化学氧化聚合法制备聚吡咯及其应用研究
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摘要
采用化学氧化聚合法在纤维素薄膜的孔隙中及表面上形成聚吡咯。研究不同氧化剂对聚吡咯／纤维素复合导电膜的电导率和热稳定性的影响以及对铝氧化膜的腐蚀作用。结果表明，过硫酸铵是适合用于聚吡咯铝电解电容器制作的氧化剂。
研究了不同掺杂剂制备的复合导电膜的电导率、热稳定性及阻抗一频率特性。结果表明，使用TSA为掺杂剂时，电导率最高；使用SDS、DBSA或HCl为掺杂剂时，热稳定性增强；使用HCl或DBSA为掺杂剂时，阻抗随频率升高而下降。研究了外加电场对复合导电膜电导率的影响，结果表明，电导率随着场强的增加而降低。合成了聚吡咯粉末并研究了其热老化情况。结果表明，氧会加速聚吡咯老化。
制作了聚吡咯铝电解电容器，研究了其各项性能及制作工艺。
PPy was synthesized in the mesh and on the surface of cellulose membrane by oxidative chemical polymerization. The effect of various oxidants on the conductivity and thermal stability of PPy/cellulose composite conducting membrane were investigated. The corrosive action of various oxidants on the aluminum oxide foil was studied. The results show that (NH4)2S2O8 was the appropriate oxidant used in the preparation of aluminum electrolytic capacitors with PPy electrolyte.
The conductivity, thermal stability and impedance-frequency characteristics of composite conducting membrane prepared by various dopants were investigated. The results show that the conductivity reached the highest when TSA was used as a dopant, the thermal stability was enhanced when SDS, DBSA or HC1 was used as a dopant, the impedance became lower with the increase of frequency when the HC1 or DBSA was used as a dopant. The effect of the applied electric field on the conductivity of composite conducting membrane was also investigated. The results show that the conductivity lowered with the increase of the applied electric field intensity. PPy powder was synthesized and its thermal aging characteristics were studied. The results show that the aging of PPy proceeded much faster in the presence of oxygen than in its absence.
Aluminum electrolytic capacitors with PPy electrolyte were fabricated. The properties of capacitors were studied. The technological process of preparation of capacitors were investigated.
研究了不同掺杂剂制备的复合导电膜的电导率、热稳定性及阻抗一频率特性。结果表明，使用TSA为掺杂剂时，电导率最高；使用SDS、DBSA或HCl为掺杂剂时，热稳定性增强；使用HCl或DBSA为掺杂剂时，阻抗随频率升高而下降。研究了外加电场对复合导电膜电导率的影响，结果表明，电导率随着场强的增加而降低。合成了聚吡咯粉末并研究了其热老化情况。结果表明，氧会加速聚吡咯老化。
制作了聚吡咯铝电解电容器，研究了其各项性能及制作工艺。
PPy was synthesized in the mesh and on the surface of cellulose membrane by oxidative chemical polymerization. The effect of various oxidants on the conductivity and thermal stability of PPy/cellulose composite conducting membrane were investigated. The corrosive action of various oxidants on the aluminum oxide foil was studied. The results show that (NH4)2S2O8 was the appropriate oxidant used in the preparation of aluminum electrolytic capacitors with PPy electrolyte.
The conductivity, thermal stability and impedance-frequency characteristics of composite conducting membrane prepared by various dopants were investigated. The results show that the conductivity reached the highest when TSA was used as a dopant, the thermal stability was enhanced when SDS, DBSA or HC1 was used as a dopant, the impedance became lower with the increase of frequency when the HC1 or DBSA was used as a dopant. The effect of the applied electric field on the conductivity of composite conducting membrane was also investigated. The results show that the conductivity lowered with the increase of the applied electric field intensity. PPy powder was synthesized and its thermal aging characteristics were studied. The results show that the aging of PPy proceeded much faster in the presence of oxygen than in its absence.
Aluminum electrolytic capacitors with PPy electrolyte were fabricated. The properties of capacitors were studied. The technological process of preparation of capacitors were investigated.
