聚苯胺及其衍生物的制备与湿敏性能研究
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摘要
本论文首先以苯胺和氯乙醇为基材制备出N-羟乙基苯胺，再以苯胺和N-羟乙基苯胺为材料，过硫酸铵为氧化剂用化学法合成出导电聚合物，并使用扫描电镜（SEM）、红外图谱XRD、X-射线衍射法即XRD（X-ray diffraction）透射电镜TEM等分析手段分别对制备产品进行了研究和表征，并通过电化学工作站测试其阻抗，对阻抗图谱进行分析，重点对合成出的导电聚合物湿敏性和导电性进行了分析、研究和比较。
分别以盐酸和高氯酸作为掺杂剂，改变反应物苯胺和N-羟乙基苯胺的比例化学法合成出导电共聚物，选用的做掺杂剂的酸不同，生成聚合物的性质有很大差别，其中盐酸做掺杂剂时合成的导电共聚物具有形貌好，分散性好聚合均匀，稳定性好等优良湿敏性特点。
盐酸掺杂的苯胺/N-羟乙基苯胺共聚物，反应物苯胺和N-羟乙基苯胺的添加比例不一样，对聚合物形貌、湿敏性和导电性、稳定性以及溶解性都有影响。其中当苯胺和N-羟乙基苯胺以1:1比例反应制备出的导电聚合物具有形貌好均匀以及适中的湿敏稳定性和溶解性能。当反应物苯胺和N-羟乙基苯胺1:1，再加入反应液质量10%的聚乙烯吡咯烷酮时，制备出的导电聚合物具有较好的形貌，电镜扫描出其形貌为均匀的空心小球，其它反应物比例下聚合的反应物扫描电镜观察均为片状或破壳结构表面负载有东西的不均匀固体，添加比例的不同，对其形貌、溶解性和湿敏性均有较大的影响。
反应物中苯胺比例增大时，虽然湿敏性能良好，但其溶解性不高，反应物中N-羟乙基苯胺的加入增加了聚合物的溶解性，但湿敏性能降低了，只有苯胺/N-羟乙基苯胺比例适当时生成的聚合物才既具有良好的湿敏性能，溶解性又好。我们采用电化学工作站对聚合物阻抗进行分析，对其阻抗变化规律进行了研究，并解释了阻抗变化原因。研究表明：各聚合物的阻抗值均随着环境湿度变化而变化。随着反应物苯胺比例的增多反应物阻值减小，溶解性减小；反之N-羟乙基苯胺比例的增多，阻值增大，但溶解性增加。所以控制苯胺与N-羟乙基苯胺比例得当，聚合物湿敏性能和溶解性能均可以良好发挥。当苯胺和N-羟乙基苯胺1:1比例反应聚合时，其湿敏性能和溶解性都可以得到良好体现。
本论文最后采用电化学循环伏安法高氯酸做掺杂剂制备了不同比例的反应物苯胺/N-羟乙基苯胺的导电聚合物，研究了不同条件下的聚合特性，在循环伏安的扫描过程中单体首先被氧化成反应中间体（一般认为是醌式结构），在反应中间体催化下反应快速进行；随电位循环扫描次数的不断增加，峰值电流以及通过电极的电量逐渐增大，沉积在工作电极上聚合物膜也逐渐加厚；扫描速率对电化学聚合过程也有影响。扫描速率太大或太小聚合电流都会降低，要得到理想的聚合物膜需要控制适当的扫描速率。
This paper first we preparation out N-Hydroxyethylaniline with aniline and2-chloroethanol asbase material, and then we use ammonium persulfate as the oxidant to synthesize conducting polymer Withaniline and N-hydroxyethyl aniline as reactant. the preparation of the products were research andcharacterization Through the use of various analysis methods,such as scanning electron microscopy(SEM),infrared mapping (IR), X-ray diffraction method (XRD), transmission electron microscopy (TEM)and so on.The key to this paper, moisture sensitivity and electrical Conductivity of those synthesis ofconductive polymers were analyzed, Researched and compared.
We respectively use hydrochloric acid and perchloric acid as doping agent and change theproportion of aniline and N-hydroxyethyl aniline to synthesize conductive copolymer with Chemicalmethods. Choosing different acids to doping agent, Properties of products make great differences. When wechoose hydrochloric acid as doping agent, synthesis of conductive polymers have high electrochemicalperformances, for example, good appearance,good dispersibility, good stability, good moisturesensitivity and so on.
We choose the same acid as doping agent, and change the proportion of aniline andN-hydroxyethyl aniline, Properties of products Make Great Differences which contains appearance,moisture sensitivity, electrical Conductivity stability and dissolubility. When the weight ratio of aniline andN-hydroxyethyl is1:1, and we put polyvinylpyrrolidone whose weight is10%of the weight of the reactionliquid, synthetic of polymers has the best electrochemical performances, which is well-distributed andsmall Hollow sphere.
When we increase the proportion of aniline on reaction, although conductive polymers havebetter moisture sensitivity, but they have bad solution. Only we adjust the proper proportion of aniline andN-hydroxyethyl aniline, Synthesised conductive polymers contain not only good moisture sensitivity,butalso good Solubility. We measure the electrical impedance of Synthetic polymer by adoptingelectrochemical workstation and analyse their laws. Research indicated, the electrical impedance ofSynthetic polymers is affected by ambient humidity, the Impedance values and Solubility of conductivepolymers Increase with the decrease of Humidity. Only the reactant proportion, synthetic of polymers contain good moisture sensitivity as well as good Solubility. When the weight ratio of aniline andN-hydroxyethyl is1:1, synthetic of polymers has the best electrochemical performances.
