樟脑磺酸掺杂制备可溶性聚苯胺
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摘要
导电聚苯胺具有结构多样化,独特的掺杂机制,优异的物理化学性能和广泛的技术应用前景等特点,成为导电高聚物领域的研究热点。多年来大量的系统研究发现,导电聚苯胺的分子结构、物理化学性能强烈依赖于合成方法与合成条件。采用化学氧化聚合法,以苯胺(An)为单体,过硫酸铵(APS)为氧化剂,在酸性介质中合成聚苯胺(PANI)。
本论文采用溶液聚合法,樟脑磺酸(CSA)作为掺杂剂,在间甲酚(m-c)与三氯甲烷(ch)的混合溶剂中对聚苯胺进行了掺杂研究,并考查了反应时间、反应温度、掺杂剂及用量和间甲酚(m-c)与三氯甲烷(ch)的混合溶剂比例对其导电性的影响。采用四探针法测量了掺杂态聚苯胺的电导率,并用红外光谱(FT-IR)、热失重(TGA)、X射线衍射(XRD)、扫描电子显微镜(SEM)等方法表征了樟脑磺酸掺杂前后聚苯胺的结构和形态。
研究发现,溶液聚合法制备的樟脑磺酸掺杂聚苯胺具有良好的溶解性。掺杂能够使聚苯胺在保持较好溶解性的同时,提高其电导率。实验结果表明,在0-25℃范围内,反应温度对PANI-CSA薄膜的电导率影响不大,在6℃,掺杂时间24h、PANI/CSA (mol/mol)为1/50、m-c/ch(V/V)为20/80的条件下,电导率的最大值为400 S·cm-1。聚苯胺具有良好的环境稳定性和结晶性。通过调整樟脑磺酸掺杂量,膜的致密均匀性显著改善,电导率增加。樟脑磺酸掺杂的聚苯胺的热稳定性较好,热失重温度可达约280℃,有利于生产加工。
Conducting polyaniline (PANI) has become the heat research area in the field of conducting polymer, because of its various structure, unique doping mechanism, excellent physical and chemical properties and wide prospect in applied technology. Many systemic studies indicate that the molecular structure, physical and chemical properties of polyaniline (PANI) doped on the synthesis method and reaction conditions, intensively. Aniline (An) was oxidized by ammonium persulfate (APS) in acidic aqueous solutions for the synthesis of polyaniline.
In this paper, the camphor sulfonic acid (CSA) doped polyaniline (PANI) was polymerized in m-cresol (m-c) and chloroform (ch) mixed solvent, and researches for effects of the doping parameters such as time, temperature, the amount of dopant and the ratio of m-cresol (m-c) and chloroform (ch) mixed solvent for doping on conductivity of polyaniline (PANI). Four-probe method was used to measure the conductivity of doped polyaniline (PANI), the conductivity of which has good environmental stability. The structure and morphology of doped polyaniline (PANI) was characterized by FT-IR, TGA, X-ray diffraction and Scanning electron microscopy.
Doped polyaniline not only can maintain a good solubility but also enhance their electrical conductivity. High conductivity of PANI-CSA was synthesized by doping temperature for 6℃, doping time for 24 h, PANI/CSA (mol/mol) for 1/50, m-c/ch (V/V) for 20/80. Maximum of conductivity was 400 S-cm-1. PANI-CSA had a good environmental stability and crystallinity. By adjusting the amount of dopant camphor sulfonic acid, the dense of membrane and uniformity was significantly improved with the increase of electrical conductivity. The thermal stability of Camphor sulfonic acid (CSA) doped polyaniline is better and the thermal gravity temperature of 280℃, is conducive to production and processing.
