Surface-Initiated Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization from Fine Particles Functionalized with Trithiocarbonates

Monodisperse silica particles (SiPs) were surface-modified with a newly designed reversible addition fragmentation chain transfer (RAFT) agent having a triethoxysilane moiety, 6-(triethoxysilyl) 2-(((methylthio)carbonothioyl)thio)-2-phenylacetate (EHT). Surface-initiated RAFT polymerization of styrene was carried out with the EHT-modified SiPs in the presence of a free RAFT agent. The polymerization proceeded in a living manner, producing SiPs coated with well-defined polystyrene of a target molecular weight with a graft density as high as 0.3 chains/nm(2). Similarly, polymerizations of methyl methacrylate (MMA), N-isopropylacrylamide, and n-butyl acrylate were conducted, providing SiPs grafted with concentrated (high-density) polymer brushes. In all examined cases, the hybrid particles were highly dispersible in solvents for graft polymers, without causing any aggregations. Owing to exceptionally high uniformity and perfect dispersibility, these hybrid particles formed two- and three-dimensionally ordered arrays at the air water interface and in suspension, respectively. In addition to the surface-grafting on SiPs, the versatility of this technique was demonstrated by carrying out surface-initiated RAFT polymerization of styrene from iron oxide nanoparticles modified with EHT.