The synthesis of new macro-RAFT agents (Z-C(=S)S-M1-M2-Mn-R) by sequential insertion of monomers (M1, M2, etc.) 'one at a time' into an initial RAFT agent (Z-C(=S)S-R) will be described. The kinetics of the various process steps have been analysed. Critical factors for precision are a high transfer constant for the RAFT agent and a high rate of addition of synthesis he radical (R�) to monomer relative to further propagation. With these conditions satisfied, the rate of reaction is largely determined by the rate of R� adding to monomer. Initiator-derived by-products (Z-C(=S)S-(M)-I) are of particular importance when R� is different from the initiator-derived radical (I�). The scope of the process will be illustrated with recent examples of optoelectronic polymers.Houshyar et al, Polym. Chem., 2012, 3, 1879-1889Chen et al, Org. Biomolecular Chem. 2011, 9, 6111-6119.

RAFT for the control of monomer sequence distribtion

246th National Meeting (2013)

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