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  • Perspective
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A comparison of RAFT and ATRP methods for controlled radical polymerization

Nature Reviews Chemistry volume 5, pages 859–869 (2021)Cite this article

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Abstract

Reversible addition–fragmentation chain-transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP) are the two most common controlled radical polymerization methods. Both methods afford functional polymers with a predefined length, composition, dispersity and end group. Further, RAFT and ATRP tame radicals by reversibly converting active polymeric radicals into dormant chains. However, the mechanisms by which the ATRP and RAFT methods control chain growth are distinct, so each method presents unique opportunities and challenges, depending on the desired application. This Perspective compares RAFT and ATRP by identifying their mechanistic strengths and weaknesses, and their latest synthetic applications.

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Fig. 1: Mechanisms of ATRP and RAFT.
Fig. 2: Common monomers and reagents used in RAFT and ATRP.
Fig. 3: Synthesis of complex multiblock copolymers with ATRP and RAFT.
Fig. 4: There are diverse methods to remove or functionalize an end group.

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Acknowledgements

A.A. gratefully acknowledges ETH Zürich for financial support. N.P.T. acknowledges the award of a DECRA Fellowship from the ARC (DE180100076). D.K. acknowledges the National Science Foundation under grant no. DMR-1749730 and the Robert H. and Nancy J. Blayney Professorship.

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Author notes

  1. These authors contributed equally: Nghia P. Truong, Glen R. Jones.

Authors and Affiliations

  1. Laboratory for Polymeric Materials, Department of Materials, ETH Zürich, Zürich, Switzerland

    Nghia P. Truong, Glen R. Jones & Athina Anastasaki

  2. Department of Chemistry and Biochemistry, Miami University, Oxford, OH, USA

    Kate G. E. Bradford & Dominik Konkolewicz

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  1. Nghia P. Truong
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  2. Glen R. Jones
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Contributions

N.P.T., G.R.J., K.G.E.B., D.K. and A.A. co-wrote the manuscript. Key concepts were developed by A.A. and D.K.

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Correspondence to Dominik Konkolewicz or Athina Anastasaki.

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Nature Reviews Chemistry thanks G. Moad, C. Barner-Kowollik and the other, anonymous, reviewers for their contribution to the peer review of this work.

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Truong, N.P., Jones, G.R., Bradford, K.G.E. et al. A comparison of RAFT and ATRP methods for controlled radical polymerization. Nat Rev Chem 5, 859–869 (2021). https://doi.org/10.1038/s41570-021-00328-8

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