Stabilized Polymer Microparticles by Precipitation with a Compressed Fluid Antisolvent. 1. Poly(fluoro acrylates)

Poly(1,1-dihydroperfluorooctyl acrylate) (poly(FOA)) based stabilizers greatly reduce, and in some cases eliminate, flocculation of amorphous poly(methyl methacrylate) (PMMA) and polystyrene (PS) microparticles formed by precipitation into liquid CO2 at 23 °C. The microparticle stabilization mechanism is explained in terms of the stabilizer−CO2 phase behavior, the spray characteristics, and the interfacial activity of the stabilizer. Compared with the homopolymer poly(FOA), the diblock copolymer PS-b-poly(FOA) produces smaller and more spherical primary particles (0.1−0.3 μm) and also prevents flocculation at lower stabilizer concentrations. These differences are due to the greater interfacial activity of PS-b-poly(FOA). Steric stabilization commences in the jet on the order of several tenths of milliseconds and continues for seconds throughout the precipitator. With the use of a coaxial nozzle, precipitation is delayed and the stabilizers become even more effective at preventing flocculation.