At last, we use perchloric acid as doping agent and adjust the proportion of aniline andN-hydroxyethyl aniline to synthesize conductive polymer by AC cyclic voltammetry. We separatelyresearch the polymerization characteristics under different conditions. During the scanning process of ACcyclic voltammetry, the monomer first was oxidated to reaction intermediate, and Reaction intermediatewas used as catalyst to speed up the reaction speed. Along with the increase of scanning times, the peakcurrent and power of electrode all increase, the membrane of polymer increases in thickness.sweep speedhas an important effect on polymerization reaction. Too fast or too slow of sweep speed both lead toPolymerization current reduce. Only control proper sweep speed we can synthesis perfect membrane ofpolymer.
分别以盐酸和高氯酸作为掺杂剂，改变反应物苯胺和N-羟乙基苯胺的比例化学法合成出导电共聚物，选用的做掺杂剂的酸不同，生成聚合物的性质有很大差别，其中盐酸做掺杂剂时合成的导电共聚物具有形貌好，分散性好聚合均匀，稳定性好等优良湿敏性特点。
盐酸掺杂的苯胺/N-羟乙基苯胺共聚物，反应物苯胺和N-羟乙基苯胺的添加比例不一样，对聚合物形貌、湿敏性和导电性、稳定性以及溶解性都有影响。其中当苯胺和N-羟乙基苯胺以1:1比例反应制备出的导电聚合物具有形貌好均匀以及适中的湿敏稳定性和溶解性能。当反应物苯胺和N-羟乙基苯胺1:1，再加入反应液质量10%的聚乙烯吡咯烷酮时，制备出的导电聚合物具有较好的形貌，电镜扫描出其形貌为均匀的空心小球，其它反应物比例下聚合的反应物扫描电镜观察均为片状或破壳结构表面负载有东西的不均匀固体，添加比例的不同，对其形貌、溶解性和湿敏性均有较大的影响。
反应物中苯胺比例增大时，虽然湿敏性能良好，但其溶解性不高，反应物中N-羟乙基苯胺的加入增加了聚合物的溶解性，但湿敏性能降低了，只有苯胺/N-羟乙基苯胺比例适当时生成的聚合物才既具有良好的湿敏性能，溶解性又好。我们采用电化学工作站对聚合物阻抗进行分析，对其阻抗变化规律进行了研究，并解释了阻抗变化原因。研究表明：各聚合物的阻抗值均随着环境湿度变化而变化。随着反应物苯胺比例的增多反应物阻值减小，溶解性减小；反之N-羟乙基苯胺比例的增多，阻值增大，但溶解性增加。所以控制苯胺与N-羟乙基苯胺比例得当，聚合物湿敏性能和溶解性能均可以良好发挥。当苯胺和N-羟乙基苯胺1:1比例反应聚合时，其湿敏性能和溶解性都可以得到良好体现。
本论文最后采用电化学循环伏安法高氯酸做掺杂剂制备了不同比例的反应物苯胺/N-羟乙基苯胺的导电聚合物，研究了不同条件下的聚合特性，在循环伏安的扫描过程中单体首先被氧化成反应中间体（一般认为是醌式结构），在反应中间体催化下反应快速进行；随电位循环扫描次数的不断增加，峰值电流以及通过电极的电量逐渐增大，沉积在工作电极上聚合物膜也逐渐加厚；扫描速率对电化学聚合过程也有影响。扫描速率太大或太小聚合电流都会降低，要得到理想的聚合物膜需要控制适当的扫描速率。
This paper first we preparation out N-Hydroxyethylaniline with aniline and2-chloroethanol asbase material, and then we use ammonium persulfate as the oxidant to synthesize conducting polymer Withaniline and N-hydroxyethyl aniline as reactant. the preparation of the products were research andcharacterization Through the use of various analysis methods,such as scanning electron microscopy(SEM),infrared mapping (IR), X-ray diffraction method (XRD), transmission electron microscopy (TEM)and so on.The key to this paper, moisture sensitivity and electrical Conductivity of those synthesis ofconductive polymers were analyzed, Researched and compared.
We respectively use hydrochloric acid and perchloric acid as doping agent and change theproportion of aniline and N-hydroxyethyl aniline to synthesize conductive copolymer with Chemicalmethods. Choosing different acids to doping agent, Properties of products make great differences. When wechoose hydrochloric acid as doping agent, synthesis of conductive polymers have high electrochemicalperformances, for example, good appearance,good dispersibility, good stability, good moisturesensitivity and so on.
We choose the same acid as doping agent, and change the proportion of aniline andN-hydroxyethyl aniline, Properties of products Make Great Differences which contains appearance,moisture sensitivity, electrical Conductivity stability and dissolubility. When the weight ratio of aniline andN-hydroxyethyl is1:1, and we put polyvinylpyrrolidone whose weight is10%of the weight of the reactionliquid, synthetic of polymers has the best electrochemical performances, which is well-distributed andsmall Hollow sphere.
