聚苯胺/聚氨酯复合导电涂层的制备与性能研究
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摘要
许多国家近年来都积极致力于研发环境友好型涂料来取代有毒涂料,水性导电高分子涂料作为新型涂料因其无毒、无污染而备受关注。本文的研究工作就是为开发水性导电防腐防污涂料提供科学和实验基础,其关键是研制出导电性好的导电聚合物并解决其在成膜物中分散性差的问题。
本论文工作从制备盐酸掺杂态聚苯胺出发,通过对化学氧化法合成的掺杂态聚苯胺的研究,找到制备出高品质聚苯胺的最佳合成工艺条件,并研究原位聚合法合成的聚苯胺/碳纳米管复合材料的性能。主要实验结果如下：
(1)随An:APS增大,PANI平均粒径、产率呈下降趋势,苯胺单体浓度与An:APS对产物产率的影响结果基本相同。低温利于获得掺杂状态良好的产物,而且,随着体系酸浓度增大,聚苯胺掺杂状态较好。HC1浓度1mol·L-1,苯胺单体浓度0.3-0.4mlL-1,An:APS在0.8-0.9在13℃反应时聚苯胺产物综合性能较好。
(2)聚苯胺/碳纳米管复合材料中的聚苯胺为盐酸掺杂的翠绿亚胺态,结构规整度较纯的盐酸掺杂态聚苯胺明显提高,聚苯胺和碳纳米管复合状况良好,且其结构都没有改变。
(3)添加碳纳米管/聚苯胺复合材料及聚苯胺导电粉体后的涂层,耐冲击性很好,导电性能得到改善,但涂层的附着力及表面形貌不理想。
(4)无论添加何种导电粉体(聚苯胺/碳纳米管、聚苯胺),其电流都较普通导电涂层高。综合交流电化学阻抗及极化曲线结果得出,聚苯胺/碳纳米管添加量为1.0%,聚苯胺添加量为0.6%的涂层具有一定导电性能的同时,还具有较好的防腐性能。
Researchers in many countries devoted themselves to the study of environment friendly coatings in order to replace toxic coatings. Waterborne conductive polymer coatings have attracted much attention because of its non-toxic, non-pollution. The work is to provide scientific and experimental basis for waterborne conductive coatings. Synthesizing of conductive polymer with high conductivity and dispersing well in matrix resin are the key of the work.
In this paper, HC1 dopped PANI was synthesized via chemical oxidative polymerization, searched the optimum conditions, and then studied properties of CNT/PANI composites prepared by in-situ polymerizaton. The main results are summarized as follows:
(1) With An:APS's incresing, grain size and productive rate of PANI decreases. PANI synthesized with differernt An:APS and [An] performs similar. The better PANI dopped with when the temperature is lower and acid concentration is higher.The optimum conditions of synthesizing PANI is 1mol·L-1Hl,13℃, [An]=0.3-0.4mol·L-1, An:APS=0.8～0.9.
(2)Polyaniline in PANI/CNT composites is emeraldine dopped by HC1, PANI and CNT compound well, structure regularity of PANI/CNT improved obviously, but remain the same.
(3)Coatings added with PANI and PANI/CNT performs good impact resistance, and its conductive performance is improved,but the adhesion and surface morphology of the coatings is not ideal.
(4)Coatings added with conductive powder performs higher current density than the ordinary conductive coating. Overall,coatings added with 1.0%PANI,0.6%PANI performs certain electrical properties,and better anti-corrosion properties.
