室温下合成导电聚苯胺/对苯二胺共聚物
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摘要
作者在室温下采用一锅法,以盐酸为酸掺杂剂,以过硫酸钾为氧化剂,以十二烷基硫酸钠为乳化剂,合成了聚苯胺/对苯二胺共聚物.与聚苯胺相比,经过优化的共聚物的电导率提高了一个数量级,达到9.5285 s/cm.进一步对有机溶剂种类、表面活性剂种类及用量等因素的研究可知,有机溶剂对电导率的影响小,而适量的表面活性剂对共聚物电导率的提高起着促进作用.通过傅立叶红外光谱(FT-IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)等分析手段对产物的结构和形貌进行表征可以看出,聚合度和聚合形貌是影响聚苯胺/对苯二胺共聚物电导率的重要因素.
A conductive poly( aniline-co-p-phenylenediamine) composite is synthesized by one-pot chemical copolymerization of aniline and p-phenylenediamine using potassium peroxydisulfate as the oxidant and sodium dodecyl sulfate as emulsifier at room temperature. Compared with polyaniline,the conductivity of optimized composite one order of magnitude increases,and the value of conductivity is 9. 5285 s / cm. The further studies on organic solvent, surfactants and their dosage show that the influence of organic solvent on the conductivity is small and proper surfactants play a promoted role in improving conductivity. The structure and morphology are analyzod by Scanning electronic microscope( SEM),Fourier transform infrared( FT-IR),X-ray diffraction spectroscopy( XRD). It indicates that the degree of polymerization and the morphology are of importance to the conductivity of copolymer.
A conductive poly( aniline-co-p-phenylenediamine) composite is synthesized by one-pot chemical copolymerization of aniline and p-phenylenediamine using potassium peroxydisulfate as the oxidant and sodium dodecyl sulfate as emulsifier at room temperature. Compared with polyaniline,the conductivity of optimized composite one order of magnitude increases,and the value of conductivity is 9. 5285 s / cm. The further studies on organic solvent, surfactants and their dosage show that the influence of organic solvent on the conductivity is small and proper surfactants play a promoted role in improving conductivity. The structure and morphology are analyzod by Scanning electronic microscope( SEM),Fourier transform infrared( FT-IR),X-ray diffraction spectroscopy( XRD). It indicates that the degree of polymerization and the morphology are of importance to the conductivity of copolymer.
引文
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[2]ZHANG Z M,WEI Z X,WANG M X.Nanostructures of Polyaniline Doped with Inorganic Acids[J].Macromolecules.2002,35(15):5937-42.
[3]DONG J Q,SHEN Q.Enhancement in Solubility and Conductivity of Polyaniline with Lignosulfonate Modified Carbon Nanotube[J].J.Polym.Sci.Part B:Polym Physics.2009,47(20):2036-2346.
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[15]PROKES J,STEJSKAL J,KRIVKA I,et al.Aniline-Phenylenediamine Copolymers[J].Synthetic Metals.1999,102(1):1205-1206.
[16]RANI M,RAMACHANDRAN R,KABILAN S.A Facile Synthesis and Characterization of Semiconducting p-PhenylenediamineAniline Copolymer[J].Synthetic Metals.2010,160:678-684.
[17]LU F L,WUDL F,NOWAK M,et al.Phenyl-Capped Octaaniline(COA):an Excellent Model for Polyaniline[J].Journal of the American Chemical Society.1986,108(26):8311-8313.
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[20]LOKSHIN N A,PYSHKINA O A,GOLUBEV V B,et al.Intermolecular Electron Transfer in Low-Molecular-Weight Polyaniline Models Associating on Protonation by Amphiphilic Acid in Organic Solvent[J].Macromolecules.2001,34(16):5480-5486.
[21]CHAO L,HO K S,SHEN S Y,et al.Short Polyaniline Nanorod Prepared in the Presence of para-Phenylenediamine[J].Journal of Applied Polymer Scinece.2013,127(3):1853-1862.
[22]CHOSROVIAN H,GREBNER D,RENTSCH S.Size-Dependent Transient Behaviour of Thiophene Oligomers Studied by Picosecond Absorption Spectroscopy[J].Synthetic Metals.1992,52(2):213-225.
[23]张东霞,王云普,曾家豫,等.HRP催化对苯二胺合成苯胺低聚物[J].宝鸡文理学院学报(自然科学版).2006,2(26):109-112.
[24]吐尔逊·阿布都热依木,张校刚.固相法制备纳米级聚对苯二胺和聚邻苯二胺[J].高分子材料科学与工程.2005,1(21):110-112.
[25]秦伟,赵旭,李福绵.芳香族二胺聚合物的合成及其性能[J].高分子学报.1993,4:502-505.
[26]左艳梅.改进化学氧化法合成聚苯胺掺杂态及表征分析[J].工程技术与应用.2011,2(8):27-29.
[27]ZHANG Z M,WAN M X,WEI Y.Highly Crystalline Polyaniline Nanostructures Doped with Dicarboxylic Acids[J].Advanced Functional Materials.2006,16(8):1100-1104.
[2]ZHANG Z M,WEI Z X,WANG M X.Nanostructures of Polyaniline Doped with Inorganic Acids[J].Macromolecules.2002,35(15):5937-42.
