多功能性聚苯胺的制备及其性能研究
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摘要
作为导电高分子材料中最具有发展前景的一种材料,聚苯胺(Polyaniline PANi)因其具有结构多样化、电导率较高、掺杂机制独特、环境稳定性良好、原料廉价易得、合成方法简便等优点一跃成为当今导电高分子研究最有前景的热点之一。聚苯胺微/纳米结构兼具低维材料和有机导体两者的优点,将聚苯胺与磁性材料复合,可以获得多功能复合材料,拓宽聚苯胺应用领域,并且还可以通过调节各组分的组成和结构实现对复合材料电、磁等性能的调控,有望成为一种性能优越的复合功能材料。本文对Fe304磁性纳米粒子的合成及转相改性处理、聚苯胺类流体的合成、Fe304磁性纳米粒子与聚苯胺复合材料的合成以及所制备材料的结构与性能进行了系统研究。
采用高温裂解法合成Fe304纳米粒子,首先制备出油酸铁前驱体,然后利用前驱体在高沸点有机溶剂下的裂解制备Fe304纳米粒子。之后采用降解后的明胶溶液对Fe304纳米粒子进行改性处理,从油溶性转为水溶性。采用TEM观察两种Fe304磁性纳米粒子的形貌。通过XRD测试分析两种Fe304磁性纳米粒子的晶型。利用TG测试两种Fe304磁性纳米粒子的热稳定性和有机含量。FT-IR测试两种Fe304磁性纳米粒子的化学结构。VSM表征两种Fe304磁性纳米粒子的磁性能。
采用壬基酚聚氧乙烯醚硫酸(NPES)在苯胺单体聚合过程中进行掺杂制备聚苯胺类流体。通过流变性能测试表征其模量及粘度随温度变化的关系。采用红外和紫外-可见光谱分析比较本征态聚苯胺和聚苯胺类流体的化学结构。XRD测试分析聚苯胺类流体的结晶形态。TEM谱图观察聚苯胺类流体的微观形貌。TG谱图说明产物的热稳定性。
通过原位聚合制备Fe3O4/PANi复合材料。通过TEM观察Fe304纳米粒子表面PANi的包裹,即Fe3O4/PANi的微观形貌。采用红外和紫外-可见光谱分析比较Fe3O4/PANi复合材料的化学结构。TG分析Fe3O4/PANi热稳定性及有机含量。流变学测试表征其模量及粘度随温度变化的关系。电导率测试表征Fe3O4/PANi复合材料的电性能。
As one of the most promising conductive polymers, Polyaniline (PANi) has various structures, a high conductivity, a unique doping mechanism, excellent physical properties and a good environmental stability. Its monomer is low-cost and easy to get, and the synthetic way is also facile. Because of these advantages, it has become one of the most promising focuses on the research of conductive polymer materials nowadays. PANi has received great attention due to its properties as low-dimension materials and organic conductors. Compounded with magnetic components can gain functional composites and widen the use of PANi. The composites of PANi and magnetic materials can be conductive and magnet. The conductivity and magnetism can be changed through the control of the content of PANi and magnetic materials in composites. In this dissertation, we described detailedly the synthesis of Fe3O4 magnetic nanoparticles, and the approach of transferring hydrophobic nanocrystals into hydrophilic, the preparation of the self-suspended PANi, and the composites of the Fe3O4/PANi, and the structure and properties of the demonstrated materials.
Fe3O4 nanoparticles were synthesized by a high temperature thermal decomposition method. Firstly we synthesized the iron-oleate complex, then the complex was decomposited in the organic solvents with high boiling point. Fe3O4 nanoparticles were modificated by the degraded gelatin solutions and were transferred from hydrophobic nanocrystals into hydrophilic. The morphology was characterized by TEM. And we utilized XRD to analyze the crystallion of the Fe3O4 nanoparticles.TG were used to analysiz the theamal stability and the organic content.The chemical structures were characterized by FT-IR and the saturation magnetization were indicated by VSM.