When we increase the proportion of aniline on reaction, although conductive polymers havebetter moisture sensitivity, but they have bad solution. Only we adjust the proper proportion of aniline andN-hydroxyethyl aniline, Synthesised conductive polymers contain not only good moisture sensitivity,butalso good Solubility. We measure the electrical impedance of Synthetic polymer by adoptingelectrochemical workstation and analyse their laws. Research indicated, the electrical impedance ofSynthetic polymers is affected by ambient humidity, the Impedance values and Solubility of conductivepolymers Increase with the decrease of Humidity. Only the reactant proportion, synthetic of polymers contain good moisture sensitivity as well as good Solubility. When the weight ratio of aniline andN-hydroxyethyl is1:1, synthetic of polymers has the best electrochemical performances.
At last, we use perchloric acid as doping agent and adjust the proportion of aniline andN-hydroxyethyl aniline to synthesize conductive polymer by AC cyclic voltammetry. We separatelyresearch the polymerization characteristics under different conditions. During the scanning process of ACcyclic voltammetry, the monomer first was oxidated to reaction intermediate, and Reaction intermediatewas used as catalyst to speed up the reaction speed. Along with the increase of scanning times, the peakcurrent and power of electrode all increase, the membrane of polymer increases in thickness.sweep speedhas an important effect on polymerization reaction. Too fast or too slow of sweep speed both lead toPolymerization current reduce. Only control proper sweep speed we can synthesis perfect membrane ofpolymer.
引文
[1]王利祥，王佛松.导电聚合物—聚苯胺的研究进展—Ⅱ.电子现象、导电机理、性质和应用[J].应用化学，1990,12-27.
[2]王碧坛.导电聚合物薄膜的电化学制备与电极性能研究[J].天津大学硕士学位论文，2009,05~11.
[3] Herod T E,Schlenoff J B.Doping-induced strain in polyaniline:stretchoelectrochemistry.Chem Mater,1993,5:951–955.
[4]李荣金，李洪祥等.聚合物场效应晶体管材料及其器件[J].化学进展，2007,21
[5]杨宏昌，李志刚.结构型导电高分子材料现状与发展趋势[J].广东化工，2010,05
[6]诸平，张文根.白川英树与导电聚合物的发现[J].大学化学，2003,01
[7]彭霞晖，刘靖宇.聚苯胺合成研究进展[J].精细化工中间体，2002,06
[8]李永航，聚合物发光电化学池的研究[J].电化学，2005,02: Vol11, No01.
[9] PeiQ B,Yang Y,L i Y F. Conjugated Polymers and Their Electroluminescent De2vices. in“RecentDevelopments of Oversea’s Polymer Science”. Chap ter9(He T B. Hu H J. edited)[M]. Beijing:Chemical Industry Press.1997.140～164.
[10] L i Y F, PeiQ B. Conjugated poly2mer light2emitting electrochemical cells [J]. Polym.Bull.,1997,8.
[11]黄美容，章家立.导电聚合物电致变色掺杂特征及表征参数[[J].化学研究与应用.2006,07.30.
[12]吕生华，王飞.聚苯胺导电聚合物应用新进展[J].化工新型材料.2008.04.15.
[13]薛怀国，沈之荃.导电聚合物传感器的研究进展[J].化学通报.2001.07.18.
[14] C. González, Jiandong Guo, J. Ortega, F. Flores, and H. H. Weitering “Mechanism of the band gapopening across the order-disorder transition of Si(111)4′1-In”.Phys.Rev.Lett.102.115501(2009).
[15]邱勇，张德强等.染料掺杂聚合物电致发光薄膜的能量传递.[J]激光与红外.1996,02: Vol26, No01.
[16]张文跟，张学英.导电高分子的应用展望.[J]上海化工.2001,07.
[17]张其锦，翟炎.聚苯胺的电化学合成．[J]大学化学，1998,4:41—43．
[18]张贵萍，龚克成.聚苯胺的结构与性能．[J]高分子材料与工程，1993,3:7—16．
[19] W．Barford，R．J．Bursill．The electronic structure of conjugated polymers．[J]Synthetic Metals，2001，119：251～252
[20]陆珉，吴益华，姜海夏.导电聚苯胺的特性及应用．[J]阴功能材料，1998，29(4)
[21] Nicola Costantini，Roberto Cagnolati，Lamberto Nucci．Electrochemical synthesis of intrinsicallyconducting polymers of3-alkylpyrroles．[J]Synthetic Metals，1998，92：139-147
[22]阮孟财.电化学法制备聚苯胺薄膜及其性能研究[D]上海大学.2009,03,01.
[23] Rita Stella，Joseph N Barisci，Giorgio Serra．Characterisation of olive oil by an electronic nose basedon conducting polymer sensors．[J]Sensors and Actuators B2000，63：1-9
[24] Chemical Synthesis and Characterization of Watersoluble,Conducting Poly (N-phenylglycine).[J]Iranian Polymer Journal,VOL17,No5(2008):365-371
[25] Mohammad Reza Nabid，Ali Akbar Entezami Polym. Comparative study on the enzymaticpolymerization of N-substituted aniline derivatives [J]. polym Adv. Technol,2005,16:305–309.
[26]缪晓波.智能传感器网络传感器信息传感器.[J]传感器世界，2000,01,15.
[27]王祁，宇航.传感器技术的新发展.[J]传感器技术，1998,02,28.
[28]黄中.传感技术与传感器.[J]世界发明，2002,05.
[29]池雪莲.传感器技术应用与发展趋势展望[J]，襄樊职业技术学院学报，2006,(1):7-9
[30]刘仰魁，郭立帅，碰昌宁等.发展中的传感器技术.[J]陇东学院学报（自然科学版）.Vol1,No16(2005):35-38
[31]陈少珠，杨园园.树枝状大分子在传感器中的应用[J]化学传感器2001,09.Vol31,No3:17-19.
