Tailored polymers by free radical processes

Ezio Rizzardo, John Chiefari, Bill Y.K. Chong, Frances Ercole, Julia Krstina, Justine Jeffrey, Tam P.T. Le, Roshan T.A. Mayadunne, Gordon F. Meijs, Catherine L. Moad, Graeme Moad, San H. Thang

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201 Citations (Scopus)


This paper describes a versatile and effective method for the control of free radical polymerization and its use in the preparation of narrow polydispersity polymers of various architectures. Living character is conferred to conventional free radical polymerization by the addition of a thiocarbonylthio compound of general structure S=C(Z)SR, for example, S=C(Ph)SC(CH3)2Ph. The mechanism involves Reversible Addition-Fragmentation chain Transfer and, for convenience of referral, we have designated it the RAFT polymerization. The process is compatible with a very wide range of monomers including functional monomers such as acrylic acid, hydroxyethyl methacrylate, and dimethylaminoethyl methacrylate. Examples of narrow polydispersity (≤1.2) homopolymers, copolymers, gradient copolymers, end-functional polymers, star polymers, A-B diblock and A-B-A triblock copolymers are presented.

Original languageEnglish
Pages (from-to)291-307
Number of pages17
JournalMacromolecular Symposia
Publication statusPublished - 1 Jan 1999

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