We applied long-chain nonylphenol ethoxylates (10) sulfuric acid (NPES) as dopants to make polyaniline effectively doped and got a novel slef-suspended polyaniline. Rheological analysis shows the modulus and viscosity vs temperature trace of self-suspended PANi. FT-IR and UV-vis were used to comfirm the chemical structures of eigenstate PANi and self-suspended PANi. XRD demonstrated the crystallion of the self-suspended PANi. TEM specctra revealed the morphology of the self-suspended PANi.TG spectra displayed the thermal stability of the self-suspended PANi.
Fe3O4/PANi composites were synthesized by an in situ polymeration. TEM spectra were used to confirm the Fe3O4 nanoparticles have been embedded in the polyaniline matrix. The chemical structures were characterized by FT-IR and UV-vis.TG exhibit the organic content and thermal stability. Rheological analysis shows the modulus and viscosity vs temperature trace of Fe3O4/PANi composites. The electrical properties were tested by the conductivity of the Fe3O4/PANi composites.
采用高温裂解法合成Fe304纳米粒子,首先制备出油酸铁前驱体,然后利用前驱体在高沸点有机溶剂下的裂解制备Fe304纳米粒子。之后采用降解后的明胶溶液对Fe304纳米粒子进行改性处理,从油溶性转为水溶性。采用TEM观察两种Fe304磁性纳米粒子的形貌。通过XRD测试分析两种Fe304磁性纳米粒子的晶型。利用TG测试两种Fe304磁性纳米粒子的热稳定性和有机含量。FT-IR测试两种Fe304磁性纳米粒子的化学结构。VSM表征两种Fe304磁性纳米粒子的磁性能。
采用壬基酚聚氧乙烯醚硫酸(NPES)在苯胺单体聚合过程中进行掺杂制备聚苯胺类流体。通过流变性能测试表征其模量及粘度随温度变化的关系。采用红外和紫外-可见光谱分析比较本征态聚苯胺和聚苯胺类流体的化学结构。XRD测试分析聚苯胺类流体的结晶形态。TEM谱图观察聚苯胺类流体的微观形貌。TG谱图说明产物的热稳定性。
通过原位聚合制备Fe3O4/PANi复合材料。通过TEM观察Fe304纳米粒子表面PANi的包裹,即Fe3O4/PANi的微观形貌。采用红外和紫外-可见光谱分析比较Fe3O4/PANi复合材料的化学结构。TG分析Fe3O4/PANi热稳定性及有机含量。流变学测试表征其模量及粘度随温度变化的关系。电导率测试表征Fe3O4/PANi复合材料的电性能。
As one of the most promising conductive polymers, Polyaniline (PANi) has various structures, a high conductivity, a unique doping mechanism, excellent physical properties and a good environmental stability. Its monomer is low-cost and easy to get, and the synthetic way is also facile. Because of these advantages, it has become one of the most promising focuses on the research of conductive polymer materials nowadays. PANi has received great attention due to its properties as low-dimension materials and organic conductors. Compounded with magnetic components can gain functional composites and widen the use of PANi. The composites of PANi and magnetic materials can be conductive and magnet. The conductivity and magnetism can be changed through the control of the content of PANi and magnetic materials in composites. In this dissertation, we described detailedly the synthesis of Fe3O4 magnetic nanoparticles, and the approach of transferring hydrophobic nanocrystals into hydrophilic, the preparation of the self-suspended PANi, and the composites of the Fe3O4/PANi, and the structure and properties of the demonstrated materials.
Fe3O4 nanoparticles were synthesized by a high temperature thermal decomposition method. Firstly we synthesized the iron-oleate complex, then the complex was decomposited in the organic solvents with high boiling point. Fe3O4 nanoparticles were modificated by the degraded gelatin solutions and were transferred from hydrophobic nanocrystals into hydrophilic. The morphology was characterized by TEM. And we utilized XRD to analyze the crystallion of the Fe3O4 nanoparticles.TG were used to analysiz the theamal stability and the organic content.The chemical structures were characterized by FT-IR and the saturation magnetization were indicated by VSM.
