聚苯胺的化学合成及其性能表征
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摘要
本课题采用溶液体系和乳液体系在不同工艺条件下制备了导电聚苯胺；采用掺杂-脱掺杂-再掺杂的技术路线，分别用溶液法及机械研磨法对本征态聚苯胺进行了再掺杂研究。采用XRD、TGA、DTA与FI-IR等分析手段对聚苯胺进行了表征和性能分析。并对聚苯胺在不同溶剂中紫外-可见光谱进行了详细的探索。研究了反应时间、反应温度、氧化剂用量和掺杂剂浓度等工艺条件对聚苯胺各项性能的影响，重点研究了聚苯胺的电导率和溶解性。结果表明：溶液法再掺杂聚苯胺有良好的电导率、溶解性及热稳定性。机械研磨法再掺杂聚苯胺的电导率较高，乳液法制备的聚苯胺溶解性较好，乳液-萃取法制备了可直接使用的聚苯胺溶液，使加工性得到了改善。
Polyaniline were prepared using solution system and emulsion system in different technical condition. Solution re-doped PANI and mechanical mixing re-doped PANI were used and researched by the technique route of dope -de-dope-re-dope PANI. Theoretical analysis was carried out, and PANI was characterized by several inspecting methods such as four-point probe conductivity measurements, XRD, TGA, DTA and FI-IR. And the UV-Vis spectra properties of PANI in different solvents were explored. The effects of technical conduction such as reaction time, reaction temperature, oxidant and dopant on several capabilities of PANI were studied, especially the conductivity and solubility. The results show that re-dope PANI has good conductivity, solubility and better thermal stability than literature. High conductivity is acquired using mechanical mixing re-dope PANI and excellent solubility is attained using emulsion polymerization. PANI solution can be prepared by emulsion polymerization-extract method and it can improve t
he process capability.
Polyaniline were prepared using solution system and emulsion system in different technical condition. Solution re-doped PANI and mechanical mixing re-doped PANI were used and researched by the technique route of dope -de-dope-re-dope PANI. Theoretical analysis was carried out, and PANI was characterized by several inspecting methods such as four-point probe conductivity measurements, XRD, TGA, DTA and FI-IR. And the UV-Vis spectra properties of PANI in different solvents were explored. The effects of technical conduction such as reaction time, reaction temperature, oxidant and dopant on several capabilities of PANI were studied, especially the conductivity and solubility. The results show that re-dope PANI has good conductivity, solubility and better thermal stability than literature. High conductivity is acquired using mechanical mixing re-dope PANI and excellent solubility is attained using emulsion polymerization. PANI solution can be prepared by emulsion polymerization-extract method and it can improve t
he process capability.
引文
1 王利祥，王佛松．导电聚苯胺的研究进展：合成链结构和凝聚态结构．应用化学．1990，7(5)：1～10
2 Labes Mm, love P, Nichols LF. Polysulfer nitride-a metallic superconducting Polymer. Chem Rev. 1979:79(1), 1
3 Shirakawa H. Synthesis of Electrically Organic Polymers: Halogen Derivatives of Polyacetylene.(CH)x J.L.S. Chem.Comm.. 1977: 578-580
4 李英，赵地顺．导电高分子材料．河北科技大学学报．2000，21(2)：9-12
5 朱道本，王佛松．有机固体．上海：上海科学技术出版社，1999
6 殷敬华．现代高分子物理学(上册)．北京：科学出版社，2001
7 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
8 王慧中，王荣顺，赵大成等．掺杂聚苯胺能带结构和导电机理的研究，高等学校化学学报．1991．12(9)：1229～1233
9 MacDiarmid A G, Chiang J C, Richter A F, et al. Polyanilne: a new concept in conducting polymers. Synth Met. 1988,25(2): 121～137
10 Konshin Takahashi, Kunihiro Nakamura, et al. Characterization of water-souble externally HCl-doped conductivity polyaniline. Synth.Met. 2002,128: 27～33