引文
1 何天白，胡汉杰．功能高分子与新技术．北京：化学工业出版社，2001
2 刘霖．导电聚苯胺的合成及其在电解电容器中的应用 (学位论文)．南京：南京理工大学，2004
3 马建标，李晨曦．功能高分子材料．北京：化学工业出版社，2000
4 陈国华，颜文礼．化学法合成导电聚吡咯的研究现状．华侨大学学报 (自然科学版)．1994，15 (2)：172-176
5 I. Mogi, K. Watanabe, M. Motokawa. Magneto-electropolymerization of conducting polypyrrole. Physica B. 1998, 246-247:412-415
6 邢存章，于跃芹．有机化学．济南：山东大学出版社，2001
7 焦剑，雷渭媛．高聚物结构、性能与测试．北京：化学工业出版社，2003
8 蓝立文．功能高分子材料．西安：西北工业大学出版社，1995
9 Yongfang Li, Gufeng He. Effect of preparation conditions on the two doping structures of polypyrrole. Synthetic Metals. 1998, 94 (1):127-129
10 Lin-Xia Wang, Xin-Gui Li, Yu-Liang Yang. Praparation, properties and applications of polypyrroles. Reactive & Functional Polymers. 2001, 47 (2): 125-139
11 尹五生．聚吡咯导电材料合成方法的进展．功能材料．1996，27 (2)：97-102
12 徐友龙，季锐，王飞．影响掺杂聚吡咯 (PPy) 导电性能的因素．电子元件与材料．2000，19 (5)：17-19
13 A. Malinauskas. Chemical deposition of conducting polymers. Polymer. 2001, 42 (9):3957-3972
14 Matthew C. Henry, Chen-Chan Hsueh, Brian P. Timko, et al.. Reaction of Pyrrole and Chlorauric acid. Journal of The Electrochemical Society. 2001, 148 (11):D155-D162
15 万本强，吴婉群．催化电合成聚吡咯的电化学性质研究．西南师范大学学报 (自然科学版)．1993，18 (1)：52-55
16 方惠群，王美全，陈洪渊．微电极研究—吡咯在微电极上的聚合及膜的生长过程．化学学报．1995，53 (8)：789-795
17 程发良，宁满霞，莫金垣等．水介质中吡咯的电化学聚合反应．分析测试学报．2002，21 (4)：30-33
18 高劲松，田中群．十二烷基苯磺酸钠掺杂的聚吡咯的电化学和现场拉曼光谱．厦门大学学报 (自然科学版)．1995，34 (2)：226-233
19 郑玉斌，张善举，柯杨船等．电聚合导电聚吡咯的合成研究．功能高分子学报．1996，9 (4)：613-615
20 陈凤恩，石高全，徐景坤等．拉曼光谱研究电化学沉积聚吡咯掺杂程度对膜厚度的依赖性．光散射学报．2002，14 (1)：54-57
21 Jianyong Ouyang, Yongfang Li. Great improvement of polypyrrole films prepared electrochemically from aqueous solutions by adding nonaphenol polyethyleneoxy (10)ether. Polymer. 1997, 38 (15):3997-3999
22 S.J. Sutton, A.S. Vaughan. On the morphology and growth of electrochemically polymerized polypyrrole. Polymer. 1995, 36 (9):1849-1857
23 贝建中，钱人元．在水溶液中电化学反应制备大面积聚吡咯膜．功能高分子学报．1991，4 (4)：320-324
24 Gouri Smitha Akundy, Jude O. Iroh. Polypyrrole coatings on aluminum-synthesis and characterization. Polymer. 2001, 42 (24):9665-9669
25 胡明，张景阳，郝嘉林等．新型铝电解电容器中导电聚吡咯对电极的形成．天津大学学报．2000，33 (2)：231-235
26 吴宇平，万春荣，姜长印等．锂离子二次电池．北京：化学工业出版社，2002
27 薛奇，严锋，陆云等．层状复合磁性导电聚合物膜及其制备方法．CN-98111335．4，1999-12-08
28 万梅香，李军朝，李素珍．一种导电高聚物微波吸收剂及其制法．CN-99100651．8，2000-08-16
29 P．J．金伦，D．C．西弗曼，C．J．哈迪曼．抑制腐蚀的多层涂料．CN-94192848．9，199B-07-24
30 Dilek Kincal, Anil Kumar, Andrew D. Child, et al..Conductivity switching in polypyrrole-coated textile fabrics as gas sensors. Synthetic Metals. 1998, 92 (1):53-56
31 林学清，洪雪宝．铝电解电容器工程技术．厦门：厦门大学出版社，2002