[32]周旭，曹阳.人体五官与感觉传感器.[J]家电检修技术，2001，No9.
[33]葛玉荣,吴冬华.数字温度传感器在动车组轴承温度检测中的应用[J].内燃机车,2005,(09).
[34]张华德.传感器与信号处理技术在机械设备故障诊断中的应用研究[J].东北大学硕士学位论文，2005,03,01.
[35]祝敏.基于霍尔传感器电参量测量系统的设计[J].现代电子技术，2009,04,05.
[36]杨德友.开拓智能传感器应用市场[J].现代制作，2010,01,17.
[37]佟玲，邹文江.航天航空Mems传感器应用及其发展现状[J].电子世界，2011,01.01.
[38]吴伟明.传感器应用与发展[J].电子制作，2007,02,08.
[39]税冬东.浅谈多传感器融合技术[J]农家科技，2011,03,25.
[40]李刚.浅谈多传感器信息融合[J]科技风，2011,02,25.
[41]韩悦文,陈海燕,黄春雄.光电技术在湿度传感器中的应用[J].光电技术应用,2008(3):33-36
[42]于晓丽，杨建.湿度传感器选用及发展趋势[J].自动化技术与应用，2008,09,02
[43]郝育文.新型湿度传感器研究进展[J].传感器与微系统，2009,Vol08,No11
[44]锦屏陈贻炽，吴，顾惕人，等.阻抗型聚合物湿度传感器HMPTAC/St共聚物感湿膜的感湿性能[J].精细化工，1998，15:24～27.
[45]王守德.碳纤维硫铝酸盐水泥复合材料的制备及其机敏特性[D].武汉理工大学,2008.
[46]张会锐.基于纳米材料的湿度传感器的研究[D].浙江大学,2004.
[47] BernardM Kulw ick i. J Am Ceram Soc,1991,74(4):697
[48] Sakai Y, Sadaoka Y, et al. Senso rs and A ctuato rs,1996,B (35～36):85
[49]刘博华,袁疆鹰,丛秀云.我国湿度敏感材料的研究现状与发展趋势[J].物理,1995,23(8):471
[50]刘崇进,沈家瑞,朱荫兰.仪表技术与传感器,1997,12:1
[51]骆如枋,化学传感器,1993,13(4):18
[52]骆如枋,化学传感器,1994,14(1):18
[53]易惠中,仪表材料,1990,21(2):118
[54]孙良偐，邱法斌，平田光.高分子电阻性湿敏元件改性研究[J].传感器与微系统，1994,05.
[55] Dunmo re FW. U S2,210,903
[56] MgCr2O4—SnO2烧结体湿敏半导体陶瓷湿度传感器与数字式温度测控仪[J].传感器技术，1984,03,01
[57]李艳辉，黄玉东.高分子湿敏材料[J].材料科学与工艺，2003,09,30
[58]王力，利小玫.湿敏原件及其发展[J].仪表技术与传感器，1987，vol1.
[59]李艳辉，黄玉东等.高分子湿敏材料[J]材料科学与工艺，2003,09..Vol11,No3:
[60] Gue-Wuu Hwang, Kuan-Ying Wu, Mu-Yi Hua et al. Structures and properties of the solublepolyanilines，N-alkylated emeraldine bases [J]. Synthetic Metals,1998,92:39-46.
[61]穆绍林等.苯胺在碱性溶液中的电化学聚合和聚合物的性质[J].电化学,1996,2(1):54-58.
[62] Gabriel A.Planes, Gustavo M.Morales, Maria C.Miras et al. A soluble and electroactive ployanilineobtained by coupling of4-sulfobenzenediazonium ion and ploy(N-methylaniline)[J].Synthetic Metals,1998,97:223-227.
[63] Akira Watanabe, Kunio Mori, Atsushi Iwabuchi et al. Electrochemical polymerization of aniline andN-alkylanilines[J]. Macromolecules,1989,22:3521-3525.
[64] Mario Leclerc, Jean Guay, Le H. Dao. Synthesis and characterization of poly(alkyanilines)[J].Macromolecules,1989,22:649-653.
[65] MICHAEL G. MIKHAEL, ANNE BUYLE PADIAS, H. K. HALL, JR. New developments inbone-forming initiation: Lewis acides accelerate spontaneous initiation of copolymerizations of olefinsand dienes [J]. Macromolecular symposia,1995,95(1):233-242.
[66] Albertas Malinauskas á Rudolf Holze. A UV-visible spectroelectrochemical study of theelectropolymerisation of N-benzylaniline[J]. J Solid State Electrochem,1999,3:429-436.
[67] Natalia V. Blinova, Jaroslav Stejskal, Miroslava Trchova. The oxidation of anline with sliver nitrate topolyaniline-sliver composites [J].2009,50(1):50-56
[68] H.H. Zhou, S.Q. Jiao, J.H. Chen,W.Z.Wei, Y.F. Kuang, Synthesis of polyaniline-sliver nanocompositeflim by unsymmetrical square wave current method [J].Thin Solid Films2004,510:164-168.
[69] A. Falcou, A. Duchene, P.Hourquebie et al. A new chemical polymerization process for substitutedanilines: Application to the synthesis of poly(N-alkylanilines) and poly(o-alkylanilines) andcomparison of their respective properties[J].Synthetic Metals,2005,149(2-3):115-122.