11 生瑜，陈建宝，朱德钦．二氧化锰化学氧化法合成导电聚苯胺．功能高分子学报．2002，15(4)：383-390
12 曾幸荣，龚克成．聚苯胺的掺杂及其性能的研究．高分子材料科学与工程．1991，6：73
13 Seddique M. Ahmed. Preparation and degradation of highly conducting polyaniline doped with picric acid. European Polymer Journal.2002,38: 1151～1158
14 Chiang J C. MacDiarmid A G.. Polyaniline, Protonic acid doping of emerldine form to the metallic regine. Synth Met. 1986, 13(1-3): 193-205
15 Yong Cao, Paul Smith, Alan J Heeger. Processible forms of electrically conductive polyaniline[P].US Patent: 5624605,1997
16 Patrick J. Emulsion-polymerization process and electrically conductive polyaniline[P].US Patent: 5863465,1999
17 Chen-chang Chen. Miscible forms of electrically conductive polyaniline[P].US Patent: 5670607, 1997
18 井新利，郑茂盛，蓝立文．反向微乳液法合成导电聚苯胺纳米粒子．高分子材料科学与工程．2000，16(2)：23-25
19 阳范文，唐建斌．导电聚苯胺的微乳液聚合．桂林工学院学报．2002，20(3)：
264-266
20 Diaz A F, Logan J A. Electroactive polyaniline film. Electrical Chem. 1980,111(1): 111
21 张超灿，宋丽娜，单松高等．嵌段及接枝改性导电聚苯胺的研究进展．材料导报．2001，15(7)：53-55
22 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．1997，3：22-28
23 刘学习，曾幸荣，杨伟，龚克成．聚苯乙烯磺酸掺杂聚苯胺的合成．功能高分子学报．2002，15(3)：73-76
24 J.Gong, Z.M.Su, Z.M.Dai et al. Synthesis, characterization and polyaniline doped with H_5SiM_(11)VO_(40) (M=Mo, W) Synth.Met.1999, 101: 751
25 Caimao Zhan, Jianjun Zeng, Yuliang Li, XiYang, Jingui Qin. Synthesis and characterization of polyaniline catalysed and doped by squaric acid. Synth.Met. 1999, 101: 731
26 乔庆东，王胜．新型共混DBSA掺杂的聚苯胺导电胶的合成．精细化工．1999．16：35-38
27 Dai Liming, Wang Qian, Wan Meixiang. Direct observation of conformational transitions for polyaniline chains intercalated in clay particles upon secondary doping. Journal of Material Science Letters. 2000(9): 1645～1647
28 牛林，陈晓，魏丰华．导电聚合物的结构与性能表征方法．功能高分子学报．2002，15(1)：91-97
29 王佛松，唐劲松，景遐斌．可溶性聚苯胺的合成及研究，高分子学报．1987，5：384～388
30 Kuo P L, Wey B S, Chen W H. Functional polymers for colloidal application. LX. The dispersing ability of copolymers as photo acid Zwitterionic aniline-formaldehyde condensates to dyes. J Appl Polym Sci.1993, 48(11): 1953～1961
31 江明，府寿宽．高分子科学的近代论题．上海：复旦大学出版社，1998
32 Gospodinova N, Terlemezyan L. Conducting polymers prepared by oxidative polymerization: polyaniline. Progr Polym Sci.. 1998,23(8): 1443～1483
33 Armes S P, Miller J F. Optimum reaction conditions for the polymerization of aniline in aqueous solution by ammonium persulphate. Synth Met. 1988,22(4): 385～389
34 Wang X H, Li J, Wang L X, et al. Synthesis and characterization of chlorinated
polyaniline. Synth Met. 1995, 69(1～3): 149～150
35 Cao Y, Andreatta A, Heeger A J, et al, Influence of chemical polymerization condition on the properties of polyaniline. Polymer. 1989, 30: 2305～2311
36 P.Rannou, M. Nechtschein, J.P. Travers, et al. Age of PANI: chemical, structure and transport consequences. Synth Met. 1999,101: 734～737
37 Cheng-Ho Chen. Thermal Studied of polyaniline doped with DBSA directly prepared via aqueous dispersions. Journal of polymer research. 2002,9: 1995～200
38 C L Gettinger, A J Heeger, D J Pine and Y Cao. Solution characterization of surfactant solubilized polyaniline. Synth Met. 1995, 70: 81～88
39 Anjali A. et al. Studies on chemically synthesized soluble acrylic acid doped polyaniline. Materials chemistry and physics.2002,73: 106～110