32 小沼博，白根浩朗，门田隆二等．固体电解电容器及其制造方法．CN-98803803．X，2001-05-30
33 Hellwig, Gerhard, Baur et al..Solid-state capacitor with an electroconductive polymer as constituent of the solid electrolyte. US-4 803 596, 1989-02-07
34 Jonas, Friedrich, Heywang et al..Solid electrolytes and electrolyte capacitors containing same. US-4 910 645, 1990-03-20
35 Kudoh, Yasuo, Tsuchiya et al..Solid electrolytic capacitor and method of
manufacturing the same. US-4 959 753, 1990-09-25
36 M. Satoh, H. Ishikawa, H. Yageta, et al..Structure and properties of polypyrrole synthesized under air and oxygen-free conditions. Synthetic Metals. 1997, 84 (1-3):167-168
37 张庆武，周啸，姜翠玲等．铝固体电解电容器电解质研究进展Ⅱ．导电聚合物型铝固体电解电容器．电子元件与材料．2002，21 (11)：24-27
38 新田幸弘，森义幸，诸隈宗宏等．固体电解电容器及其制造方法和导电性聚合物聚合用的氧化剂溶液．CN-00801780．8，2001-11-07
39 白根浩朗，门田隆二，坂井厚等．导电性聚合物固体电解电容器及其制造方法．CN-99801076．6，2000-11-15
40 小泽正人．固体电解电容器的制作方法及其制造装置．CN-02104604．2，2002-09-25
41 Dal-Woo Shin, Cheongju, Jong-Joo Park et al..Method for manufacturing solid electrolytic capacitor using functional polymer electrolytic composition. US-6 454 817 B1, 2002-09-24
42 山田和明，本田伸浩．固体电解电容器及其制造方法和制造装置．CN-01101528．4，2001-08-01
43 M.S. Kim, H.K. Kim, S.W. Byun, et al..PET fabric/polypyrrole composite with high electrical conductivity for EMI shilding. Synthetic Metals. 2002, 126 (2-3):233-239
44 李言荣，恽正中．电子材料导论．北京：清华大学出版社，2001
45 徐友龙，王杰，秦继伟．影响聚吡咯铝电解电容器漏电流的因素及改进措施．西安交通大学学报．2002，36 (3)：300-304
46 吴瑞山，王兆宏，李晖等．阳极氧化膜形成液中的氯离子检测．电子元件与材料．2001，20 (5)：14-15
47 Jianyong Ouyang, Yongfang Li. Enhancement of the electrical conductivity of polypyrrole films on applying higher voltage. Synthetic Metals. 1995, 75 (1):1-3
48 Jaroslav Stejskal, Mária Omastová, Svetlana Fedorova, et al..Polyaniline and polypyrrole prepared in the presence of surfactants:a comparative conductivity study. Polymer. 2003, 44 (5):1353-1358
49 H.C. Kang, K.E. Geckeler. Enhanced electrical conductivity of polypyrrole prepared by chemical oxidantive polymerization:effect of the preparation technique and polymer additive. Polymer. 2000, 41 (18):6931-6934
50 赵文元，王亦军．功能高分子材料化学．北京：化学工业出版社，1996
51 陆昌伟，奚同庚．热分析质谱法．上海：上海科学技术文献出版社，2002
52 Jude O. Iroh, Greg A. Wood. Control of carbon fiber-polypyrrole interphases by aqueous electrochemical process. Composites PartB: engineering. 1998, 29 (2):181-188
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54 江建民，戚慰先，仲蕾兰等．化学氧化聚吡咯的结构及导电性的研究．中国纺织大学学报．1991，17 (1)：38-44
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56 荆煦瑛，陈式棣，么恩云．红外光谱实用指南．天津：天津科学技术出版社，1992
