Synthesis, Characterization And Properties Of PEG-g-PAn Comb-Shaped Copolymers

In this dissertation, two derivatives of aniline containing polyoxyethylene (PEO) substituent m-phenylene diamino formyl alkylenediamine poly(ethyleneoxy) acetate (MPAE) and poly(ethyleneoxy)-3-aminobenzoate (PEAB) were designed and synthesized. And then, comb-shaped polyaniline grafted by PEO were prepared by chemical oxidation copolymerization. The structure of copolymers were characterized by FTIR, ultraviolet-visible spectrum, elemental analysis and TEM etc.. The optimal process conditions of each derivative were discussed respectively. Main factors for the copolymerization reaction have been investigated. In addition, conductivity of the copolymers complexed with hydrochloric acid and /or LiClO4, solubility of the copolymers and their ability to form membrane were studied in detail. Relationship between the chemical composition, structure and properties of copolymers was investigated as well.The results showed that the yield of copolymer declined from 28% or 37% to nearly zero when the molar feed content of the derivative changed from 10% to 100%. And the inherent viscosity of PEO-grafted polyaniline also decreased. On the other hand, the EO content of copolymer enhanced with increase of MPAE (or PEAB) molar feed content. For the PEO-grafted polyaniline series with different contents of EO units, the benzenoid absorption peaks exhibited blue shifts in comparison with polyaniline, the shifts became greater as the content of EO units increased. Copolymers with, microphase separation were obtained. The structure of PEO phase domains changed from homogeneously dispersed sphere with regular interface to steric continuous network when the EO content reached 52.16%.The copolymers had a better film-forming property and solubility in polarorganic solvents such as N-methyl pyrrolidone (NMP), N, N-dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) etc. than polyaniline. And the solubility of Poly(An-co-PEAB) was superior to that of Poly(An-co-MPAE). While the thermal stability of the copolymers were inferior to polyaniline, and their, thermal decomposition temperature was 300℃ or so. The conductivity of Poly(An-co-PEAB) was higher than that of Poly(An-co-MPAE). The electronic conductivity of the complexes doped with hydrochloric acid were lower than that of doped polyaniline, and declined with increase of the EO content. The relationship between temperature and the ionic conductivity of copolymers complexed with LiClO4 approximately followed the Arrhenius equation. Moreover, the maximum of ionic conductivity at room temperature may be obtained when the molar ratio of [Li+]/[EO] equals to 0.10. The copolymers complexed with hydrochloric acid and LiClO4 showed mixed conductivity between ionic conductivity and electronic conductivity. The mixed conductivity of copolymer whose EO content was 52.16% reached 4.45x10-2S/cm after doping with hydrochloric acid and LiClO4 ([Li+]/[EO]=0.10).