本论文采用溶液聚合法,樟脑磺酸(CSA)作为掺杂剂,在间甲酚(m-c)与三氯甲烷(ch)的混合溶剂中对聚苯胺进行了掺杂研究,并考查了反应时间、反应温度、掺杂剂及用量和间甲酚(m-c)与三氯甲烷(ch)的混合溶剂比例对其导电性的影响。采用四探针法测量了掺杂态聚苯胺的电导率,并用红外光谱(FT-IR)、热失重(TGA)、X射线衍射(XRD)、扫描电子显微镜(SEM)等方法表征了樟脑磺酸掺杂前后聚苯胺的结构和形态。
研究发现,溶液聚合法制备的樟脑磺酸掺杂聚苯胺具有良好的溶解性。掺杂能够使聚苯胺在保持较好溶解性的同时,提高其电导率。实验结果表明,在0-25℃范围内,反应温度对PANI-CSA薄膜的电导率影响不大,在6℃,掺杂时间24h、PANI/CSA (mol/mol)为1/50、m-c/ch(V/V)为20/80的条件下,电导率的最大值为400 S·cm-1。聚苯胺具有良好的环境稳定性和结晶性。通过调整樟脑磺酸掺杂量,膜的致密均匀性显著改善,电导率增加。樟脑磺酸掺杂的聚苯胺的热稳定性较好,热失重温度可达约280℃,有利于生产加工。
Conducting polyaniline (PANI) has become the heat research area in the field of conducting polymer, because of its various structure, unique doping mechanism, excellent physical and chemical properties and wide prospect in applied technology. Many systemic studies indicate that the molecular structure, physical and chemical properties of polyaniline (PANI) doped on the synthesis method and reaction conditions, intensively. Aniline (An) was oxidized by ammonium persulfate (APS) in acidic aqueous solutions for the synthesis of polyaniline.
In this paper, the camphor sulfonic acid (CSA) doped polyaniline (PANI) was polymerized in m-cresol (m-c) and chloroform (ch) mixed solvent, and researches for effects of the doping parameters such as time, temperature, the amount of dopant and the ratio of m-cresol (m-c) and chloroform (ch) mixed solvent for doping on conductivity of polyaniline (PANI). Four-probe method was used to measure the conductivity of doped polyaniline (PANI), the conductivity of which has good environmental stability. The structure and morphology of doped polyaniline (PANI) was characterized by FT-IR, TGA, X-ray diffraction and Scanning electron microscopy.
Doped polyaniline not only can maintain a good solubility but also enhance their electrical conductivity. High conductivity of PANI-CSA was synthesized by doping temperature for 6℃, doping time for 24 h, PANI/CSA (mol/mol) for 1/50, m-c/ch (V/V) for 20/80. Maximum of conductivity was 400 S-cm-1. PANI-CSA had a good environmental stability and crystallinity. By adjusting the amount of dopant camphor sulfonic acid, the dense of membrane and uniformity was significantly improved with the increase of electrical conductivity. The thermal stability of Camphor sulfonic acid (CSA) doped polyaniline is better and the thermal gravity temperature of 280℃, is conducive to production and processing.
引文
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[9]Li J, Ishrat M K. Highly conductive solid polymer electrolytes prepared by blending high molecular weight poly(ethyleneoxide), poly(2,4-vinylpyridine), and lithium perchlorate[J].Macromolecules.1993,26:4544-4550.
[10]雀部博之主编.导电高分子材料[M].北京：北京科学出版社,1989.
[11]Macdiarmid A G, Chiang J C, Richter A F, et al. Polyaniline:a new concept in conducting polymers [J]. Synthetic Metals,1987,18:285-290.
[12]朱道本,王佛松.有机固体[M].上海：上海科学技术出版社,1999.89-126.
[13]陆珉,吴益华,姜海,夏李勇.导电聚苯胺的特性及应用[J].化工新型材料,1997,11：16-20.
[14]赵文元,王亦军.功能高分子材料化学[M].北京：化学工业出版社,1996.
[15]王慧忠,王荣顺,赵大成.掺杂聚苯胺能带结构和导电机理的研究[J].高等学校化学学报,1991,9(12)：1229-1233.
[16]Xia Y, MacDiarmid A G, Epstein A J. Camphor sulfonic acid fully doped polyaniline emeraldine salt:in situ observation of electronic and conformational changes induced by organic vapors by an ultraviolet/visible/near-infrared spectroscopic method [J]. Macromolecules,1994,27:7212-7214.
[17]殷敬华,莫志深.现代高分子物理学[M].北京：科学出版社,2001.298-327.
[18]周震涛,杨洪业,王克俭,刘芳.聚苯胺掺杂、除掺杂和再掺杂与结构性能的研究[J].华南理工大学学报(自然科学版),1995,23(10)：66-71.
[19]Wan Meixiang. Absorption spectra of thin film of polyaniline[J]. Journal of polymer science,1992, A(30):543-549.
[20]耿延候,万梅香,王军,景遐斌,王佛松.高性能掺杂态聚苯胺[J].高分子材料科学与工程,1997,13(6)：124-127.