40 Yen Wei, Kesyin F. Hsueh, Guang-way Jang, A study of leucoemeraldine and the effect of redox reaction on the molecular weight of chemically prepared polyaniline. Macromolecules. 1994,27: 518～525
41 Dvid W.Hatchett. et al. Acid doping of polyaniline: spectroscopic and electrochemical studies.J.Phys.Chem.B. 1999,103: 10992～10998
42 Anton J. Dominis, Geoffrey M. Spinks. et al. A de-doping/re-doping study of organic soluble polyaniline. Synth Met.2002,129: 165～172
43 L.H.Huo, L.X.Cao, D.M.Wang. et al. Preparation and characterization of doped polyaniline films. Thin solid films. 1999, 350: 5～9
44 Pereira da silva, J.E.Temperini, M.L.A, Cordoba de Torresi, S.L. Secondary doping of polyaniline studied by resonance Raman spectroscopy. Electrochemica Acta. 1999,12: 1887～1891
45 P.Rannou, M. Nechtschein. Aging studies on polyaniline: conductivity and thermal stability. Synth Met. 1997, 84
46 X H Wang, Y H Geng, L X Wang X B Jing, F S Wang. Thermal behavior ofdeped polyaniline. Synth Met. 1995, 69: 265～266
47 Yin Wusheng, Ruckenstein EIL. Soluble polyaniline co-doped with dodecyl benzene sulfonic acid and hydrochloric acid. Synth Met.2000, 108: 39～46
48 W H Jang. et al. Synthesis and electrorheology of camphor sulfonic acid doped polyaniline suspensions. Colloid Polym Sci.2001,279: 823～827
49 K levon, K H Ho, W Y Zheng, et al. Thermal doping of polyaniline with dodecylbenzene sulfonic acid without auxiliary solvents. Polymer. 1994,36(14): 2733～2738
50 P.J.Kinlen. et al. Synthesis and characterization of organically soluble and polyaniline block copolymers. Synth Met. 1999, 101: 758～761
51 Xuehong Lu, Chiang Yang Tan, Jianwei Xu, Chaobin He. Thermal degradation of electrical conductivity of polyacrylic acid doped polyaniline: effect of molecular weight of the dopants. Synth Met.2003, 138: 429～440
52 P. Swapna Rao et al. Inverse emulsion polymerization: a new route for the synthesis of conducting polyaniline. Synth Met.2002, 128: 311～316
53 Chin-Tsoukuo, Show-An Chen. Comparison of electroluminescent quantum efficiencies of PPV and a PPV-related alternating block copolymer. Synth Met.1998, 93: 156～157
54 Pokhodenko V.D., Kurys Ya.L.,Posudievsky O.Yu. Heteropolyacid/m-cresol system as a primary/secondary dopant combination for polyaniline. Synth Met.2001, 1: 199～201
55 Cao Y. et al. Electrically conducting polyaniline: Method fou emulsion polymerization.Wo,94,03252B
56 郑裕东，李吉波，黄炯亮．乳液聚合法合成聚苯胺的结构及性能研究．高分子材料科学与工程．1996，12(6)：30～31
57 Byoung Jin Kim, Seong Geun Oh, Moon-Gyu Han,Seung-Soon Im. Synthesis and characterization of polyaniline nanoparticles in SDS micellar solutions. Synth Met.2001, 122: 297～304
58 L.W.Shacklette, R.L.Elsenbaumer, R.R.Chance, H.Eckhardt, J.E.Frommer, R.H.Baughman. Conducting complexes of polyphenylent sulfides. J Chem Phys. 1981,75(4): 1919～1927
59 H.Sato, J.Tanaka, K.Kaeriyama, Souble conducting polythiophenes. J.Chem.Soc.,Chem.Commun. 1986,11: 873～874
60 [德]赖卡特著，唐培方译．有机化学中的溶剂效应．北京：化学工业出版社，1987
2 Labes Mm, love P, Nichols LF. Polysulfer nitride-a metallic superconducting Polymer. Chem Rev. 1979:79(1), 1
3 Shirakawa H. Synthesis of Electrically Organic Polymers: Halogen Derivatives of Polyacetylene.(CH)x J.L.S. Chem.Comm.. 1977: 578-580
4 李英，赵地顺．导电高分子材料．河北科技大学学报．2000，21(2)：9-12
5 朱道本，王佛松．有机固体．上海：上海科学技术出版社，1999
6 殷敬华．现代高分子物理学(上册)．北京：科学出版社，2001
7 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
