Spinodal phase separation in semi-interpenetrating polymer networks—polystyrene-cross-polymethacrylate

Morphology control in semi-interpenetrating polymer networks has been achieved by means of a two-step process, separating morphology formation and polymerization/crosslinking. Phase textures formed during spinodal liquid/liquid demixing of a solution of atactic polystyrene in methacrylate monomers were arrested by thermoreversible gelation of the polymer-rich phase as this phase passed its glass transition temperature. The phase separated structure was permanently stabilized by low-temperature crosslinking ultraviolet (UV) polymerization of the methacrylate monomer, and studied by transmission electron microscopy. Thus, it was directly observed how the initial demixing process depended on the initial viscosity of the polymer solution and the mode of quenching. Arrest of the earliest stage of spinodal demixing resulted in separated domains of 0.05–0.08 μm thickness, which were separated by a distance of the spinodal wavelength λ. A cocontinuous network only developed in a relatively late stage of demixing. ©1995 John Wiley & Sons, Inc.