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Radical addition–fragmentation chemistry in polymer synthesis
Open accessAbstract
This review traces the development of addition–fragmentation chain transfer agents and related ring-opening monomers highlighting recent innovation in these areas. The major part of this review deals with reagents that give reversible addition–fragmentation chain transfer (RAFT). These reagents include dithioesters, trithiocarbonates, dithiocarbamates and xanthates. The RAFT process is a versatile method for conferring living characteristics on radical polymerizations providing unprecedented control over molecular weight, molecular weight distribution, composition and architecture. It is suitable for most monomers polymerizable by radical polymerization and is robust under a wide range of reaction conditions. It provides a route to functional polymers, cyclopolymers, gradient copolymers, block polymers and star polymers.
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“In these reactions, β-scission of the intermediate radical formed upon radical addition to the sulfur atom of the C=S double bond plays a vital role (Figure 1A).”
From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [2]
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“Thiocarbonyl compounds are fundamentally useful in radical chemistry and are extensively utilized to produce various molecules and macromolecules in reactions such as the Barton–McCombie reaction and reversible addition–fragmentation chain transfer (RAFT) polymerization.1−4”
From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [2]
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Metadata
- Authors
- Moad, G., Rizzardo, E., & Thang, S. H.
- Affiliations
- Commonwealth Scientific and Industrial Research Organisation (AU)
- Corresponding author
- Moad, Graeme
- Rizzardo, Ezio
- Thang, San H.
- Venue
- Polymer
- Publisher
- Elsevier BV
- Published
- 2008-03
- Volume
- 49
- Issue
- 5
- Pages
- 1079-1131
- ISSN
- 0032-3861 (ISSN-L)
- OpenAlex
- W2040062577
- Cited by
- 1,397
- References
- 528
- Citations by year
- 2026: 13 · 2025: 29 · 2024: 41 · 2023: 29 · 2022: 41 · 2021: 71 · 2020: 64 · 2019: 92 · 2018: 76 · 2017: 79 · 2016: 85 · 2015: 93 · 2014: 90 · 2013: 100 · 2012: 117
- FWCI
- 46.82
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- Locations
- Polymer (publishedVersion, cc-by-nc-nd)
- Funders
- Commonwealth Scientific and Industrial Research Organisation
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Photopolymerization techniques and applications
- Keywords
- RAFT polymerization, RAFT agents, dithioesters, trithiocarbonates, dithiocarbamates, xanthates, controlled radical polymerization, block copolymers, star polymers, cyclopolymers, gradient copolymers, molecular weight control
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