[70] Xu-Yuan Peng, Feng Luan, Xiao-Xia Liu.PH-controlled morphological structure of polyaniline duringelectrochemical deposition [J]. Electrochimica Acta.54(26):6172-6177.
[71] A.Michael,R.N.Hartmann,Ber.,40,142(1907)
[72] B.Rugheimer,R.Hoffmann,Ber.,17,739(1884)
[73] MILIND V. KULKARNI, ANJALI A. ATHAWALE.Poly(2,3-dimethylaniline) as a competent materialfor humidity sensor. P(2,3-DMA) AS HUMIDITY SENSOR[J],2009,09,18.
[74] Narsimha Parvatikar,1Shilpa Jain,2S. V. Bhoraskar,2M. V. N. Ambika Prasad3. Spectroscopic andelectrical properties of polyaniline--CeO2composites and their application as humidity sensor.PARVATIKAR ET AL[J].2006,02,12
[75] Salaneck WR, Liedberg B, Inganas O, Erlandsson R, Lundstrom I, MacDiarmid AG, Halpern M,Somasiri NLD. Phsical characterization of some polyaniline[J].(PHIN) X. Mol. Cryst. Liq. Cryst,1985,121:191.
[76] Cao Y, Smith Heeger A J．Spectroscopic studies of polyaniline in solution and in spin-castfilms[J]．Synth Met，1989，32(3):263-281.
[77] Xiao-Xia Liu, Yu-Qian Dou, Jian Wu, Xu-Yuan Peng. Chemical anchoring of silica nanoparticles ontopolyaniline chains via electro-co-polymerization of aniline and N-substituted aniline grafted onsurfaces of SiO2[J].Electrochimica Acta.2008,53:4693–4698.
[78]邓建，王晓芳，张正泉．用部分相干光衍射理论研究光栅成像系统．[J]光学学报，1997.04
[79] Wen-Yue Zheng, Kalle Levon, Jukka Laakso et al. Characterization and Solid-State Properties ofProcessable N-Alkylated Polyanilines in the Neutral State[J]. Macromolecules,1994,27,7754-7768.
[80] Y.Tan, Y.Zhang, J. Kan, Tan et al-Express polymer Letters vol20093(6)333-339
[81] Kinlen P J，Frushour B G， Ding Y el a1．Synthesis and characterization of organically solublepolyaniline and polyaniline block copolymers[J]．Synth Met，1999，101(1-3)：758-761．
[82] Sapurina J, Stejskal J. Preparation and characterization of polyaniline-silver composites [J]. polymInt,2008,57:1295.
[83]薛涛，高电导率聚苯胺膜和可溶性聚苯胺涂料的制备及功能PCB板的探索[D].天津:天津大学，2005.
[84]唐劲松，王宝沈等.聚苯胺的合成_结构_性能及应用.高分子材料与工程[J].1987,02.
[85] Boyland，E.，etal，J.Chem.Soe.，1953，，3623
[86] Jozefowiez，M.，etal，Eleetroehim.Aeta1968，L3，151
[87] Gupta，R.C.，rivastava，S.P.，ndiaoJ.Chem.，1972，10，706
[88] Green，A.G.，etal，J.Chem.Soe.，1910，97，2355;1912，101，1127，Ber.，1913，46，5769
[89]贺举.导电高分子聚苯胺的合成和应用.科技信息[J].2008,06,20
[90]刘平云,张长瑞等.层层自主装原位聚合聚苯胺复合膜成膜机理研究[J].化学学报.Vol65,2007
[91] Narsimha Parvatikar,1Shilpa Jain,2S. V. Bhoraskar,2M. V. N. Ambika Prasad3. Spectroscopic andelectrical properties of polyaniline--CeO2composites and their application as humidity sensor.PARVATIKAR ET AL[J].2006,02,12
[92] Milind V. Kulkarni, Annamraju Kasi Viswanath. Sulphonic acids doped poly(N-ethyl aniline)--Amaterial for humidity sensing application. POLYMER ENGINEERING AND SCIENCE[J].2007
[93]刘晓磊.纳米复合聚苯胺的制备及其湿敏性能研究[D].南京航天航空大学.2007,03
[94]周铁利，赵纯.聚苯胺及其衍生物薄膜的制备和湿敏性研究[D].吉林大学，2009,10~11
[95] Shilpa Jain a, Sanjay Chakane a, A.B. Samui b, V.N. Krishnamurthy c, S.V. Bhoraskar a.Humiditysensing with weak acid-doped polyaniline and its composites. Sensors and Actuators[J].96(2003)124–129.
[96]刘代俊,马克承,石炎福.盐饱和溶液气相的相对湿度.四川大学学报(工程科学版)[J].1991年第04期
[97]沙占友，薛树琦，葛家怡.湿度传感器的发展趋势.电子技术应用[J]2003年第7期
[98] Dig.Int.Conf.on Laugmuir Blodgett films1987,272-273.
[99]宋晓辉,任道远.传感器功能材料现状与展望.传感器世界[J].2007,01
[100]彭霞辉，黄可龙，焦飞鹏等。聚苯胺的合成及性能[J],中南大学学报，2004，35:394-397.
[101]傅谊，马建标，何炳林，恒电位条件下制备聚苯胺PAn及其电化学行为[J]，化学研究与应用，1998，10(2)：133—137.
[102]方惠群，李根喜，陈洪渊．低电流密度下恒电流法制备的聚苯胺修饰电极[J高等学校化学学报．1994，15(3)：348—351.
