Preparation of porous membrane by combined use of thermally induced phase separation and immersion precipitation

By immersion in the cooled nonsolvent, PMMA porous membrane was prepared by the combined use of thermally induced phase separation (TIPS) and immersion precipitation. As nonsolvent, water with low mutual affinity with cyclohexanol (diluent) and methanol with high affinity were used. In the case of water, the porous structure was formed by TIPS immediately after the immersion. Near the top surface contacted with the nonsolvent, the thin skin layer was formed due to the outflow of the diluent. After the long immersion period, macrovoids were formed near the top surface due to the penetration of the nonsolvent. Thus, TIPS and the immersion precipitation occurred serially. On the contrary, TIPS and the immersion precipitation occurred simultaneously in the case of methanol because the inflow of methanol was fast. Therefore, the membrane obtained after the short immersion period had the larger pores near the top surface due to the nonsolvent induced phase separation and the smaller pores near the bottom surface due to TIPS. These two modes of the phase separations were confirmed by the changes in light transmittance through the polymer solutions.