57 Yongfang Li, Renyuan Qian. Electrochemical overoxidation of conducting polypyrrole nitrate film in aqueous solutions. Electrochimica Acta. 2000, 45 (11):1727-1731
58 G. I. Mathys, V.T. Truong. Spectroscopic study of thermo-oxidative degradation of polypyrrole powder by FT-IR. Synthetic Metals. 1997, 89 (2):103-109
59 J.Y. Lee, D.Y. Kim, C.Y. Kim. Synthesis of soluble polypyrrole of the doped state in organic solvents. Synthetic Metals. 1995, 74 (2):103-106
60 季锐，徐友龙．聚吡咯固体电解电容器．电子元件与材料．1999，18 (4)：4-6
61 雷彤，赵孔双．导电高分子膜的电化学阻抗谱研究进展．化学通报．2001，64 (1)：11-16
62 刘江，宋永辉，兰新哲．片状银粉的制备研究．有色金属．2002，54 (B07)：64-68
63 杨守生．银系复合导电膏的研制．云南化工．2000，27 (6)：1-2
64 杨小峰，洪衍涛．环氧—低分子聚酰胺—银粉导电胶体系的研究．中国胶粘剂．1995，5 (5)：12-16
65 Katsuhiko Naoi, Masayuki Takeda, Hiroshi Kanno, et al..Simultaneous electrochemical formation of Al_2O_3/polypyrrole layers (Ⅰ):effect of electrolyte anion in formation process. Electrochimica Acta. 2000,45 (20):3413-3421
2 刘霖．导电聚苯胺的合成及其在电解电容器中的应用 (学位论文)．南京：南京理工大学，2004
3 马建标，李晨曦．功能高分子材料．北京：化学工业出版社，2000
4 陈国华，颜文礼．化学法合成导电聚吡咯的研究现状．华侨大学学报 (自然科学版)．1994，15 (2)：172-176
5 I. Mogi, K. Watanabe, M. Motokawa. Magneto-electropolymerization of conducting polypyrrole. Physica B. 1998, 246-247:412-415
6 邢存章，于跃芹．有机化学．济南：山东大学出版社，2001
7 焦剑，雷渭媛．高聚物结构、性能与测试．北京：化学工业出版社，2003
8 蓝立文．功能高分子材料．西安：西北工业大学出版社，1995
9 Yongfang Li, Gufeng He. Effect of preparation conditions on the two doping structures of polypyrrole. Synthetic Metals. 1998, 94 (1):127-129
10 Lin-Xia Wang, Xin-Gui Li, Yu-Liang Yang. Praparation, properties and applications of polypyrroles. Reactive & Functional Polymers. 2001, 47 (2): 125-139
11 尹五生．聚吡咯导电材料合成方法的进展．功能材料．1996，27 (2)：97-102
12 徐友龙，季锐，王飞．影响掺杂聚吡咯 (PPy) 导电性能的因素．电子元件与材料．2000，19 (5)：17-19
13 A. Malinauskas. Chemical deposition of conducting polymers. Polymer. 2001, 42 (9):3957-3972
14 Matthew C. Henry, Chen-Chan Hsueh, Brian P. Timko, et al.. Reaction of Pyrrole and Chlorauric acid. Journal of The Electrochemical Society. 2001, 148 (11):D155-D162
15 万本强，吴婉群．催化电合成聚吡咯的电化学性质研究．西南师范大学学报 (自然科学版)．1993，18 (1)：52-55
16 方惠群，王美全，陈洪渊．微电极研究—吡咯在微电极上的聚合及膜的生长过程．化学学报．1995，53 (8)：789-795
17 程发良，宁满霞，莫金垣等．水介质中吡咯的电化学聚合反应．分析测试学报．2002，21 (4)：30-33
18 高劲松，田中群．十二烷基苯磺酸钠掺杂的聚吡咯的电化学和现场拉曼光谱．厦门大学学报 (自然科学版)．1995，34 (2)：226-233
19 郑玉斌，张善举，柯杨船等．电聚合导电聚吡咯的合成研究．功能高分子学报．1996，9 (4)：613-615
20 陈凤恩，石高全，徐景坤等．拉曼光谱研究电化学沉积聚吡咯掺杂程度对膜厚度的依赖性．光散射学报．2002，14 (1)：54-57