本论文工作从制备盐酸掺杂态聚苯胺出发,通过对化学氧化法合成的掺杂态聚苯胺的研究,找到制备出高品质聚苯胺的最佳合成工艺条件,并研究原位聚合法合成的聚苯胺/碳纳米管复合材料的性能。主要实验结果如下：
(1)随An:APS增大,PANI平均粒径、产率呈下降趋势,苯胺单体浓度与An:APS对产物产率的影响结果基本相同。低温利于获得掺杂状态良好的产物,而且,随着体系酸浓度增大,聚苯胺掺杂状态较好。HC1浓度1mol·L-1,苯胺单体浓度0.3-0.4mlL-1,An:APS在0.8-0.9在13℃反应时聚苯胺产物综合性能较好。
(2)聚苯胺/碳纳米管复合材料中的聚苯胺为盐酸掺杂的翠绿亚胺态,结构规整度较纯的盐酸掺杂态聚苯胺明显提高,聚苯胺和碳纳米管复合状况良好,且其结构都没有改变。
(3)添加碳纳米管/聚苯胺复合材料及聚苯胺导电粉体后的涂层,耐冲击性很好,导电性能得到改善,但涂层的附着力及表面形貌不理想。
(4)无论添加何种导电粉体(聚苯胺/碳纳米管、聚苯胺),其电流都较普通导电涂层高。综合交流电化学阻抗及极化曲线结果得出,聚苯胺/碳纳米管添加量为1.0%,聚苯胺添加量为0.6%的涂层具有一定导电性能的同时,还具有较好的防腐性能。
Researchers in many countries devoted themselves to the study of environment friendly coatings in order to replace toxic coatings. Waterborne conductive polymer coatings have attracted much attention because of its non-toxic, non-pollution. The work is to provide scientific and experimental basis for waterborne conductive coatings. Synthesizing of conductive polymer with high conductivity and dispersing well in matrix resin are the key of the work.
In this paper, HC1 dopped PANI was synthesized via chemical oxidative polymerization, searched the optimum conditions, and then studied properties of CNT/PANI composites prepared by in-situ polymerizaton. The main results are summarized as follows:
(1) With An:APS's incresing, grain size and productive rate of PANI decreases. PANI synthesized with differernt An:APS and [An] performs similar. The better PANI dopped with when the temperature is lower and acid concentration is higher.The optimum conditions of synthesizing PANI is 1mol·L-1Hl,13℃, [An]=0.3-0.4mol·L-1, An:APS=0.8～0.9.
(2)Polyaniline in PANI/CNT composites is emeraldine dopped by HC1, PANI and CNT compound well, structure regularity of PANI/CNT improved obviously, but remain the same.
(3)Coatings added with PANI and PANI/CNT performs good impact resistance, and its conductive performance is improved,but the adhesion and surface morphology of the coatings is not ideal.
(4)Coatings added with conductive powder performs higher current density than the ordinary conductive coating. Overall,coatings added with 1.0%PANI,0.6%PANI performs certain electrical properties,and better anti-corrosion properties.
引文
[1]Yebra D M, Kiil S, Dam-Johansen K. Antifouling technology-past, present and future steps towards efficient and environmentally friendly antifouling coatings[J]. Progress in Organic Coatings,2004, (50):75-104.
[2]黄宗国.航洋无损生物及其防除.北京：海洋出版社,2008.
[3]Chambers L D, Stokes K R, Walsh F C et al. Modern approaches to marine antifouling coatings[J]. Surface & Coatings Technology,2006, (201):3642-3652.
[4]Deberry D W, Modification of the electrochemical and corrosion behavior of stainless-steels with an electroactive coating[J]. Journal of the Electrochemical Society,1985,132(5):1022-1026.
[5]王东红,刘利文.聚苯胺防腐性能及应用研究[J].防腐涂料与涂装,2011,26(10)：10-14.
[6]李应平,王献红,李季等.聚苯胺-新一代环境友好防腐材料[J].中国材料进展,2011,30(8)：17-23.
[7]Schauer T, Joos A, Dulog L et al. Protection of iron against corrosion with polyaniline primers[J]. Progress in Organic Coatings,1998,33(1):20-27.
[8]Jain F C, Rosato J J, Kalonia K S et al. Formation of an active electronic barrier at alsemiconductor interfaces-a novel-approach in Corrosion prevention[J]. Corrosion,1986,42(12):700-707.
[9]Yan M C, Tallman D E, Rasmussen S C et al. Corrosion control coatings for aluminum alloys based on Neutral and n-doped conjugated polymers[J]. Journal of the Electrochemical Society,2009,156(10):C360-C366.
[10]Lv Jinlong, Liu Nianjiang, Wang Xianhong et al. Mechanism and life study on polyaniline anti-corrosion coating[J]. Synthetic Metals,2003,135-136(4):237-238.
[11]Wessling B, Posdorfer J. Corrosion prevention with an organic metal(polyaniline):corrosion test results[J]. Electrochimica Acta,1999,44 (12):2139-2147.
[12]Wessling B. Dispersion as the link between basic research and commercial applications of conductive polymers(polyaniline)[J]Synthetic Metals,1998,93(2):143-154.
[13]Alam J,Riaz U, Ahmad S.High performance corrosion resistant polyaniline/alkyd ecofriendly coatings[J]. Current Applied Physics,2009,9(1):80-86.