8 王慧中，王荣顺，赵大成等．掺杂聚苯胺能带结构和导电机理的研究，高等学校化学学报．1991．12(9)：1229～1233
9 MacDiarmid A G, Chiang J C, Richter A F, et al. Polyanilne: a new concept in conducting polymers. Synth Met. 1988,25(2): 121～137
10 Konshin Takahashi, Kunihiro Nakamura, et al. Characterization of water-souble externally HCl-doped conductivity polyaniline. Synth.Met. 2002,128: 27～33
11 生瑜，陈建宝，朱德钦．二氧化锰化学氧化法合成导电聚苯胺．功能高分子学报．2002，15(4)：383-390
12 曾幸荣，龚克成．聚苯胺的掺杂及其性能的研究．高分子材料科学与工程．1991，6：73
13 Seddique M. Ahmed. Preparation and degradation of highly conducting polyaniline doped with picric acid. European Polymer Journal.2002,38: 1151～1158
14 Chiang J C. MacDiarmid A G.. Polyaniline, Protonic acid doping of emerldine form to the metallic regine. Synth Met. 1986, 13(1-3): 193-205
15 Yong Cao, Paul Smith, Alan J Heeger. Processible forms of electrically conductive polyaniline[P].US Patent: 5624605,1997
16 Patrick J. Emulsion-polymerization process and electrically conductive polyaniline[P].US Patent: 5863465,1999
17 Chen-chang Chen. Miscible forms of electrically conductive polyaniline[P].US Patent: 5670607, 1997
18 井新利，郑茂盛，蓝立文．反向微乳液法合成导电聚苯胺纳米粒子．高分子材料科学与工程．2000，16(2)：23-25
19 阳范文，唐建斌．导电聚苯胺的微乳液聚合．桂林工学院学报．2002，20(3)：
264-266
20 Diaz A F, Logan J A. Electroactive polyaniline film. Electrical Chem. 1980,111(1): 111
21 张超灿，宋丽娜，单松高等．嵌段及接枝改性导电聚苯胺的研究进展．材料导报．2001，15(7)：53-55
22 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．1997，3：22-28
23 刘学习，曾幸荣，杨伟，龚克成．聚苯乙烯磺酸掺杂聚苯胺的合成．功能高分子学报．2002，15(3)：73-76
24 J.Gong, Z.M.Su, Z.M.Dai et al. Synthesis, characterization and polyaniline doped with H_5SiM_(11)VO_(40) (M=Mo, W) Synth.Met.1999, 101: 751
25 Caimao Zhan, Jianjun Zeng, Yuliang Li, XiYang, Jingui Qin. Synthesis and characterization of polyaniline catalysed and doped by squaric acid. Synth.Met. 1999, 101: 731
26 乔庆东，王胜．新型共混DBSA掺杂的聚苯胺导电胶的合成．精细化工．1999．16：35-38
27 Dai Liming, Wang Qian, Wan Meixiang. Direct observation of conformational transitions for polyaniline chains intercalated in clay particles upon secondary doping. Journal of Material Science Letters. 2000(9): 1645～1647
28 牛林，陈晓，魏丰华．导电聚合物的结构与性能表征方法．功能高分子学报．2002，15(1)：91-97
29 王佛松，唐劲松，景遐斌．可溶性聚苯胺的合成及研究，高分子学报．1987，5：384～388
30 Kuo P L, Wey B S, Chen W H. Functional polymers for colloidal application. LX. The dispersing ability of copolymers as photo acid Zwitterionic aniline-formaldehyde condensates to dyes. J Appl Polym Sci.1993, 48(11): 1953～1961
31 江明，府寿宽．高分子科学的近代论题．上海：复旦大学出版社，1998
32 Gospodinova N, Terlemezyan L. Conducting polymers prepared by oxidative polymerization: polyaniline. Progr Polym Sci.. 1998,23(8): 1443～1483
33 Armes S P, Miller J F. Optimum reaction conditions for the polymerization of aniline in aqueous solution by ammonium persulphate. Synth Met. 1988,22(4): 385～389
34 Wang X H, Li J, Wang L X, et al. Synthesis and characterization of chlorinated
polyaniline. Synth Met. 1995, 69(1～3): 149～150
35 Cao Y, Andreatta A, Heeger A J, et al, Influence of chemical polymerization condition on the properties of polyaniline. Polymer. 1989, 30: 2305～2311
36 P.Rannou, M. Nechtschein, J.P. Travers, et al. Age of PANI: chemical, structure and transport consequences. Synth Met. 1999,101: 734～737
37 Cheng-Ho Chen. Thermal Studied of polyaniline doped with DBSA directly prepared via aqueous dispersions. Journal of polymer research. 2002,9: 1995～200
