Swelling behavior of PMMA-g-PEO microgel particles by organic solvents

Aqueous dispersions of cross-linked poly(methylmethacrylate)-g-poly(ethylene oxide) [PMMA-g-PEO] microgel particles have been prepared from mixtures of methylmethacrylate [MMA] and MMA-PEO macromonomer, with ethylene glycol dimethacrylate [EGDM] as the cross-linking monomer (0.2-0.5% wt%). The hydrodynamic radius of these (unswollen) microgel particles ranged from 73 to 85 nm, and the particles were essentially monodisperse with regard to their size distribution. Their swelling behavior has been investigated in the presence of both water-miscible and water-immiscible organic solvents. In general, with the addition of a water-miscible solvent, deswelling behavior was observed. However, the microgel particles were swollen on addition of 1,4-dioxan, which is a good solvent for PMMA. With water-immiscible organic solvents, the extent of swelling depended on the solvency properties of the organic liquid for PMMA. In the presence of benzene, the somewhat large increases in particle size have been attributed to weak flocculation. This has been assumed from an estimate of the van der Waals attraction energy between the swollen microgel particles.