[14]Bagherzadeh M R, Mahdavi F, Ghasemi M et al. Using nanoemeraldine salt-polyaniline for preparation of a new anticorrosive water-based epoxy coating[J]. Progress in Organic Coatings,2010,68(4):319-322.
[15]Li Ji,Lv Jinlong, Wang Xianhong. A polyaniline anti-corrosion coating and its preparation method. [P], CN03121402.2003.
[16]Wang Xianhong, Li Ji, Zhang Jinyong et al. Polyaniline as marine antifouling and corrosion-prevention agent[J]. Synthetic Metals,1999,102(1):1377-1380.
[17]孙祖信,叶章基,吴诤等.微米尺度内痕量C1O-浓度测定方法的研究[J].上海涂料,2001,(2)：3-7.
[18]金晓鸿.海洋污损生物防除技术和发展(111)-世界防污技术的历史和发展[J].材料开发与应用,2006,2：44-46.
[19]张占平,齐育红,刘述锡等.船舶防污涂料与防污剂的研究进展[J].大连水产学院学报,2006,21(2)：175-179.
[20]尾野真史著,边蕴静译.海洋涂料发展趋势[J].中国涂料,2005,20(3)：4-5.
[21]金光羊,金钟成,韩相秀等.海水电解型偏二氯乙烯-氯乙烯共聚树脂系列无公害防污涂料及其涂覆体系：中国,1385480[P].2001-05-11.
[22]丁凡,高宏,许丽敏.环境友好型海洋船舶防污涂料的研究进展[J].材料保护,2010,43(7)：47-49.
[23]孙祖信.聚苯胺及其防污涂料[J].船舶科学技术,1997,(3)：62-65.
[24]曹廷.船舶防污涂料的最新概况[J].论文精选,2005,6：60-61.
[25]王献红,孙祖信,耿延侯等.导电聚苯胺防污防腐涂料的制备方法.中国,[P],CN1215744.2002.
[26]孙博,邱星林.船舶防污涂料的研究现状及进展[J].广州化工,2008,36(3)：13-16.
[27]张建华.船体污损及处理方法[J].机电设备,2011,(4)：43-45.
[28]Huang J R,Lin W T, Huang R et al. Marine biofouling inhibition by polyurethane conductive coatings used for fishing net[J]. Journal of Coatings Technology and Research,2010,7(1):111-117.
[29]朱赞赞.功能化碳纳米管复合材料的构筑及在电催化中的应用：(硕士学位论文).兰州：兰州大学,2008.
[30]Srinivasan P, Amalraj J. Polyaniline materials by emulsion polymerization pathway[J]. Progress in Polymer Science,2008,33:732-758.
[31]Chao D M,Chen J Y, Lu X F et al.SEM study of the morphology of high molecular weight polyaniline[J]Synthetic Metals,2005,150:47-51.
[32]Wang X H, Li J, Zhang J Y et al. Polyaniline as marine antifouling and corrosion-prevention agent[J]. Synthetic Metals,1999,102:1377-1380.
[33]马利,汤琪.导电高分子材料聚苯胺的研究进展[J].重庆大学学报,2002,25(2)：124-127.
[34]曾幸荣,龚克成.聚苯胺的掺杂及其性能的研究[J].高分子材料科学与工程,1991,(6)：73.
[35]Kulikov A V, Bogatyrenko V R, Belonogova 0 V et al. ESR study of mechanism of polyaniline conductivity[J]. Russian Chemical Bulletin, Intenational Edition,2002.51(12):2216-2223.
[36]高宇.导电聚合物聚苯胺的研究进展[J].渝州大学学报,2001,18(1)：68-74.
[37]李新贵,高维威,黄美荣.含氟聚苯胺的合成及其特种功能修饰剂[J].精细化工,2005,22(6)：412-416.
[38]卢向军,窦辉,陈达Bronsted酸性离子液体掺杂聚苯胺的无溶剂制备及其表征[J].高分子学报,2009,4：385-389.
[39]Long Y Z, Chen Z J, Wang N L et al. Resistivity study of polyaniline doped with protonic acids[J]. Physica B-Condensed Matter,2003,325:208-213.
[40]赵玮婷.导电高分子聚苯胺的合成与掺杂及其对导电性能的研究：(硕士学位论文).北京：北京化工大学,2005.