[3]DONG J Q,SHEN Q.Enhancement in Solubility and Conductivity of Polyaniline with Lignosulfonate Modified Carbon Nanotube[J].J.Polym.Sci.Part B:Polym Physics.2009,47(20):2036-2346.
[4]JESSICA A M,BLUMA G S.A Facile and Inexpensive Method for The Preparation of Conducting Polyaniline-Clay Composite Nanofibers[J].Synthetic Metals.2012,162(23):2087-94.
[5]LIU L,YANG J,JIANG Y P,et al.The Structure Characteristic and Electrochemical Performance of Graphene/Polyaniline Composites[J].Synthetic Metals.2013,170:57-62.
[6]DOMINGUES S H,SALVATIERRA R V,OLIVEIRA M M,et al.Transparent and Conductive Thin Films of Graphene/Polyaniline Nanocomposites Prepared Through Interfacial Polymerization[J].Chemical Communications.2011,47(9):2592.
[7]CATALDO F.On the Polymerization of p-Phenylenediamine[J].European Polymer Journal.1996,32(1):43-50.
[8]AVADHANI C V,VERNEKAR S P.Synthesis and Characterization of Alternating Copolyimides Containing Aliphatic Spacers[J].Polymer Bulletin.1990,24(5):487-492.
[9]RHEE S B,PARK J W,MOON B S.Synthesis of Alternating Aromatic Copolyimides[J].Macromolecules.1993,26(2):404-406.
[10]TANG H,KITANI A,MAITANI S,et al.Electropolymerization of Aniline Modified by para-Phenylenediamine[J].Electrochimica Acta.1995,40(7):849-857.
[11]TANG C H,WEN T C.Electrochemical Copolymerization of Aniline and para-Phenylenediamine on IrO2 Coated Titanium Electrode[J].Journal of Applied Electrochemistry.1994,24(12):166-178.
[12]孙莉,张汉昌,姜春明,等.苯二胺对聚苯胺电化学合成及其降解的影响.高分子学报.2005,2:219-222.
[13]YAO B,WANG G C,LI X W,et al.Anticorrosive Properties of Epoxy Resin Coatings Cured by Aniline/p-Phenylenediamine Copolymer[J].Journal of Applied Polymer Science.2009,112(4):1988-1993.
[14]李学良,刘庆海,王凯,等.含对苯二胺的聚苯胺制备及其超电容性能[J].电源技术.2012,36(8):1119-1123.
[15]PROKES J,STEJSKAL J,KRIVKA I,et al.Aniline-Phenylenediamine Copolymers[J].Synthetic Metals.1999,102(1):1205-1206.
[16]RANI M,RAMACHANDRAN R,KABILAN S.A Facile Synthesis and Characterization of Semiconducting p-PhenylenediamineAniline Copolymer[J].Synthetic Metals.2010,160:678-684.
[17]LU F L,WUDL F,NOWAK M,et al.Phenyl-Capped Octaaniline(COA):an Excellent Model for Polyaniline[J].Journal of the American Chemical Society.1986,108(26):8311-8313.
[18]SHACKLETTE L W,WOLF J F,GOULD S,et al.Structure and Properties of Polyaniline as Modeled by Single-Crystal Oligomers[J].Journal of Chemical Physics.1988,88(6):3955-3961.
[19]WEI Y,YANG C C,WEI G,et al.A new Synthesis of Aniline Oligomers with Three to Eight Amine Units[J].Synthetic Metals.1997,84:289-291.
[20]LOKSHIN N A,PYSHKINA O A,GOLUBEV V B,et al.Intermolecular Electron Transfer in Low-Molecular-Weight Polyaniline Models Associating on Protonation by Amphiphilic Acid in Organic Solvent[J].Macromolecules.2001,34(16):5480-5486.
[21]CHAO L,HO K S,SHEN S Y,et al.Short Polyaniline Nanorod Prepared in the Presence of para-Phenylenediamine[J].Journal of Applied Polymer Scinece.2013,127(3):1853-1862.
[22]CHOSROVIAN H,GREBNER D,RENTSCH S.Size-Dependent Transient Behaviour of Thiophene Oligomers Studied by Picosecond Absorption Spectroscopy[J].Synthetic Metals.1992,52(2):213-225.
[23]张东霞,王云普,曾家豫,等.HRP催化对苯二胺合成苯胺低聚物[J].宝鸡文理学院学报(自然科学版).2006,2(26):109-112.
[24]吐尔逊·阿布都热依木,张校刚.固相法制备纳米级聚对苯二胺和聚邻苯二胺[J].高分子材料科学与工程.2005,1(21):110-112.
[25]秦伟,赵旭,李福绵.芳香族二胺聚合物的合成及其性能[J].高分子学报.1993,4:502-505.
[26]左艳梅.改进化学氧化法合成聚苯胺掺杂态及表征分析[J].工程技术与应用.2011,2(8):27-29.
[27]ZHANG Z M,WAN M X,WEI Y.Highly Crystalline Polyaniline Nanostructures Doped with Dicarboxylic Acids[J].Advanced Functional Materials.2006,16(8):1100-1104.
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