[21]陆珉,吴益华,姜海,夏李勇.高电导率聚苯胺[J].功能材料,1998,29(5)：455-460.
[22]陆珉,吴益华,姜海,夏李勇.导电聚苯胺的特性及应用[J].功能材料,1998,29(4)：353-358.
[23]Asturias G E, Macdiarmid A G. The oxidation state of"emeraldinebase[J]. Synthetic Metals,1989,29:157-162.
[24]Wang L X, Jing X B, Wang F S. Polytoluidines with different degrees of oxidation and their doping with HCl[J]. Synthetic Metals,1989,29:363-370.
[25]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(自然科学版).2002,25：124-127.
[26]C.O. Yoon, J.H. Kim, H.K. Sung, et al. Transport studies of emeraldine salt protonated by phosphoric acids[J]. Synthetic Metals,1996,81:75-80.
[27]Cao Y. Smith P, Heeger A J. [J]. Synthetic Metals,1993,55-57:3514-3519.
[28]MacDiarmid A G, Epstein A J[J]. Synthetic Metals,1995,69:85-92.
[29]宋月贤,王红理,郑元锁等.高导电聚苯胺薄膜的制备及其电磁屏蔽性能的研究[J].高分子学报,2002,(1)：94-97.
[30]MacDiarmid A G. Polyaniline:a Novel Class of Conducting polymers[J]. Faraday Discuss Chem Soc,1989,88:317-320.
[31]Tang J S, Jing X B, Wang B C, et al. Infrared Spectra of Soluble Polyaniline [J]. Synthetic Metals,1988,24:231-235.
[32]Warren L F, Walker J A, Anderson D P, et al. A Study of Conduction Polymer Morphology [J]. Electro chem Soc,135:2286-2290.
[33]DIAZAF, LOGANJA. Electroactive polyaniline film[J]. Electroanal Chem,1980, 111(1):111-115.
[34]Sathiyanarayanan S, Dhawan S K, Trivedi D C. Soluble conducting polyethoxy aniline as an inhibitor for iron in HCl[J]. Corrosion Science,1992,33:1831-1835.
[35]Troch-Nagels G, Winand R, Weymeersch A, et al. Electron conducting organic coating of mild steel by electropolymerization[J]. J Appl Electrochem,1992,22: 756-764.
[36]祝伟,祝海峰,田艳秋.苯胺的化学催化聚合[J].黎明化工.1995,(3)：1-4.
[37]马利,胡睿,王成章.导电聚苯胺材料的乳液聚合研究进展[J].包装工程,2002,23：1-4.
[38]Haba Y, Segal E, Narkis M, Titelman G J, Siegmann A. Polymerization of aniline in the presence of DBS A in an aqueous dispersion [J]. SyntheticMetals,1999,106: 59-66.
[39]Choi B Y, Chung I J, Chun J H, Ko J M. Electrochemical characteristics of dopecylbenzene sulfonic acid-doped polyaniline in aqueous solutions[J]. Synthetic Metals,1999,99:253-256.
[40]Dominis A J, Spinks G M, Kane-Maguire L A P, Wallace G G. A de-doping/re-doping study of organic soluble polyaniline[J]. Synthetic Metals, 2002,129:165-172.
[41]Motheo A J, Santos Jr J R, Venancio E C, Mattoso L H C. Influence of different types of acidic dopant on the electrodeposition and properties of polyaniline films [J], Polymer,1998,39(26):6977-6982.
[42]Han M G, Cho S K, Oh S G, Im S S Preparation and characterization of polyaniline nanoparticles synthesized from DBSA micellar solution [J], Synthetic Metals,2002, 126:53-60.
[43]Roy B. C., Gupta M. D., Bhowmik L., Ray J. K.:Studies on water soluble conducting polymer:aniline initiated polymerization of m-aminobenzene sulfonic acid[J], Synthetic Metals,1999,100:233-236.
[44]MacDiarmid A G, Epstein A J. Secondary doping in polyaniline [J], Synthetic Metals,1995,69:85-92.
[45]Jiang H, Geng Y H, Li J, Jing X B, Wang F S. Organic acid doped polyaniline derivatives [J], Synthetic Metals,1997,84:125-126.
[46]MacDiarmid A G, Avlyanov J K, Huang Z, et al. Polyaniline and polypyrrole:effect of molecular conformation on electronic and related propersities [J], Polymeric Materials Science and Engineering,1995,72,395-399.
