Monodisperse highly cross-linked “living” microspheres prepared via photoinitiated RAFT dispersion polymerization

Cross-linked PMMA microspheres have been synthesized by photoinitiated RAFT dispersion polymerization with dipropylene glycol diacrylate (DPGDA) or trimethylolpropane triacrylate (TMPTA) as the cross-linker. Monodisperse microspheres were obtained in the presence of 0.5 wt% S,S′-bis(α,α′-dimethyl-α′′-acetic acid) trithiocarbonate (BDMAT, a RAFT agent) with DPGDA concentration up to 5 wt% or TMPTA concentration up to 2 wt%. The particle formation process was investigated, and the results reveal that the cross-linking reaction was retarded to a certain extent by the RAFT process, which is crucial for the formation of uniform particles under high cross-linker concentrations. The phase diagrams for the methodology have been built up, and show that the procedure could only give polydisperse microspheres at a low DPGDA concentration or coagulum at a high DPGDA concentration in the absence of a RAFT agent, and monodisperse microspheres were obtained at DPGDA concentration up to 5 wt% when the RAFT agent concentration reached an appropriately high level, e.g. 0.5 wt% BDMAT or 0.75 wt% DDMAT. By adjusting the reaction conditions, we have prepared monodisperse cross-linked PMMA microspheres with 10 wt% DPGDA added at the beginning of the reaction. Furthermore, we have functionalized the cross-linked microspheres by adding a functional comonomer to the system at the beginning of polymerization, or by surface-initiated RAFT polymerization via the RAFT groups attached on the particle surface.