[41]马利,王成章.导电聚苯胺材料的乳液聚合研究进展[J].包装工程,2002,23(4)：1-3.
[42]王杨勇,强军锋,井新利.聚苯胺防腐涂料的研究进展[J].宇航材料工艺,2002,(4)：1-6.
[43]王杨勇,强军锋,井新利等.导电高分子聚苯胺及其应用[J].化工新型材料,2003,31(3)：1-3.
[44]刘展晴.聚苯胺导电性能的研究进展[J].中国科技信息,2010,(6)：24-25.
[45]王科,张旺玺.导电聚苯胺的研究进展[J].合成技术及应用,2004,19(1)：23-27.
[46]曹丰,李东旭,管自生.导电高分子聚苯胺研究进展.材料导报,2007,21(8)：48-50.
[47]乔欣,杜建功,夏勇等.原位聚合法制备聚苯胺导电纤维的研究进展.现代纺织技术,2010,(4)：65-68.
[48]李秀秀,李晓东,杨荣杰.碳纳米管的功能化研究进展[J].炭素技术,2004,23(2)：23-27
[49]孙晓刚.碳纳米管／聚合物复合材料研究和应用进展[J].塑料,2003,32(5)：1-6
[50]Carroll D L, Redlich P, Ajayan P M et al. Electronic structure and localized states at carbon nanotubes[J], Physical Review Letters,1997,78(14):2811-2814.
[51]Goyanes S, Rubiolo G R, Salazar A et al. Carboxylation treatment of multiwalled carbon nanotubes monitored bu infrared and ultraviolet spectroscopies and scanning probe microscopy[J]. Diamond and Related Materials,2007,16(2):412-417.
[52]陈北明,杨德安.聚合物基复合材料制备中碳纳米管的分散方法[J].材料导报,2007,21：99-101.
[53]黄可龙.还原态与掺杂聚苯胺的制备及其防腐性能研究：(硕士学位论文).长沙：中南大学,2007.
[54]周震涛,刘芳,杨洪业等.(NH4)2S208体系聚苯胺合成结构与性能研究[J].华南理工大学学报,1995,23(2)：47-51.
[55]贺举.导电高分子聚苯胺的合成及其应用[J].科技信息,2008,18：391-392.
[56]杨小刚.聚苯胺纳米结构的制备及其防腐性能的研究：(博士学位论文).北京：中国科学院,2008.
[57]饶喜梅,许戈文,鲍俊杰等.聚苯胺／聚氨酯抗静电涂料的制备与性能研究.涂料工业,2007,37(2)：23-25.
[58]Pawar S G, Patil S L, Chougule M A. Microstructural and optoelectronic studies on polyaniline:TiO2 Nanocomposities [J]. International Journal of Polymeric Materials,2011,60:244-254.
[59]马娟娟,刘霖,朱绪飞等.盐酸掺杂聚苯胺的制备及性能研究[J].化学研究与应用,2007,19(11)：1233-1237.
[60]王杨勇,井新利,强军锋.聚苯胺／碳纳米管的原位复合[J].复合材料学 报,2004,21(3)：38-43.
[61]李丹丹.聚苯胺／碳纳米管复合材料的制备及性能研究：(硕士学位论文).天津：河北工业大学,2010.
[62]曾宪伟,赵东林.碳纳米管／聚苯胺复合材料的原位合成及其形成机理[J].碳素技术,2004,23(4)：15-19.
[63]赵晓峰,江奇,郭亚楠等.有机化学合成法制备碳纳米管／聚苯胺复合材料[J].无机材料学报,2010,25(1)：91-95.
[64]晁单明,陈靖禹,卢晓峰等.高分子量聚苯胺／碳纳米管复合材料的合成与表征[J].高等学校化学学报,2005,26(11)：2167-2178.
[65]史君君.聚苯胺及其复合材料的制备与性能研究：(硕士学位论文).天津：天津大学,2009.
[66]宿凯.聚苯胺／碳纳米管原位聚合：(硕士学位论文).黑龙江：黑龙江大学,2008.
[67]赵东宇,金政,宿凯等.碳纳米管／聚苯胺复合材料的制备及电性能[J].高分子材料科学与工程,2010,26(5)：133-135.
[68]陈金兰.导电高分子材料聚苯胺的合成及性能研究：(硕士学位论文).沈阳：沈阳理工大学,2007.
[69]哈恩华,黄大庆,哈恩平等.碳纳米管／导电聚合物纳米复合物的合成与表征[J].材料工程,2008,(10)：122-125.