38 C L Gettinger, A J Heeger, D J Pine and Y Cao. Solution characterization of surfactant solubilized polyaniline. Synth Met. 1995, 70: 81～88
39 Anjali A. et al. Studies on chemically synthesized soluble acrylic acid doped polyaniline. Materials chemistry and physics.2002,73: 106～110
40 Yen Wei, Kesyin F. Hsueh, Guang-way Jang, A study of leucoemeraldine and the effect of redox reaction on the molecular weight of chemically prepared polyaniline. Macromolecules. 1994,27: 518～525
41 Dvid W.Hatchett. et al. Acid doping of polyaniline: spectroscopic and electrochemical studies.J.Phys.Chem.B. 1999,103: 10992～10998
42 Anton J. Dominis, Geoffrey M. Spinks. et al. A de-doping/re-doping study of organic soluble polyaniline. Synth Met.2002,129: 165～172
43 L.H.Huo, L.X.Cao, D.M.Wang. et al. Preparation and characterization of doped polyaniline films. Thin solid films. 1999, 350: 5～9
44 Pereira da silva, J.E.Temperini, M.L.A, Cordoba de Torresi, S.L. Secondary doping of polyaniline studied by resonance Raman spectroscopy. Electrochemica Acta. 1999,12: 1887～1891
45 P.Rannou, M. Nechtschein. Aging studies on polyaniline: conductivity and thermal stability. Synth Met. 1997, 84
46 X H Wang, Y H Geng, L X Wang X B Jing, F S Wang. Thermal behavior ofdeped polyaniline. Synth Met. 1995, 69: 265～266
47 Yin Wusheng, Ruckenstein EIL. Soluble polyaniline co-doped with dodecyl benzene sulfonic acid and hydrochloric acid. Synth Met.2000, 108: 39～46
48 W H Jang. et al. Synthesis and electrorheology of camphor sulfonic acid doped polyaniline suspensions. Colloid Polym Sci.2001,279: 823～827
49 K levon, K H Ho, W Y Zheng, et al. Thermal doping of polyaniline with dodecylbenzene sulfonic acid without auxiliary solvents. Polymer. 1994,36(14): 2733～2738
50 P.J.Kinlen. et al. Synthesis and characterization of organically soluble and polyaniline block copolymers. Synth Met. 1999, 101: 758～761
51 Xuehong Lu, Chiang Yang Tan, Jianwei Xu, Chaobin He. Thermal degradation of electrical conductivity of polyacrylic acid doped polyaniline: effect of molecular weight of the dopants. Synth Met.2003, 138: 429～440
52 P. Swapna Rao et al. Inverse emulsion polymerization: a new route for the synthesis of conducting polyaniline. Synth Met.2002, 128: 311～316
53 Chin-Tsoukuo, Show-An Chen. Comparison of electroluminescent quantum efficiencies of PPV and a PPV-related alternating block copolymer. Synth Met.1998, 93: 156～157
54 Pokhodenko V.D., Kurys Ya.L.,Posudievsky O.Yu. Heteropolyacid/m-cresol system as a primary/secondary dopant combination for polyaniline. Synth Met.2001, 1: 199～201
55 Cao Y. et al. Electrically conducting polyaniline: Method fou emulsion polymerization.Wo,94,03252B
56 郑裕东，李吉波，黄炯亮．乳液聚合法合成聚苯胺的结构及性能研究．高分子材料科学与工程．1996，12(6)：30～31
57 Byoung Jin Kim, Seong Geun Oh, Moon-Gyu Han,Seung-Soon Im. Synthesis and characterization of polyaniline nanoparticles in SDS micellar solutions. Synth Met.2001, 122: 297～304
58 L.W.Shacklette, R.L.Elsenbaumer, R.R.Chance, H.Eckhardt, J.E.Frommer, R.H.Baughman. Conducting complexes of polyphenylent sulfides. J Chem Phys. 1981,75(4): 1919～1927
59 H.Sato, J.Tanaka, K.Kaeriyama, Souble conducting polythiophenes. J.Chem.Soc.,Chem.Commun. 1986,11: 873～874
60 [德]赖卡特著，唐培方译．有机化学中的溶剂效应．北京：化学工业出版社，1987