[47]Epstein A J, Ginger J M, Richter A F, et al. In A lcacer L, ed. Conducting Polymers: Special Applications M. Dordrecht, Holland:D.Reidel Publishing Company,1987: 121-140.
[48]耿延侯,李季,景遐斌,王佛松,刘振兴,万梅香.聚苯胺的电荷传输特性及其分子量依赖性[J],中国科学(B辑),1998,28(5)：477-480.
[49]王佛松,王利祥,景遐斌.聚苯胺的掺杂反应[J].武汉大学学报,1993,(6)： 65-73.
[50]Angelopoulos M. Conducting Polymers as Lithograaphic Materials [J]. Polym Eng Soc,1992,32:153-158.
[51]Chiang J C, MacDiarmid A G. Polyaniline:Protonic acid doping of the emeraldine form to the metallic regime [J]. Synthetic Metals,1986, (13):193-196.
[52]Rannou P, Nechtschein M, Travers J P, etc. Age of PANI:chemical, structure and transport consequences. Synthetic Metals,1999,101:734-737.
[2]赵文元,王亦军.海外高分子研究进展[M].北京：科学出版社,1999.
[3]陆珉,吴益华,姜海夏.导电聚苯胺的特性及应用[J].化工新型材料,1997,(11)：16-20.
[4]李新玮.苯胺及其衍生物聚合物的合成、性能与应用研究[学位论文].南京：南京理工大学,2001.
[5]Kinlen P J, Silverman D C, Jeffreys C R. Corrosion protection using polyaniline coating formulations [J]. Synthetic Metals.1997,85:1327-1332.
[6]Deberry D W.Modification of the electrochemical and corrosion behavior of stainless steels with an electroactive coating [J]. Electro chem,1985,132:1022-1026.
[7]苏慈生.聚苯胺在防腐蚀涂料中的应用[J].现代涂料与涂装,2001,1：11-14.
[8]倪余伟.聚苯胺在腐蚀防护中的应用[J].腐蚀与防护,2000,21(1)：27-29.
[9]Li J, Ishrat M K. Highly conductive solid polymer electrolytes prepared by blending high molecular weight poly(ethyleneoxide), poly(2,4-vinylpyridine), and lithium perchlorate[J].Macromolecules.1993,26:4544-4550.
[10]雀部博之主编.导电高分子材料[M].北京：北京科学出版社,1989.
[11]Macdiarmid A G, Chiang J C, Richter A F, et al. Polyaniline:a new concept in conducting polymers [J]. Synthetic Metals,1987,18:285-290.
[12]朱道本,王佛松.有机固体[M].上海：上海科学技术出版社,1999.89-126.
[13]陆珉,吴益华,姜海,夏李勇.导电聚苯胺的特性及应用[J].化工新型材料,1997,11：16-20.
[14]赵文元,王亦军.功能高分子材料化学[M].北京：化学工业出版社,1996.
[15]王慧忠,王荣顺,赵大成.掺杂聚苯胺能带结构和导电机理的研究[J].高等学校化学学报,1991,9(12)：1229-1233.
[16]Xia Y, MacDiarmid A G, Epstein A J. Camphor sulfonic acid fully doped polyaniline emeraldine salt:in situ observation of electronic and conformational changes induced by organic vapors by an ultraviolet/visible/near-infrared spectroscopic method [J]. Macromolecules,1994,27:7212-7214.
[17]殷敬华,莫志深.现代高分子物理学[M].北京：科学出版社,2001.298-327.
[18]周震涛,杨洪业,王克俭,刘芳.聚苯胺掺杂、除掺杂和再掺杂与结构性能的研究[J].华南理工大学学报(自然科学版),1995,23(10)：66-71.
[19]Wan Meixiang. Absorption spectra of thin film of polyaniline[J]. Journal of polymer science,1992, A(30):543-549.
[20]耿延候,万梅香,王军,景遐斌,王佛松.高性能掺杂态聚苯胺[J].高分子材料科学与工程,1997,13(6)：124-127.
[21]陆珉,吴益华,姜海,夏李勇.高电导率聚苯胺[J].功能材料,1998,29(5)：455-460.
[22]陆珉,吴益华,姜海,夏李勇.导电聚苯胺的特性及应用[J].功能材料,1998,29(4)：353-358.
[23]Asturias G E, Macdiarmid A G. The oxidation state of"emeraldinebase[J]. Synthetic Metals,1989,29:157-162.