[70]肖元化,唐新村,王志敏等.分级结构聚苯胺／多壁碳纳米管纳米复合物的制备、表征及其气敏性研究[J].无机材料学报,2010,25(10)：1092-1098.
[71]Ghatak S, Chakraborty G, Meikap A K et al. Synthesis and Characterization of polyaniline/carbon nanotube composites[J]. Applied Polymer,2011,119:1016-1025.
[72]Wu Tzong-ming, Lin Yen-wen, Liao Chien-Shiun. Doped polyaniline/multi-walled carbon nanotube composites:preparatation, characterization and properties [J]. Polymer,2006,47:3576-3582.
[73]郭俊鹏,谢政,连彦青等.水溶性聚苯胺／碳纳米管复合材料的制备及光限幅性能[J].清华大学学报,2009,49(6)：864-867.
[74]Panhuis M, Sainz R,Innis P C et al. Optically active polymer carbon nanotube composite[J]. Physical Chemistry B,2005,109(48):22725-22729.
[75]Sainz R, Benito A M,Martinez M T et al. Soluble self-aligned carbon nanotube/polyaniline composites[J]. Advanced Materials,2005,17(3):278-281.
[76]许军,姚(?),姜忠义等.磺化聚苯胺接枝多壁碳纳米管复合材料的结构与性能[J].天津大学学报,2011,44(4)：297-302.
[77]S.G.Pawar, S. L, Patil, M, A. Chougule. Microstructural and optoelectronic atudies on polyaniline:Ti02 Nanocomposites[J]. International Journal of Polymeric Materials,2011,60:244-254.
[78]Chaudhari H K, Kelkar D S. Electrochemical characteristics of anodically prepared conducting polyaniline films on carbon fiber supports [J].Polymer International,1997,42(4):380.
[79]许军,姚(?),邹云玲等.聚苯胺接枝多壁碳纳米管复合材料的结构与性能研究[J].材料导报,2010,24(1)：33-37.
[80]Feng W, Bai X D, Lian Y Q. Well-aligned polyaniline/carbon-nanotube composite films grown by in-situ aniline polymerization[J]. Carbon,2003,41 (8):1551.
[81]Gupta M C, Umare S S.Studies on poly(o-methoxyaniline)[J]. Macromolecules,1992,25(1):138-142.
[82]许军,刘利涛,姚(?)等.可溶性DBSA掺杂PANI接枝MWNTs复合材料的结构与性能[J].纳米技术与精密工程,2011,9(2)：105-112.
[83]刘家和.纳米聚苯胺的合成与性能研究：(硕士学位论文).重庆：重庆大学,2004.
[84]吴璐莹,游革新,赵润锋.掺杂聚苯胺填料改善环氧涂层的抗静电性能[J].腐蚀与防护,2009,30(9)：645-647.
[85]邱武高.有机硅海洋防污涂层研究：(硕士学位论文).大连：大连海事大学,2011.
[86]沈新元.高分子材料加工原理.北京：中国纺织出版社,2000.
[87]倪春花.防污涂层的组成设计及其防污作用研究：(硕士学位论文).青岛：中国海洋大学,2010.
[88]高焕方,张胜涛,彭超等.聚苯胺丙烯酸涂层的防腐蚀性能[J].腐蚀与防护,2010,31(5)：353-354.
[2]黄宗国.航洋无损生物及其防除.北京：海洋出版社,2008.
[3]Chambers L D, Stokes K R, Walsh F C et al. Modern approaches to marine antifouling coatings[J]. Surface & Coatings Technology,2006, (201):3642-3652.
[4]Deberry D W, Modification of the electrochemical and corrosion behavior of stainless-steels with an electroactive coating[J]. Journal of the Electrochemical Society,1985,132(5):1022-1026.
[5]王东红,刘利文.聚苯胺防腐性能及应用研究[J].防腐涂料与涂装,2011,26(10)：10-14.
[6]李应平,王献红,李季等.聚苯胺-新一代环境友好防腐材料[J].中国材料进展,2011,30(8)：17-23.
[7]Schauer T, Joos A, Dulog L et al. Protection of iron against corrosion with polyaniline primers[J]. Progress in Organic Coatings,1998,33(1):20-27.
[8]Jain F C, Rosato J J, Kalonia K S et al. Formation of an active electronic barrier at alsemiconductor interfaces-a novel-approach in Corrosion prevention[J]. Corrosion,1986,42(12):700-707.
