Micro-nanostructures Of PPP And PPP/ZnS Composites Fabricated By Self-assembly

In this work, by nonsolvent vapor method, poly(2,5-dialkoxyphenylene)s are used to self-assembly to prepare the various micro-nanostructures, such as porous film, nanowire, crosslinked network, microflower, and microsphere, which can be controlled by the adjustment of the nonsolvent vapor atmosphere, good solvent, and alkoxy side chain length firstly. And then flower-like ZnS, PPP and PPP/ZnS composite microspheres are prepared by poly(2,5-dialkoxyphenylene)s, zinc nitrate and thioacetamide via solvothermal method, respectively.The nonsolvent method is a fast, convenient and repeatable method to self-assembly conjugated polymeric micro-nanostructures. And the process is a process of phase separation induced by nonsolvent. Generally, poly(2,5-dialkoxyphenylene)s with long side chain can self-assembly into porous film, microsphere and crosslinked network structures in the atmospheres of water vapor, alcohol vapor and hexane vapor, respectively. It is difficult for poly(2,5-dialkoxyphenylene)s with shorter side chains to self-assembly polymeric microspheres, because of the rigid backbone.The contact angles of the morphologies obtained from the chlorobenzene solution of poly(2,5-diethyloxy-p-phenylene)s, poly(2,5-dihexoxy-p-phenylene)s and poly(2,5-dioctyloxy-p-phenylene)s and the chloroform solution of poly(2,5-dihexoxy-p-phenylene)s self-assemblied in ethanol vapor atmosphere were 150.5°,153.5°,152.4 ° and 150.1°, respectively, which can be used as the super-hydrophobic polymer materials. When heated at 200℃ after 120 min, poly(2,5-diethyloxy-p-phenylene)s micro-nanostructure from chlorobenzene/ethanol vapor atmosphere can still maintain high hydrophobicity with contact angle of 120° Fluorescence wavelength can be adjusted by the different distortion degree of polymer molecules in different self-assembly conditions. The twisting and shrinking granular structures will lead to blue shift, while the relative stretched film structures lead to red shift.Flower-like ZnS micro-nanostructure exhibits excellent photocatalytic activity with degradation of 98.2% under visible light. The degradation still retains 80.1% after six recycling. The particle sizes of PPP prepared by solvothermal method can be controlled with a range from 1.94 to 5.65 μm. UV absorption wavelengths of PPP flower-like structures prepared by prolonging the reaction time or using chlorobenzene as the solvent, have significant red shifts. When the mass ratios of poly(2,5-dibutoxy-p-phenylene)s and ZnS are 3:1、1:1 and 1:3, and the mass ratios of poly(2,5-dioctyloxy-p-phenylene)s and ZnS are 1:5、1:3 and 3:1, the regular flower-like PPP/ZnS composite micro-nanostructures can be prepared.