微结构可控的聚乙撑二氧噻吩的化学合成及其性能研究
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摘要
通过酸掺杂方法,成功地在水体系中合成出了聚乙撑二氧噻吩,并用傅立叶变换红外光谱证明了产物的分子结构。扫描电子显微镜和透射电子显微镜照片表明,合成的聚乙撑二氧噻吩是由长度约为55nm的短棒聚集而形成的颗粒。研究了掺杂剂,反应温度和氧化剂对乙撑二氧噻吩在水体系下聚合的反应速率的影响。提出了有利于在水体系中合成聚乙撑二氧噻吩的条件。分别以冰乙酸和盐酸为掺杂剂,通过控制掺杂剂的初始浓度,合成了聚乙撑二氧噻吩的薄膜。利用傅立叶变换红外光谱,差示扫描量热法和紫外-可见光吸收光谱分析了薄膜形成的机理。研究发现氢离子的浓度在薄膜形成的过程中起关键作用。提出了以乙撑二氧噻吩单体和氢离子之间的氢键为推动力的自组装成膜机理,以及乙撑二氧噻吩聚合过程中共价键和氢键生长竞争的机理。在自组装成膜的过程中,引入气泡作为模板,成功地合成了聚乙撑二氧噻吩的空心球并用扫描电子显微镜证明了其微观结构。研究了聚乙撑二氧噻吩薄膜与聚乙撑二氧噻吩颗粒的光学性能,电学性能和溶解性能的差异。研究发现氢键自组装法合成的聚乙撑二氧噻吩薄膜的电学性能比聚乙撑二氧噻吩颗粒的更加优秀。其光学吸收具有可调控性能。冰乙酸掺杂制得的聚乙撑二氧噻吩的溶解性有所提高;盐酸掺杂制得的聚乙撑二氧噻吩薄膜的溶解性能虽然有所降低,但生成的膜有很大的比表面积,且无须溶解便可直接使用,有很广泛的应用前景。
Poly(3,4-ethylenedioxythiophene) (PEDOT) was successfully synthesized in aqueous system by an acid doping method. The molecular structures of the products were approved by Fourier Transform Infrared (FTIR) Spectrums. Photographers taken by scanning electron microscope (SEM) and transmission electron microscope revealed that particles of the PEDOT were aggregations of nanorod with length of 55nm. The influences on the PEDOT reaction rates in aqueous system of dopants, temperature and oxidants were discussed. Membranes of PEDOT were synthesized by an acid doping method in which the initial concentration of acetic acid or hydrochloric acid was controlled. The mechanism of the formation of membrane was researched by FTIR, differential scanning calorimeter and ultra-visible spectrum. It was found that the concentration of hydrogen ion plays an important role. A hydrogen bond driven self-assembly process was proposed and a growing competition mechanism between hydrogen bond and covalent bond was found. Hollow spheres of PEDOT were synthesized by inducing bubbles into the self-assemble system and the structures of the spheres were characterized by SEM. The influence on the properties of morphologies of PEDOT was characterized and it was found that self-assemble method can improve the properties of PEDOT. PEDOT membranes have better electric properties and controllable absorption spectrums. The solubility of PEDOT can be improved by doping with acetic acid. When doped with hydrochloric acid, the solubility was reduced, however, PEDOT membranes doped with hydrochloric possess large specific surface area and have promising applications in many fields.
Poly(3,4-ethylenedioxythiophene) (PEDOT) was successfully synthesized in aqueous system by an acid doping method. The molecular structures of the products were approved by Fourier Transform Infrared (FTIR) Spectrums. Photographers taken by scanning electron microscope (SEM) and transmission electron microscope revealed that particles of the PEDOT were aggregations of nanorod with length of 55nm. The influences on the PEDOT reaction rates in aqueous system of dopants, temperature and oxidants were discussed. Membranes of PEDOT were synthesized by an acid doping method in which the initial concentration of acetic acid or hydrochloric acid was controlled. The mechanism of the formation of membrane was researched by FTIR, differential scanning calorimeter and ultra-visible spectrum. It was found that the concentration of hydrogen ion plays an important role. A hydrogen bond driven self-assembly process was proposed and a growing competition mechanism between hydrogen bond and covalent bond was found. Hollow spheres of PEDOT were synthesized by inducing bubbles into the self-assemble system and the structures of the spheres were characterized by SEM. The influence on the properties of morphologies of PEDOT was characterized and it was found that self-assemble method can improve the properties of PEDOT. PEDOT membranes have better electric properties and controllable absorption spectrums. The solubility of PEDOT can be improved by doping with acetic acid. When doped with hydrochloric acid, the solubility was reduced, however, PEDOT membranes doped with hydrochloric possess large specific surface area and have promising applications in many fields.