21 Jianyong Ouyang, Yongfang Li. Great improvement of polypyrrole films prepared electrochemically from aqueous solutions by adding nonaphenol polyethyleneoxy (10)ether. Polymer. 1997, 38 (15):3997-3999
22 S.J. Sutton, A.S. Vaughan. On the morphology and growth of electrochemically polymerized polypyrrole. Polymer. 1995, 36 (9):1849-1857
23 贝建中，钱人元．在水溶液中电化学反应制备大面积聚吡咯膜．功能高分子学报．1991，4 (4)：320-324
24 Gouri Smitha Akundy, Jude O. Iroh. Polypyrrole coatings on aluminum-synthesis and characterization. Polymer. 2001, 42 (24):9665-9669
25 胡明，张景阳，郝嘉林等．新型铝电解电容器中导电聚吡咯对电极的形成．天津大学学报．2000，33 (2)：231-235
26 吴宇平，万春荣，姜长印等．锂离子二次电池．北京：化学工业出版社，2002
27 薛奇，严锋，陆云等．层状复合磁性导电聚合物膜及其制备方法．CN-98111335．4，1999-12-08
28 万梅香，李军朝，李素珍．一种导电高聚物微波吸收剂及其制法．CN-99100651．8，2000-08-16
29 P．J．金伦，D．C．西弗曼，C．J．哈迪曼．抑制腐蚀的多层涂料．CN-94192848．9，199B-07-24
30 Dilek Kincal, Anil Kumar, Andrew D. Child, et al..Conductivity switching in polypyrrole-coated textile fabrics as gas sensors. Synthetic Metals. 1998, 92 (1):53-56
31 林学清，洪雪宝．铝电解电容器工程技术．厦门：厦门大学出版社，2002
32 小沼博，白根浩朗，门田隆二等．固体电解电容器及其制造方法．CN-98803803．X，2001-05-30
33 Hellwig, Gerhard, Baur et al..Solid-state capacitor with an electroconductive polymer as constituent of the solid electrolyte. US-4 803 596, 1989-02-07
34 Jonas, Friedrich, Heywang et al..Solid electrolytes and electrolyte capacitors containing same. US-4 910 645, 1990-03-20
35 Kudoh, Yasuo, Tsuchiya et al..Solid electrolytic capacitor and method of
manufacturing the same. US-4 959 753, 1990-09-25
36 M. Satoh, H. Ishikawa, H. Yageta, et al..Structure and properties of polypyrrole synthesized under air and oxygen-free conditions. Synthetic Metals. 1997, 84 (1-3):167-168
37 张庆武，周啸，姜翠玲等．铝固体电解电容器电解质研究进展Ⅱ．导电聚合物型铝固体电解电容器．电子元件与材料．2002，21 (11)：24-27
38 新田幸弘，森义幸，诸隈宗宏等．固体电解电容器及其制造方法和导电性聚合物聚合用的氧化剂溶液．CN-00801780．8，2001-11-07
39 白根浩朗，门田隆二，坂井厚等．导电性聚合物固体电解电容器及其制造方法．CN-99801076．6，2000-11-15
40 小泽正人．固体电解电容器的制作方法及其制造装置．CN-02104604．2，2002-09-25
41 Dal-Woo Shin, Cheongju, Jong-Joo Park et al..Method for manufacturing solid electrolytic capacitor using functional polymer electrolytic composition. US-6 454 817 B1, 2002-09-24
42 山田和明，本田伸浩．固体电解电容器及其制造方法和制造装置．CN-01101528．4，2001-08-01
43 M.S. Kim, H.K. Kim, S.W. Byun, et al..PET fabric/polypyrrole composite with high electrical conductivity for EMI shilding. Synthetic Metals. 2002, 126 (2-3):233-239
44 李言荣，恽正中．电子材料导论．北京：清华大学出版社，2001
45 徐友龙，王杰，秦继伟．影响聚吡咯铝电解电容器漏电流的因素及改进措施．西安交通大学学报．2002，36 (3)：300-304
46 吴瑞山，王兆宏，李晖等．阳极氧化膜形成液中的氯离子检测．电子元件与材料．2001，20 (5)：14-15
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