[9]Yan M C, Tallman D E, Rasmussen S C et al. Corrosion control coatings for aluminum alloys based on Neutral and n-doped conjugated polymers[J]. Journal of the Electrochemical Society,2009,156(10):C360-C366.
[10]Lv Jinlong, Liu Nianjiang, Wang Xianhong et al. Mechanism and life study on polyaniline anti-corrosion coating[J]. Synthetic Metals,2003,135-136(4):237-238.
[11]Wessling B, Posdorfer J. Corrosion prevention with an organic metal(polyaniline):corrosion test results[J]. Electrochimica Acta,1999,44 (12):2139-2147.
[12]Wessling B. Dispersion as the link between basic research and commercial applications of conductive polymers(polyaniline)[J]Synthetic Metals,1998,93(2):143-154.
[13]Alam J,Riaz U, Ahmad S.High performance corrosion resistant polyaniline/alkyd ecofriendly coatings[J]. Current Applied Physics,2009,9(1):80-86.
[14]Bagherzadeh M R, Mahdavi F, Ghasemi M et al. Using nanoemeraldine salt-polyaniline for preparation of a new anticorrosive water-based epoxy coating[J]. Progress in Organic Coatings,2010,68(4):319-322.
[15]Li Ji,Lv Jinlong, Wang Xianhong. A polyaniline anti-corrosion coating and its preparation method. [P], CN03121402.2003.
[16]Wang Xianhong, Li Ji, Zhang Jinyong et al. Polyaniline as marine antifouling and corrosion-prevention agent[J]. Synthetic Metals,1999,102(1):1377-1380.
[17]孙祖信,叶章基,吴诤等.微米尺度内痕量C1O-浓度测定方法的研究[J].上海涂料,2001,(2)：3-7.
[18]金晓鸿.海洋污损生物防除技术和发展(111)-世界防污技术的历史和发展[J].材料开发与应用,2006,2：44-46.
[19]张占平,齐育红,刘述锡等.船舶防污涂料与防污剂的研究进展[J].大连水产学院学报,2006,21(2)：175-179.
[20]尾野真史著,边蕴静译.海洋涂料发展趋势[J].中国涂料,2005,20(3)：4-5.
[21]金光羊,金钟成,韩相秀等.海水电解型偏二氯乙烯-氯乙烯共聚树脂系列无公害防污涂料及其涂覆体系：中国,1385480[P].2001-05-11.
[22]丁凡,高宏,许丽敏.环境友好型海洋船舶防污涂料的研究进展[J].材料保护,2010,43(7)：47-49.
[23]孙祖信.聚苯胺及其防污涂料[J].船舶科学技术,1997,(3)：62-65.
[24]曹廷.船舶防污涂料的最新概况[J].论文精选,2005,6：60-61.
[25]王献红,孙祖信,耿延侯等.导电聚苯胺防污防腐涂料的制备方法.中国,[P],CN1215744.2002.
[26]孙博,邱星林.船舶防污涂料的研究现状及进展[J].广州化工,2008,36(3)：13-16.
[27]张建华.船体污损及处理方法[J].机电设备,2011,(4)：43-45.
[28]Huang J R,Lin W T, Huang R et al. Marine biofouling inhibition by polyurethane conductive coatings used for fishing net[J]. Journal of Coatings Technology and Research,2010,7(1):111-117.
[29]朱赞赞.功能化碳纳米管复合材料的构筑及在电催化中的应用：(硕士学位论文).兰州：兰州大学,2008.
[30]Srinivasan P, Amalraj J. Polyaniline materials by emulsion polymerization pathway[J]. Progress in Polymer Science,2008,33:732-758.
[31]Chao D M,Chen J Y, Lu X F et al.SEM study of the morphology of high molecular weight polyaniline[J]Synthetic Metals,2005,150:47-51.
[32]Wang X H, Li J, Zhang J Y et al. Polyaniline as marine antifouling and corrosion-prevention agent[J]. Synthetic Metals,1999,102:1377-1380.
[33]马利,汤琪.导电高分子材料聚苯胺的研究进展[J].重庆大学学报,2002,25(2)：124-127.
[34]曾幸荣,龚克成.聚苯胺的掺杂及其性能的研究[J].高分子材料科学与工程,1991,(6)：73.
