Synthesis And Properties Of Functional Substituted Polyaniline And Ferrocene-Aniline Derivatives

In this paper, poly(o-toludine)(POT) and poly(o-methoxyaniline)(POMA) micro/nanostructures with controlled morphologies were synthesized by using a new oxidant [(NH4)3[CoMo6O24H6]·7H2O](CoMo6). The properties of polymer products were investigated. The possible oxidized mechanism of CoMo6 was discussed; To further improve the processibility of polyaniline and endow more properties, two new types of aniline derivatives containing two-arm alkylferrocene amide unit have been prepared by N-acylation of N-phenyl-p-phenylenediamine with 1,1’-alkylferrocene and these two compounds as sensors for H2PO4- have been investigated. All main results and conclusions are listed below.1. Uniform poly(o-toludine)(POT) and poly(o-methoxyaniline)(POMA) micro/nanospheres and micro/nanosheets were prepared using CoMo6 as a new oxidant through chemical oxidative polymerization. It was found that the concentration of monomer and oxidant, the reaction temperature and the initial acidity had obvious effects on the final morphology of POT and POMA. When the concentration of monomer and oxidant were relatively low, such as 0.02 M and 4 mM respectively, uniform POT and POMA micro/nanospheres with diameters of about 400-500 nm were synthesizd. When the concentration of monomer increased, POT micro/nanospheres tended to fused together, while the size of POMA micro/nanospheres rised and the uniformity was better than POT micro/nanospheres synthesized using the same monomer concentration; when the concentration of oxidant increased, the micro/nanospheres fused together into block products. Especically, when the initial acidity of reaction synterm incresed to pH ≤ 1, micro/nanosheets with lateral dimensions of about 6 μm were obtained. Besides, when a little surfactant(AOT) was added into the intial reaction systerm, poly(o-toludine) micro/nanorods with square sections were obtained.FT-IR, UV-vis, NMR, Elemental analysis, XRD and TGA reasults showed that the final products(POT and POMA) were doped with CoMo6; the products showed pH-sensitive fluorescencent properties; the fluorescence intensity of POT and POMA doped with CoMo6 decreased with the decrease of pH value from 4.94 to 0.98, and was higher than the POT and POMA prepared without CoMo6 indicating CoMo6 play a important role in enhancing the fluorescene intensity of POT and POMA.2. Two types of new aniline derivatives containing alkylferrocene unit had been prepared by N-acylation of N-phenyl-p-phenylenediamine with 1,1’-alkylferrocene.These two aniline derivatives included 1-methoxycarbony-1’-(N-diphenylamino)-amide-1,1’-bis(1,1-dimethyl-ethy)ferrocene(MCAABEFc) and 1,1’-bis[1-(N-diphenylamino)- amide-1,1-dimethyl-ethy]ferrocene(BAAEFc). The structures and purity of these two compounds were characterized by 1H NMR, 13 C NMR, FT-IR and MS Spectra. The results of TGA showed that the decomposition temperature(T10) of MCAABEFc and BAAEFC was 80℃ and 95℃, higher than N-phenyl-p-phenylenediamine after introduction of alkylferrocene. The compound BAAEFc can sense effectively to H2PO4- anions using flurescent technique. BAAEFc was sensitive to H2PO4- anions than MCAABEFc; The compound BAAEFc and MCAABEFc showed good electrochemical properties and confirmed the complex of BAAEFc and MCAABEFc with H2PO4- anions.