We applied long-chain nonylphenol ethoxylates (10) sulfuric acid (NPES) as dopants to make polyaniline effectively doped and got a novel slef-suspended polyaniline. Rheological analysis shows the modulus and viscosity vs temperature trace of self-suspended PANi. FT-IR and UV-vis were used to comfirm the chemical structures of eigenstate PANi and self-suspended PANi. XRD demonstrated the crystallion of the self-suspended PANi. TEM specctra revealed the morphology of the self-suspended PANi.TG spectra displayed the thermal stability of the self-suspended PANi.
Fe3O4/PANi composites were synthesized by an in situ polymeration. TEM spectra were used to confirm the Fe3O4 nanoparticles have been embedded in the polyaniline matrix. The chemical structures were characterized by FT-IR and UV-vis.TG exhibit the organic content and thermal stability. Rheological analysis shows the modulus and viscosity vs temperature trace of Fe3O4/PANi composites. The electrical properties were tested by the conductivity of the Fe3O4/PANi composites.
引文
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[3]李永舫.导电聚吡咯的研究.高分子通报,2005,8(4)：51-57.
[4]钟传健,田中群,田昭武.吡咯电化学聚合的现声ESR波谱和Raman光谱研究.中国科学B辑,1989,9(12)：1233-1238.
[5]江建明,戚慰先,仲蕾兰.化学氧化吡咯的结构及导电性的研究.高分子材料科学与工程,1991.7(5)：94-98.
[6]Trivedi D C, Dhawan S K. Synthesis and properties of polyaniline obtained using sulphamic acid. J.Appl.Electro.chem.,1992.22(6):563-570.
[7]Li S L, Macosko C W, H.S.White. Electrochemical Processing of Electrically Conductive Polymer Fibers. Advanced Materials,1993.5(7-8):575-576.
[8]Macdiarmid A G, Chiang J C, Halpern M. et al. "Polyaniline":Interconversion of metallic and insulated forms. Mol.Cryst. Liq.Cryst.,1985.121:173-180.
[9]Macdiarmid A G, Mu S L, Wu W Q, et al. Electrochemical characteristics of "Polyaniline" cathodes and anodes in aqueous electrolytes. Mol.Cryst.Liq.Cryst.,1985.121:187-190.
[10]Macdiarmid A G, Chiang J C, Huang W S, et al. Protonic acid doping to the metallic regime. Mol.Cryst. Liq.Cryst.,1985.125:309-318.
[11]Chiang J C, Macdiarmid A G. "Polyaniline":Protonic acid doping of the emeraldine form to the metall is regime. Synth. Met.,1986.13:192-205.
[12]Macdiarmid A Q, Chiang J C, Richter A F. "Polyaniline":A new concept in conducting polymers. Synth. Met.,1987.18:285-290.
[13]王杨勇,强军锋,井新利等.导电高分子聚苯胺及其应用.化工新型材料,2003.31(3)：1-3.
[14]范俊华,万梅香,朱道本.可溶性导电聚苯胺的研究进展.高分子通报,1997,1：22-28.
[15]陈国华,陈琳.纳米磁性材料及器件的发展与应用.电子元器件应用,2002,4(1-2)：1-3.
[16]Vladimir S Z, Dmitry S F, Igor A P, et al. Physical and chemical properties of magnetite and magnetite-polymer nanoparticles and their colloidal dispersions. Journal of Colloid and Interface Science,1999,212(1):49-57.
[17]Park S J, Kim S, Lee S, et al. Synthesis and magnetic studies of uniform iron nanorods and nanospheres. J. Am. Chem. Soc,2000,122:8581-8582.
[18]Chen Y, Liew K Y, Li J L. Size controlled synthesis of Co nanoparticles by combination of organic solvent and surfactant. Applied Surface Science,2009,255(7):4039-4044.
[19]Neveu S, Bee A, Robineau M, et al. Size-selective chemical synthesis of tartrate stabilized cobalt ferrite ionic magnetic fluid. J. Colloid Interface Sci,2002,255:293-298.
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