[24]Wang L X, Jing X B, Wang F S. Polytoluidines with different degrees of oxidation and their doping with HCl[J]. Synthetic Metals,1989,29:363-370.
[25]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(自然科学版).2002,25：124-127.
[26]C.O. Yoon, J.H. Kim, H.K. Sung, et al. Transport studies of emeraldine salt protonated by phosphoric acids[J]. Synthetic Metals,1996,81:75-80.
[27]Cao Y. Smith P, Heeger A J. [J]. Synthetic Metals,1993,55-57:3514-3519.
[28]MacDiarmid A G, Epstein A J[J]. Synthetic Metals,1995,69:85-92.
[29]宋月贤,王红理,郑元锁等.高导电聚苯胺薄膜的制备及其电磁屏蔽性能的研究[J].高分子学报,2002,(1)：94-97.
[30]MacDiarmid A G. Polyaniline:a Novel Class of Conducting polymers[J]. Faraday Discuss Chem Soc,1989,88:317-320.
[31]Tang J S, Jing X B, Wang B C, et al. Infrared Spectra of Soluble Polyaniline [J]. Synthetic Metals,1988,24:231-235.
[32]Warren L F, Walker J A, Anderson D P, et al. A Study of Conduction Polymer Morphology [J]. Electro chem Soc,135:2286-2290.
[33]DIAZAF, LOGANJA. Electroactive polyaniline film[J]. Electroanal Chem,1980, 111(1):111-115.
[34]Sathiyanarayanan S, Dhawan S K, Trivedi D C. Soluble conducting polyethoxy aniline as an inhibitor for iron in HCl[J]. Corrosion Science,1992,33:1831-1835.
[35]Troch-Nagels G, Winand R, Weymeersch A, et al. Electron conducting organic coating of mild steel by electropolymerization[J]. J Appl Electrochem,1992,22: 756-764.
[36]祝伟,祝海峰,田艳秋.苯胺的化学催化聚合[J].黎明化工.1995,(3)：1-4.
[37]马利,胡睿,王成章.导电聚苯胺材料的乳液聚合研究进展[J].包装工程,2002,23：1-4.
[38]Haba Y, Segal E, Narkis M, Titelman G J, Siegmann A. Polymerization of aniline in the presence of DBS A in an aqueous dispersion [J]. SyntheticMetals,1999,106: 59-66.
[39]Choi B Y, Chung I J, Chun J H, Ko J M. Electrochemical characteristics of dopecylbenzene sulfonic acid-doped polyaniline in aqueous solutions[J]. Synthetic Metals,1999,99:253-256.
[40]Dominis A J, Spinks G M, Kane-Maguire L A P, Wallace G G. A de-doping/re-doping study of organic soluble polyaniline[J]. Synthetic Metals, 2002,129:165-172.
[41]Motheo A J, Santos Jr J R, Venancio E C, Mattoso L H C. Influence of different types of acidic dopant on the electrodeposition and properties of polyaniline films [J], Polymer,1998,39(26):6977-6982.
[42]Han M G, Cho S K, Oh S G, Im S S Preparation and characterization of polyaniline nanoparticles synthesized from DBSA micellar solution [J], Synthetic Metals,2002, 126:53-60.
[43]Roy B. C., Gupta M. D., Bhowmik L., Ray J. K.:Studies on water soluble conducting polymer:aniline initiated polymerization of m-aminobenzene sulfonic acid[J], Synthetic Metals,1999,100:233-236.
[44]MacDiarmid A G, Epstein A J. Secondary doping in polyaniline [J], Synthetic Metals,1995,69:85-92.
[45]Jiang H, Geng Y H, Li J, Jing X B, Wang F S. Organic acid doped polyaniline derivatives [J], Synthetic Metals,1997,84:125-126.
[46]MacDiarmid A G, Avlyanov J K, Huang Z, et al. Polyaniline and polypyrrole:effect of molecular conformation on electronic and related propersities [J], Polymeric Materials Science and Engineering,1995,72,395-399.
[47]Epstein A J, Ginger J M, Richter A F, et al. In A lcacer L, ed. Conducting Polymers: Special Applications M. Dordrecht, Holland:D.Reidel Publishing Company,1987: 121-140.
[48]耿延侯,李季,景遐斌,王佛松,刘振兴,万梅香.聚苯胺的电荷传输特性及其分子量依赖性[J],中国科学(B辑),1998,28(5)：477-480.
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