Polymethyl methacrylate/tetrabutyl titanate (PMMA/TBT) organic-inorganic hybrid films with honeycomb patterns were prepared by breath figures method. The casting solutions were prepared by adding directly TBT into the chloroform solutions of polymethyl methacrylate. The prepared PMMA/TBT film was used as precursor film to prepared honeycomb patterned TiO(2) film. The prepared films were characterized by SEM, FTIR and XRD. Effects of PMMA concentration,PMMA/TBT ratio and hydrolysis inhibitor were investigated. It was showed that when the PMMA concentration was too low, the condensed water drop could not be wrapped and stabled by PMMA, on the other hand, when the PMMA concentration was too high, the condensed water drop could not sink into the solution and gathered on the surface, resulting in combination of condensed water drops, the perfect honeycomb patterned films were obtained at the suitable PMMA concentration range from 20 mg/mL to 30 mg/mL. It was also found that the honeycomb patterned structure could not be formed at PMMA/TBT ratio not more than 1 owing to the increase in the hydrophilicity of casting solutions with more TBT. The honeycomb patterned pores were not perforative. The perfection of honeycomb structure could be improved and the diameter of the pores could be decreased by addition of iso-propanol to depress the thorough hydrolysis of TBT, and the suitable iso-propanol concentration was less than 10 mg/mL. It was deduced from FTIR and XRD results that, during the formation of the film, partial hydrolysis of TBT occurred and titanium hydrogen oxide hydrates were formed. These hydrates combined to the ester group of PMMA by covalent or hydrogen band, as a result, the inorganic components were anchored to PMMA. This hybrid film could be used to prepare honeycomb patterned porous TiO(2) films.
