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Reversible addition fragmentation chain transfer (RAFT) polymerizations of styrene in fluid CO 2  have been carried out at 80°C and 300 bar using cumyl dithiobenzoate as the controlling agent in the concentration range of 3.5·10 -3  to 2.1·10 -2  mol/L. This is the first report on RAFT polymerization in fluid CO 2 . The polymerization rates were retarded depending on the employed RAFT agent concentration with no significant difference between the RAFT polymerization performed in fluid CO 2  and in toluene. Full chain length distributions were analyzed with respect to peak molecular weights, indicating the successful control of radical polymerization in fluid CO 2 . A characterization of the peak widths may suggest a minor influence of fluid CO 2  on the addition reaction of macroradicals on the dithiobenzoate group.

Reversible addition fragmentation chain transfer (RAFT) polymerization of styrene in fluid CO 2