[103] Rajendrana V，Gopalana A，Vasudevana T,et al.Crowth behaviour of polyaniline films deposited bypulsepotentiostatic method[J]， Materials Chemistry andPhysics，2000(65)：320—328
[104]侯丽波，贾梦秋，胡刚。聚苯胺薄膜电极的制备及性能研究[J].北京化工大学学报，2004,31:65-69.
[105]陈忠平，陈君华，郭家豪等.循环伏安法的电扫描方式对苯胺聚合产物形貌影响的观察[J]。高分子学报,2007.(6):536-540.
[106] Kobayashi T，Yoneyana H．Tamura H．Journal of Electroanalytical Chemistry，1984，161(2)：419～423
[2]王碧坛.导电聚合物薄膜的电化学制备与电极性能研究[J].天津大学硕士学位论文，2009,05~11.
[3] Herod T E,Schlenoff J B.Doping-induced strain in polyaniline:stretchoelectrochemistry.Chem Mater,1993,5:951–955.
[4]李荣金，李洪祥等.聚合物场效应晶体管材料及其器件[J].化学进展，2007,21
[5]杨宏昌，李志刚.结构型导电高分子材料现状与发展趋势[J].广东化工，2010,05
[6]诸平，张文根.白川英树与导电聚合物的发现[J].大学化学，2003,01
[7]彭霞晖，刘靖宇.聚苯胺合成研究进展[J].精细化工中间体，2002,06
[8]李永航，聚合物发光电化学池的研究[J].电化学，2005,02: Vol11, No01.
[9] PeiQ B,Yang Y,L i Y F. Conjugated Polymers and Their Electroluminescent De2vices. in“RecentDevelopments of Oversea’s Polymer Science”. Chap ter9(He T B. Hu H J. edited)[M]. Beijing:Chemical Industry Press.1997.140～164.
[10] L i Y F, PeiQ B. Conjugated poly2mer light2emitting electrochemical cells [J]. Polym.Bull.,1997,8.
[11]黄美容，章家立.导电聚合物电致变色掺杂特征及表征参数[[J].化学研究与应用.2006,07.30.
[12]吕生华，王飞.聚苯胺导电聚合物应用新进展[J].化工新型材料.2008.04.15.
[13]薛怀国，沈之荃.导电聚合物传感器的研究进展[J].化学通报.2001.07.18.
[14] C. González, Jiandong Guo, J. Ortega, F. Flores, and H. H. Weitering “Mechanism of the band gapopening across the order-disorder transition of Si(111)4′1-In”.Phys.Rev.Lett.102.115501(2009).
[15]邱勇，张德强等.染料掺杂聚合物电致发光薄膜的能量传递.[J]激光与红外.1996,02: Vol26, No01.
[16]张文跟，张学英.导电高分子的应用展望.[J]上海化工.2001,07.
[17]张其锦，翟炎.聚苯胺的电化学合成．[J]大学化学，1998,4:41—43．
[18]张贵萍，龚克成.聚苯胺的结构与性能．[J]高分子材料与工程，1993,3:7—16．
[19] W．Barford，R．J．Bursill．The electronic structure of conjugated polymers．[J]Synthetic Metals，2001，119：251～252
[20]陆珉，吴益华，姜海夏.导电聚苯胺的特性及应用．[J]阴功能材料，1998，29(4)
[21] Nicola Costantini，Roberto Cagnolati，Lamberto Nucci．Electrochemical synthesis of intrinsicallyconducting polymers of3-alkylpyrroles．[J]Synthetic Metals，1998，92：139-147
[22]阮孟财.电化学法制备聚苯胺薄膜及其性能研究[D]上海大学.2009,03,01.
[23] Rita Stella，Joseph N Barisci，Giorgio Serra．Characterisation of olive oil by an electronic nose basedon conducting polymer sensors．[J]Sensors and Actuators B2000，63：1-9
[24] Chemical Synthesis and Characterization of Watersoluble,Conducting Poly (N-phenylglycine).[J]Iranian Polymer Journal,VOL17,No5(2008):365-371
[25] Mohammad Reza Nabid，Ali Akbar Entezami Polym. Comparative study on the enzymaticpolymerization of N-substituted aniline derivatives [J]. polym Adv. Technol,2005,16:305–309.
[26]缪晓波.智能传感器网络传感器信息传感器.[J]传感器世界，2000,01,15.
[27]王祁，宇航.传感器技术的新发展.[J]传感器技术，1998,02,28.
[28]黄中.传感技术与传感器.[J]世界发明，2002,05.
[29]池雪莲.传感器技术应用与发展趋势展望[J]，襄樊职业技术学院学报，2006,(1):7-9
[30]刘仰魁，郭立帅，碰昌宁等.发展中的传感器技术.[J]陇东学院学报（自然科学版）.Vol1,No16(2005):35-38
[31]陈少珠，杨园园.树枝状大分子在传感器中的应用[J]化学传感器2001,09.Vol31,No3:17-19.
[32]周旭，曹阳.人体五官与感觉传感器.[J]家电检修技术，2001，No9.
[33]葛玉荣,吴冬华.数字温度传感器在动车组轴承温度检测中的应用[J].内燃机车,2005,(09).
[34]张华德.传感器与信号处理技术在机械设备故障诊断中的应用研究[J].东北大学硕士学位论文，2005,03,01.
[35]祝敏.基于霍尔传感器电参量测量系统的设计[J].现代电子技术，2009,04,05.
[36]杨德友.开拓智能传感器应用市场[J].现代制作，2010,01,17.
