蝌蚪型POSS接枝含氟丙烯酸酯类杂化聚合物多孔膜的制备研究

Preparation of Porous Films with Tadpole-shaped POSS-Poly( fluorinated acrylate) s

以本实验室合成的3种结构的蝌蚪型POSS杂化聚甲基丙烯酸三氟乙酯（POSS-PTFEMA）、POSS杂化聚甲基丙烯酸三氟乙酯嵌段共聚聚甲基丙烯酸甲酯（POSS-PMMA-PTFEMA）及POSS杂化聚甲基丙烯酸甲酯嵌段共聚聚甲基丙烯酸三氟乙酯为成膜材质，利用呼吸图案法制备规整结构的蜂窝状聚合物多孔薄膜.利用扫描电镜（SEM）对薄膜表观形貌进行观察，分析了孔形貌的影响因素，并研究了多孔膜的疏水疏油性和耐温性.研究表明，以氯仿为成膜溶剂，3种不同结构的杂化聚合物均可以在较大的浓度范围下（5-30 mg/mL）制备规整的杂化聚合物多孔膜，膜的孔径随聚合物浓度的增大而增大；聚合物POSS-PTFEMA由于化学结构中含有最多的TFEMA结构单元，其规整性最好；相对疏水的硅片也有利于这类疏水的聚合物多孔膜的制备.所形成的多孔膜具有良好的耐温性能和疏水拒油性，其对水接触角介于98°-116°之间，对正十二烷的接触角则介于43°-66°之间.

Well-defined tadpole-shaped hybrid copolymers including POSS-poly（trifluoroethyl acrylate） （POSS-PTFEMA）, POSS-poly（trifluoroethyl acrylate-b-methyl methacrylate） （POSS-PTFEMA-PMMA） and POSS-poly（methyl methacrylate-b-trifluoroethyl acrylate） （POSS-PTFEMA-PMMA） were used as precursors for the formation of well-ordered honeycomb porous films via breath figure method, and the film morphologies were characterized by scanning electron microscope （SEM）. The effects for porous formation including molecular architectures, solvents utilized, solution concentrations and substrates selection were investigated, and the hydrophobic and oleophobic properties along with thermal resistance were also analyzed simultaneously. It was found that all of the three hybrid copolymers were good candidates for honeycomb films and could form highly ordered porous structures under solution concentrations ranging from 5 mg/mL to 30 mg/mL, and the pore sizes increased with the solution concentrations. The regularity of pore structures would also increase with the inducing of TFEMA groups. Compared with dichloromethane, toluene and tetrahydrofuran, chloroform was proven to be the robust solvent to form the well-ordered porous film owing its suitable volatility as well as the solubility for the hybrid copolymer. With the substrate changed from the glass slide to silicon wafer, the average pore sizes decreased, accompanying a reduction of regularity. The obtained films were proven to have well heat-resistance, hydrophobicity and oleophobicity, with contact angles for water in the range of 98°-116° and 43°-66° for dihexyl.