[35]Kulikov A V, Bogatyrenko V R, Belonogova 0 V et al. ESR study of mechanism of polyaniline conductivity[J]. Russian Chemical Bulletin, Intenational Edition,2002.51(12):2216-2223.
[36]高宇.导电聚合物聚苯胺的研究进展[J].渝州大学学报,2001,18(1)：68-74.
[37]李新贵,高维威,黄美荣.含氟聚苯胺的合成及其特种功能修饰剂[J].精细化工,2005,22(6)：412-416.
[38]卢向军,窦辉,陈达Bronsted酸性离子液体掺杂聚苯胺的无溶剂制备及其表征[J].高分子学报,2009,4：385-389.
[39]Long Y Z, Chen Z J, Wang N L et al. Resistivity study of polyaniline doped with protonic acids[J]. Physica B-Condensed Matter,2003,325:208-213.
[40]赵玮婷.导电高分子聚苯胺的合成与掺杂及其对导电性能的研究：(硕士学位论文).北京：北京化工大学,2005.
[41]马利,王成章.导电聚苯胺材料的乳液聚合研究进展[J].包装工程,2002,23(4)：1-3.
[42]王杨勇,强军锋,井新利.聚苯胺防腐涂料的研究进展[J].宇航材料工艺,2002,(4)：1-6.
[43]王杨勇,强军锋,井新利等.导电高分子聚苯胺及其应用[J].化工新型材料,2003,31(3)：1-3.
[44]刘展晴.聚苯胺导电性能的研究进展[J].中国科技信息,2010,(6)：24-25.
[45]王科,张旺玺.导电聚苯胺的研究进展[J].合成技术及应用,2004,19(1)：23-27.
[46]曹丰,李东旭,管自生.导电高分子聚苯胺研究进展.材料导报,2007,21(8)：48-50.
[47]乔欣,杜建功,夏勇等.原位聚合法制备聚苯胺导电纤维的研究进展.现代纺织技术,2010,(4)：65-68.
[48]李秀秀,李晓东,杨荣杰.碳纳米管的功能化研究进展[J].炭素技术,2004,23(2)：23-27
[49]孙晓刚.碳纳米管／聚合物复合材料研究和应用进展[J].塑料,2003,32(5)：1-6
[50]Carroll D L, Redlich P, Ajayan P M et al. Electronic structure and localized states at carbon nanotubes[J], Physical Review Letters,1997,78(14):2811-2814.
[51]Goyanes S, Rubiolo G R, Salazar A et al. Carboxylation treatment of multiwalled carbon nanotubes monitored bu infrared and ultraviolet spectroscopies and scanning probe microscopy[J]. Diamond and Related Materials,2007,16(2):412-417.
[52]陈北明,杨德安.聚合物基复合材料制备中碳纳米管的分散方法[J].材料导报,2007,21：99-101.
[53]黄可龙.还原态与掺杂聚苯胺的制备及其防腐性能研究：(硕士学位论文).长沙：中南大学,2007.
[54]周震涛,刘芳,杨洪业等.(NH4)2S208体系聚苯胺合成结构与性能研究[J].华南理工大学学报,1995,23(2)：47-51.
[55]贺举.导电高分子聚苯胺的合成及其应用[J].科技信息,2008,18：391-392.
[56]杨小刚.聚苯胺纳米结构的制备及其防腐性能的研究：(博士学位论文).北京：中国科学院,2008.
[57]饶喜梅,许戈文,鲍俊杰等.聚苯胺／聚氨酯抗静电涂料的制备与性能研究.涂料工业,2007,37(2)：23-25.
[58]Pawar S G, Patil S L, Chougule M A. Microstructural and optoelectronic studies on polyaniline:TiO2 Nanocomposities [J]. International Journal of Polymeric Materials,2011,60:244-254.
[59]马娟娟,刘霖,朱绪飞等.盐酸掺杂聚苯胺的制备及性能研究[J].化学研究与应用,2007,19(11)：1233-1237.
[60]王杨勇,井新利,强军锋.聚苯胺／碳纳米管的原位复合[J].复合材料学 报,2004,21(3)：38-43.
[61]李丹丹.聚苯胺／碳纳米管复合材料的制备及性能研究：(硕士学位论文).天津：河北工业大学,2010.
[62]曾宪伟,赵东林.碳纳米管／聚苯胺复合材料的原位合成及其形成机理[J].碳素技术,2004,23(4)：15-19.
