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The temperature-concentration behavior of Solutions of atactic poly(methy1 methacrylate) in 1-butanol and cyclohexanol was investigated. A liquid-liquid demixing interferes with a glass transition. In the high-concentration region, outside the demising region, Tg decreanes with decreasing polymer concentration. For concentrations in the demixing region, a slight increase of TI with decreasing polymer concentration is observed. This is ascribed to the influence of the polymer polydispersity on the concentration of the coexisting phases. The extent of this increase depends strongly on the polydispersity of the polymer and on the nature of the solvent. The combination of these two thermal transitions leads to the formation of amorphous, glassy gels at room temperature. After elimination of the solvent, different morphologies can be obtained. They range from glassy particle dispersions to porous, glassy materials. The morphology can be controlled by overall polymer concentration and cooling rate.

macromolecules

Temperature-concentration behavior of solutions of polydisperse, atactic poly(methyl methacrylate) and its influence on the formation of amorphous, microporous membranes