One-stage photoinitiated RAFT dispersion polymerization – Reaction parameters for achieving high particle size uniformity

One-stage photoinitiated RAFT dispersion polymerization (PRDP) has been studied. It was found that the structure of the RAFT agent has a strong influence on the particle morphology. Carboxyl-functionalized trithiocarbonates, including S,S′-bis(α,α′-dimethyl-α″-acetic acid) trithiocarbonate (BDMAT), S-1-dodecyl-S′-(α,α′-dimethyl-α″-acetic acid) trithiocarbonate (DDMAT), S-1-ethyl-S′-(α,α′-dimethyl-α″-acetic acid) trithiocarbonate (EDMAT), were found to be suitable RAFT agents for preparing highly monodisperse microspheres. GPC traces suggested that the polymerization does not follow the typical controlled/living process due to the low RAFT agent concentration in comparison with photoinitiator concentration. Particle size and uniformity changed very little with a wide range of concentrations of the stabilizer and photoinitiator. Highly monodisperse microspheres were obtained even at low stabilizer concentration (5 wt% PVP). Increasing the monomer concentration led to an increase in particle diameter with an exponent of 0.63, which is similar in scale to conventional dispersion polymerization. The microspheres were monodisperse at monomer concentrations ranging from 5 to 15 wt%.