Sulfur-Free Radical RAFT Polymerization of Methacrylates in Homogeneous Solution: Design of exo-Olefin Chain-Transfer Agents (R-CH 2 C(=CH 2 )Z).

In this work, the development of exo-olefin compounds (R-CH 2 C(=CH 2 )Z) as chain-transfer agents for the sulfur-free reversible addition-fragmentation chain transfer (RAFT) radical polymerization of methacrylates in homogeneous solution is described. A series of exo-olefin compounds with a methyl methacrylate (MMA) dimer structure as the R group and a substituted α-methylstyrene unit as the -CH 2 C(=CH 2 )Z (Z: Ph-Y) group were synthesized and used for the radical polymerization of MMA in toluene and PhC(CF 3 ) 2 OH. These compounds underwent transfer of the CH 2 C(=CH 2 )Z group via addition-fragmentation of the propagating methacryloyl radical. More electron-donating (Y) substituents, such as methoxy and dimethylamino groups, produced polymers with narrower molecular weight distributions. A continuous monomer addition method further improved molecular weight control and enabled the synthesis of colorless, sulfur-free, multiblock copolymers of methacrylates in homogeneous solutions.