[37]佟玲，邹文江.航天航空Mems传感器应用及其发展现状[J].电子世界，2011,01.01.
[38]吴伟明.传感器应用与发展[J].电子制作，2007,02,08.
[39]税冬东.浅谈多传感器融合技术[J]农家科技，2011,03,25.
[40]李刚.浅谈多传感器信息融合[J]科技风，2011,02,25.
[41]韩悦文,陈海燕,黄春雄.光电技术在湿度传感器中的应用[J].光电技术应用,2008(3):33-36
[42]于晓丽，杨建.湿度传感器选用及发展趋势[J].自动化技术与应用，2008,09,02
[43]郝育文.新型湿度传感器研究进展[J].传感器与微系统，2009,Vol08,No11
[44]锦屏陈贻炽，吴，顾惕人，等.阻抗型聚合物湿度传感器HMPTAC/St共聚物感湿膜的感湿性能[J].精细化工，1998，15:24～27.
[45]王守德.碳纤维硫铝酸盐水泥复合材料的制备及其机敏特性[D].武汉理工大学,2008.
[46]张会锐.基于纳米材料的湿度传感器的研究[D].浙江大学,2004.
[47] BernardM Kulw ick i. J Am Ceram Soc,1991,74(4):697
[48] Sakai Y, Sadaoka Y, et al. Senso rs and A ctuato rs,1996,B (35～36):85
[49]刘博华,袁疆鹰,丛秀云.我国湿度敏感材料的研究现状与发展趋势[J].物理,1995,23(8):471
[50]刘崇进,沈家瑞,朱荫兰.仪表技术与传感器,1997,12:1
[51]骆如枋,化学传感器,1993,13(4):18
[52]骆如枋,化学传感器,1994,14(1):18
[53]易惠中,仪表材料,1990,21(2):118
[54]孙良偐，邱法斌，平田光.高分子电阻性湿敏元件改性研究[J].传感器与微系统，1994,05.
[55] Dunmo re FW. U S2,210,903
[56] MgCr2O4—SnO2烧结体湿敏半导体陶瓷湿度传感器与数字式温度测控仪[J].传感器技术，1984,03,01
[57]李艳辉，黄玉东.高分子湿敏材料[J].材料科学与工艺，2003,09,30
[58]王力，利小玫.湿敏原件及其发展[J].仪表技术与传感器，1987，vol1.
[59]李艳辉，黄玉东等.高分子湿敏材料[J]材料科学与工艺，2003,09..Vol11,No3:
[60] Gue-Wuu Hwang, Kuan-Ying Wu, Mu-Yi Hua et al. Structures and properties of the solublepolyanilines，N-alkylated emeraldine bases [J]. Synthetic Metals,1998,92:39-46.
[61]穆绍林等.苯胺在碱性溶液中的电化学聚合和聚合物的性质[J].电化学,1996,2(1):54-58.
[62] Gabriel A.Planes, Gustavo M.Morales, Maria C.Miras et al. A soluble and electroactive ployanilineobtained by coupling of4-sulfobenzenediazonium ion and ploy(N-methylaniline)[J].Synthetic Metals,1998,97:223-227.
[63] Akira Watanabe, Kunio Mori, Atsushi Iwabuchi et al. Electrochemical polymerization of aniline andN-alkylanilines[J]. Macromolecules,1989,22:3521-3525.
[64] Mario Leclerc, Jean Guay, Le H. Dao. Synthesis and characterization of poly(alkyanilines)[J].Macromolecules,1989,22:649-653.
[65] MICHAEL G. MIKHAEL, ANNE BUYLE PADIAS, H. K. HALL, JR. New developments inbone-forming initiation: Lewis acides accelerate spontaneous initiation of copolymerizations of olefinsand dienes [J]. Macromolecular symposia,1995,95(1):233-242.
[66] Albertas Malinauskas á Rudolf Holze. A UV-visible spectroelectrochemical study of theelectropolymerisation of N-benzylaniline[J]. J Solid State Electrochem,1999,3:429-436.
[67] Natalia V. Blinova, Jaroslav Stejskal, Miroslava Trchova. The oxidation of anline with sliver nitrate topolyaniline-sliver composites [J].2009,50(1):50-56
[68] H.H. Zhou, S.Q. Jiao, J.H. Chen,W.Z.Wei, Y.F. Kuang, Synthesis of polyaniline-sliver nanocompositeflim by unsymmetrical square wave current method [J].Thin Solid Films2004,510:164-168.
[69] A. Falcou, A. Duchene, P.Hourquebie et al. A new chemical polymerization process for substitutedanilines: Application to the synthesis of poly(N-alkylanilines) and poly(o-alkylanilines) andcomparison of their respective properties[J].Synthetic Metals,2005,149(2-3):115-122.
[70] Xu-Yuan Peng, Feng Luan, Xiao-Xia Liu.PH-controlled morphological structure of polyaniline duringelectrochemical deposition [J]. Electrochimica Acta.54(26):6172-6177.
[71] A.Michael,R.N.Hartmann,Ber.,40,142(1907)
[72] B.Rugheimer,R.Hoffmann,Ber.,17,739(1884)
[73] MILIND V. KULKARNI, ANJALI A. ATHAWALE.Poly(2,3-dimethylaniline) as a competent materialfor humidity sensor. P(2,3-DMA) AS HUMIDITY SENSOR[J],2009,09,18.