[63]赵晓峰,江奇,郭亚楠等.有机化学合成法制备碳纳米管／聚苯胺复合材料[J].无机材料学报,2010,25(1)：91-95.
[64]晁单明,陈靖禹,卢晓峰等.高分子量聚苯胺／碳纳米管复合材料的合成与表征[J].高等学校化学学报,2005,26(11)：2167-2178.
[65]史君君.聚苯胺及其复合材料的制备与性能研究：(硕士学位论文).天津：天津大学,2009.
[66]宿凯.聚苯胺／碳纳米管原位聚合：(硕士学位论文).黑龙江：黑龙江大学,2008.
[67]赵东宇,金政,宿凯等.碳纳米管／聚苯胺复合材料的制备及电性能[J].高分子材料科学与工程,2010,26(5)：133-135.
[68]陈金兰.导电高分子材料聚苯胺的合成及性能研究：(硕士学位论文).沈阳：沈阳理工大学,2007.
[69]哈恩华,黄大庆,哈恩平等.碳纳米管／导电聚合物纳米复合物的合成与表征[J].材料工程,2008,(10)：122-125.
[70]肖元化,唐新村,王志敏等.分级结构聚苯胺／多壁碳纳米管纳米复合物的制备、表征及其气敏性研究[J].无机材料学报,2010,25(10)：1092-1098.
[71]Ghatak S, Chakraborty G, Meikap A K et al. Synthesis and Characterization of polyaniline/carbon nanotube composites[J]. Applied Polymer,2011,119:1016-1025.
[72]Wu Tzong-ming, Lin Yen-wen, Liao Chien-Shiun. Doped polyaniline/multi-walled carbon nanotube composites:preparatation, characterization and properties [J]. Polymer,2006,47:3576-3582.
[73]郭俊鹏,谢政,连彦青等.水溶性聚苯胺／碳纳米管复合材料的制备及光限幅性能[J].清华大学学报,2009,49(6)：864-867.
[74]Panhuis M, Sainz R,Innis P C et al. Optically active polymer carbon nanotube composite[J]. Physical Chemistry B,2005,109(48):22725-22729.
[75]Sainz R, Benito A M,Martinez M T et al. Soluble self-aligned carbon nanotube/polyaniline composites[J]. Advanced Materials,2005,17(3):278-281.
[76]许军,姚(?),姜忠义等.磺化聚苯胺接枝多壁碳纳米管复合材料的结构与性能[J].天津大学学报,2011,44(4)：297-302.
[77]S.G.Pawar, S. L, Patil, M, A. Chougule. Microstructural and optoelectronic atudies on polyaniline:Ti02 Nanocomposites[J]. International Journal of Polymeric Materials,2011,60:244-254.
[78]Chaudhari H K, Kelkar D S. Electrochemical characteristics of anodically prepared conducting polyaniline films on carbon fiber supports [J].Polymer International,1997,42(4):380.
[79]许军,姚(?),邹云玲等.聚苯胺接枝多壁碳纳米管复合材料的结构与性能研究[J].材料导报,2010,24(1)：33-37.
[80]Feng W, Bai X D, Lian Y Q. Well-aligned polyaniline/carbon-nanotube composite films grown by in-situ aniline polymerization[J]. Carbon,2003,41 (8):1551.
[81]Gupta M C, Umare S S.Studies on poly(o-methoxyaniline)[J]. Macromolecules,1992,25(1):138-142.
[82]许军,刘利涛,姚(?)等.可溶性DBSA掺杂PANI接枝MWNTs复合材料的结构与性能[J].纳米技术与精密工程,2011,9(2)：105-112.
[83]刘家和.纳米聚苯胺的合成与性能研究：(硕士学位论文).重庆：重庆大学,2004.
[84]吴璐莹,游革新,赵润锋.掺杂聚苯胺填料改善环氧涂层的抗静电性能[J].腐蚀与防护,2009,30(9)：645-647.
[85]邱武高.有机硅海洋防污涂层研究：(硕士学位论文).大连：大连海事大学,2011.
[86]沈新元.高分子材料加工原理.北京：中国纺织出版社,2000.
[87]倪春花.防污涂层的组成设计及其防污作用研究：(硕士学位论文).青岛：中国海洋大学,2010.
[88]高焕方,张胜涛,彭超等.聚苯胺丙烯酸涂层的防腐蚀性能[J].腐蚀与防护,2010,31(5)：353-354.