community. For a detailed account of specific features of RAFT, the reader is referred to the more specialized reviews on the range of materials obtainable by RAFT, in terms of architectures (block, star, branched, hyper-branched, network, stimuli-responsive, and surface-grafted copolymers), nanoparticles and nanocomposites, green and sustainable materials, and bioapplications.
The RAFT mechanism is depicted in Scheme 1. Following activation (step I), the radical species add to the RAFT agent (chain transfer agent, CTA) to enter equilibrium between active and dormant species (steps III and V). The chain transfers steps that form the basis of the RAFT mechanism are degenerate as they involve a reversible transfer of the functional chain end-group (typically a thiocarbonylthio group, Z-C(=S)S-R) between the dormant chains (macroRAFT agent or macroCTA) and the propagating radicals. In an effective process, the