[74] Narsimha Parvatikar,1Shilpa Jain,2S. V. Bhoraskar,2M. V. N. Ambika Prasad3. Spectroscopic andelectrical properties of polyaniline--CeO2composites and their application as humidity sensor.PARVATIKAR ET AL[J].2006,02,12
[75] Salaneck WR, Liedberg B, Inganas O, Erlandsson R, Lundstrom I, MacDiarmid AG, Halpern M,Somasiri NLD. Phsical characterization of some polyaniline[J].(PHIN) X. Mol. Cryst. Liq. Cryst,1985,121:191.
[76] Cao Y, Smith Heeger A J．Spectroscopic studies of polyaniline in solution and in spin-castfilms[J]．Synth Met，1989，32(3):263-281.
[77] Xiao-Xia Liu, Yu-Qian Dou, Jian Wu, Xu-Yuan Peng. Chemical anchoring of silica nanoparticles ontopolyaniline chains via electro-co-polymerization of aniline and N-substituted aniline grafted onsurfaces of SiO2[J].Electrochimica Acta.2008,53:4693–4698.
[78]邓建，王晓芳，张正泉．用部分相干光衍射理论研究光栅成像系统．[J]光学学报，1997.04
[79] Wen-Yue Zheng, Kalle Levon, Jukka Laakso et al. Characterization and Solid-State Properties ofProcessable N-Alkylated Polyanilines in the Neutral State[J]. Macromolecules,1994,27,7754-7768.
[80] Y.Tan, Y.Zhang, J. Kan, Tan et al-Express polymer Letters vol20093(6)333-339
[81] Kinlen P J，Frushour B G， Ding Y el a1．Synthesis and characterization of organically solublepolyaniline and polyaniline block copolymers[J]．Synth Met，1999，101(1-3)：758-761．
[82] Sapurina J, Stejskal J. Preparation and characterization of polyaniline-silver composites [J]. polymInt,2008,57:1295.
[83]薛涛，高电导率聚苯胺膜和可溶性聚苯胺涂料的制备及功能PCB板的探索[D].天津:天津大学，2005.
[84]唐劲松，王宝沈等.聚苯胺的合成_结构_性能及应用.高分子材料与工程[J].1987,02.
[85] Boyland，E.，etal，J.Chem.Soe.，1953，，3623
[86] Jozefowiez，M.，etal，Eleetroehim.Aeta1968，L3，151
[87] Gupta，R.C.，rivastava，S.P.，ndiaoJ.Chem.，1972，10，706
[88] Green，A.G.，etal，J.Chem.Soe.，1910，97，2355;1912，101，1127，Ber.，1913，46，5769
[89]贺举.导电高分子聚苯胺的合成和应用.科技信息[J].2008,06,20
[90]刘平云,张长瑞等.层层自主装原位聚合聚苯胺复合膜成膜机理研究[J].化学学报.Vol65,2007
[91] Narsimha Parvatikar,1Shilpa Jain,2S. V. Bhoraskar,2M. V. N. Ambika Prasad3. Spectroscopic andelectrical properties of polyaniline--CeO2composites and their application as humidity sensor.PARVATIKAR ET AL[J].2006,02,12
[92] Milind V. Kulkarni, Annamraju Kasi Viswanath. Sulphonic acids doped poly(N-ethyl aniline)--Amaterial for humidity sensing application. POLYMER ENGINEERING AND SCIENCE[J].2007
[93]刘晓磊.纳米复合聚苯胺的制备及其湿敏性能研究[D].南京航天航空大学.2007,03
[94]周铁利，赵纯.聚苯胺及其衍生物薄膜的制备和湿敏性研究[D].吉林大学，2009,10~11
[95] Shilpa Jain a, Sanjay Chakane a, A.B. Samui b, V.N. Krishnamurthy c, S.V. Bhoraskar a.Humiditysensing with weak acid-doped polyaniline and its composites. Sensors and Actuators[J].96(2003)124–129.
[96]刘代俊,马克承,石炎福.盐饱和溶液气相的相对湿度.四川大学学报(工程科学版)[J].1991年第04期
[97]沙占友，薛树琦，葛家怡.湿度传感器的发展趋势.电子技术应用[J]2003年第7期
[98] Dig.Int.Conf.on Laugmuir Blodgett films1987,272-273.
[99]宋晓辉,任道远.传感器功能材料现状与展望.传感器世界[J].2007,01
[100]彭霞辉，黄可龙，焦飞鹏等。聚苯胺的合成及性能[J],中南大学学报，2004，35:394-397.
[101]傅谊，马建标，何炳林，恒电位条件下制备聚苯胺PAn及其电化学行为[J]，化学研究与应用，1998，10(2)：133—137.
[102]方惠群，李根喜，陈洪渊．低电流密度下恒电流法制备的聚苯胺修饰电极[J高等学校化学学报．1994，15(3)：348—351.
[103] Rajendrana V，Gopalana A，Vasudevana T,et al.Crowth behaviour of polyaniline films deposited bypulsepotentiostatic method[J]， Materials Chemistry andPhysics，2000(65)：320—328
[104]侯丽波，贾梦秋，胡刚。聚苯胺薄膜电极的制备及性能研究[J].北京化工大学学报，2004,31:65-69.
[105]陈忠平，陈君华，郭家豪等.循环伏安法的电扫描方式对苯胺聚合产物形貌影响的观察[J]。高分子学报,2007.(6):536-540.
[106] Kobayashi T，Yoneyana H．Tamura H．Journal of Electroanalytical Chemistry，1984，161(2)：419～423
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