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The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into the...

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Updated: Jul 2, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Published on: April 22, 2016

Toward living radical polymerization.

Graeme Moad¹, Ezio Rizzardo, San H Thang

¹Commonwealth Scientific and Industrial Research Organisation (CSIRO) Molecular and Health Technologies, Bayview Avenue, Clayton, Victoria 3168, Australia. graeme.moad@csiro.au

Accounts of Chemical Research

|August 15, 2008

Summary

Controlled radical polymerization using nitroxide-mediated polymerization (NMP) and reversible addition-fragmentation chain transfer (RAFT) allows precise control over polymer properties. These methods enable the synthesis of complex polymer architectures with diverse applications.

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3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization

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Area of Science:

Polymer Chemistry
Materials Science
Organic Synthesis

Background:

Radical polymerization is a cornerstone of industrial polymer production due to its versatility and cost-effectiveness.
Conventional radical polymerization offers limited control over polymer molecular weight, composition, and architecture.
The development of controlled radical polymerization techniques is crucial for advanced material design.

Purpose of the Study:

To review and highlight the advancements in controlled radical polymerization, specifically nitroxide-mediated polymerization (NMP) and reversible addition-fragmentation chain transfer (RAFT).
To discuss the mechanisms by which NMP and RAFT achieve living polymerization characteristics.
To showcase the versatility and applications of polymers synthesized via these controlled methods.

Main Methods:

Nitroxide-mediated polymerization (NMP) utilizes reversible deactivation of propagating radicals.
Reversible addition-fragmentation chain transfer (RAFT) employs reversible chain transfer agents to control polymerization.
Guidelines for selecting appropriate RAFT agents for various monomers and reaction conditions are discussed.

Main Results:

NMP, while effective for styrenic and acrylic polymers, is limited to a narrower range of monomers.
RAFT polymerization offers greater versatility, applicable to a majority of monomers, with appropriate RAFT agent selection.
Both NMP and RAFT enable the synthesis of well-defined polymers, including block copolymers and complex architectures like microgels and polymer brushes.

Conclusions:

NMP and RAFT represent significant progress in achieving living characteristics in radical polymerization.
The judicious selection of RAFT agents is key to successful and controlled polymerization for a wide array of monomers.
Polymers synthesized through these controlled methods have broad applications in areas such as biomaterials, coatings, and nanomaterials.