| Macro or nano-patterned structures have shown great potentials in functional materials. As a recent developed process for preparing patterned. materials, the breath figure method holds many advantages including simplicity, high efficiency and low cost. It has been widely used to fabricate materials with regular pores from polymers having various structures. In this paper, porphyrin with four hydroxyl groups was used as the initiator of atom transfer radical polymerization (ATRP). Then star polystyrene and star block copolymer were synthesized and they were used to prepare honeycomb films. The affects of solvent, molecule weight, cast solution composition to honeycomb film were investigated. Our specific studies are concentrated on the following aspects:Tetra(meso-hydroxyphenyl) porphyrin (THPP) was synthesized by Adler-Longo method, which was used as the initiator of ATRP by reacting with 2-bromoisobutyryl bromide. Then star polystyrene with different molecular weights were synthesized. After hydrolysis of the star polystyrene, the molecular weight and its distribution of each arm were determined.2-Hydroxyethyl methacrylate was introduced into star polystyrene by chain extension to prepare star block copolymer. FT-IR,1H NMR, UV, and fluorescence spectroscopy were utilized for the characterization of the polymers.Honeycomb films were fabricated from the resultant star polystyrene and star block copolymer through breath figure method. With chloroform as the solvent, star PS mixed with linear PS formed regular honeycomb film and the influence of solution concentration, molecular weight, proportion of star to linear were studied. With carbon disulfide and chloroform as the solvent, star block copolymer mixed with linear polystyrene formed regular honeycomb film and the influence of solution concentration, molecular weight, proportion of star to linear were also investigated and the optimized condition for honeycomb film preparation was obtained.
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