引文
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[15]钟汉权,刘维锦,聚苯胺导电纤维的研究动态,纺织科学研究,2000,11(2):18~21
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[23]陈雨萍,漆宗能,聚合物分子复合材料研究进展,化学通报,1990,(5):1~8
[24]Vidal J.C., Garcia E., Castillo J.R., In situ preparation of a cholesterol biosensor, Anal. Chim. Acta., 1999, 385(1-3):213~222
[25]Genies E.M., Lapkowiski M., Santier C., et al, Polyaniline spectroelectrochemistry display and battery, Synth. Met., 1987, 18(1-3):631~636
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[27]汪菊英,张兴华,曹有名,导电高分子聚吡咯纳米复合材料的研究进展,塑料,2005,34(6):84~91
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[30]Mattu J., Johansson T., Leach G.W., Third-order nonlinear optical response from polythiophene-based thin films, J. Phys. Chem. C, 2007, 111(18):6868~6874
[31]Dhanabalan A., Van D., Janssen H.M., Synthesis, characterization, and electrooptical properties of a new alternating N-dodecylpyrrole- Benzothiadiaxole copolymer, Macromolecules, 2001, 34(8):2495~2501
[32]Tan Z., Hou J.H., He Y.J., et al, Synthesis and photovoltaic properties of a donor-acceptor double-cable polythiophene with high content of C-60 pendant, Macromolecules, 2007, 40(6):1868~1873
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[35]Wan M.X., Wei Z.X., Zhang Z.M., Studies on nanostructures of conducting polymers via self-assembly method, Synth. Met., 2003, 135-136:175~176
[36]Martin C.R., Nanomaterials: a membrane-based synthetic approach, Science, 1994, 266:1961~1966
[37]Menon V.P., Lei J., Martin C.R., Investigation of molecular and supermolecular structure in template-synthesized polypyrrole tubules and fibrils, Chem. Mater., 1996, 8(9):2382~2390
[38]Wan M.X., Liu J., Qiu H.J., et al, Template-free synthesized microtubules of conducting polymers, Synth. Met., 2001, 119:71~72
[39]Shi G.Q., Li C., Liang Y.Q., High-strength conducting polymers prepared by electrochemical polymerization in boron trifluoride diethyl etherate solution, Adv. Mater., 1999, 11:1145~1146
[40]Velev O.D., Tessier P.M., Lenhoff A.M., Materials a class of porous metallic nanostructures, Nature, 1999, 401:548~548
[41]Long Y.Z., Chen Z.J., Zhang Z.M., et al, Resistivity and magnetic susceptibility of nanotubular polyaniline doped with protonic acids, ACTA Physica Sinica, 2003, 52(1):175~179
[42]Long Y.Z., Chen Z.J., Wang N.L., et al, Resistivity study of polyaniline doped with protonic acids, Physica B, 2003, 325:208~213
[43]Long Y.Z., Zheng P.,Zhang Z.M., et al, Low temperature resistivity of conducting nanotubular polyaniline doped with naphthalenesulfonic acid, ACTA Physica Sinica, 2002, 51(9):2090~2095
[44]Marc D., Jannick D., Roger L., Chemical and electrochemical synthesis of polyaniline micro- and nano-tubules, Synth. Met., 2000, 113:275~280
[45]Yamato H., Ohwa M., Wernet W., et al, Stability of polypyrrole and poly(3,4-ethylenedioxythiophene) for biosensor application, J. Electroanal. Chem., 1995, 397(1-2):163~170
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