自掺杂磺酸化聚苯胺之最优化实验设计(英文)

电化学（中英文） ›› 2005, Vol. 11 ›› Issue (4): 360-368.

自掺杂磺酸化聚苯胺之最优化实验设计(英文)

李文亚;胡启章;

中正大学化学工程系,中正大学化学工程系嘉义621,嘉义,嘉义621,嘉义

收稿日期:2005-11-28 修回日期:2005-11-28 出版日期:2005-11-28 发布日期:2005-11-28

The Optimal Sulfonation Conditions of Self-doped Polyaniline Obtained by Using Experimental Strategies

LI Wen-yar,HUChi-chang*

(Department of Chemical Engineering,Chung Cheng University,Chia-Yi 621,Taiwan,China

Received:2005-11-28 Revised:2005-11-28 Published:2005-11-28 Online:2005-11-28

摘要/Abstract

摘要： 应用实验设计法包括部分析因设计与中心组合设计,优化自掺杂磺酸化聚苯胺的导电性.部分析因设计发现,需用低温(4℃)、短反应时间(1 h)和少量发烟硫酸(10 mL)等实验条件进行磺酸化反应才能得到好的导电性(ca.127 mS.cm-1);中心组合设计与确认实验表明,其最佳导电性(ca.141 mS/cm)的磺酸化条件是4℃、75 m in反应时间以及8 mL 30%的发烟硫酸.应用傅立叶变换红外光谱(FTIR)、四探针与X光光电子能谱等分析制备的材料.此外,发现磺酸化速率与程度与聚合反应时所使用的酸有关.

关键词: 自掺杂聚苯胺, 磺酸化, 导电性, 部分析因设计, 中心组合设计

Abstract: The optimal sulfonation condition of self-doped sulfonated polyaniline(prepared from leucoemeraldinebase;denoted as LEB-SPANI) with a high electronic conductivity was obtained by experimental strategies,includingthe fractional factorial design(FFD) and central composite design(CCD).From the FFD experiment,the self-doped LEB-SPANI prepared at a lowtemperature(4oC),a short reaction time(1 h),and a small volume of fumingsulfuric acid(10 mL) showed a better conductivity(ca.127 mS/cm).In the CCD study coupled with a confirmationtest,the highest conductivity(ca.141 mS/cm) of the LEB-SPANI film was obtained under a sulfonation temperatureof 4oC,a sulfonation time of75 minutes,and a volume of8 mLof30% fuming sulfuric acid.The textural cha-racter-istics of self-doped LEB-SPANI were characterized by Fourier transform infrared(FTIR) spectroscopy,four-pointprobe method,and X-ray photoelectron spectroscopy(XPS).The sulfonation rate and degree of LEB-SPANI werefound to be dependent upon the acid used in the polymerization step of PANI.

Key words: Self-doped polyaniline, Sulfonation, Conductivity, Fractional factorial design, Central composite de-sign

中图分类号:

O633.22

李文亚;胡启章;. 自掺杂磺酸化聚苯胺之最优化实验设计(英文)[J]. 电化学（中英文）, 2005, 11(4): 360-368.

LI Wen-yar,HUChi-chang*. The Optimal Sulfonation Conditions of Self-doped Polyaniline Obtained by Using Experimental Strategies[J]. Journal of Electrochemistry, 2005, 11(4): 360-368.

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参考文献

[1]Skotheim TA.Handbook of Conducting Polymers Vol.1and 2[M].New York:Marcel Dekker,Inc.,1988. [2]Patil A Q,Heeger A J,Wudl F.Optical properties ofconducting polymers[J].Chem.Rev.,1988,88:183. [3]Bredas J L,Chance R R.Conjugates Polymeric Materi-als:Opportunities in Electronics,Optoelectronics andMolecular Electronics[M].Dordrecht:KluwerAcadamic Pub.,1990. [4]Skotheim TA.Electroresponsive Molecular and Polymer-ic Systems Vol.II[M].New York:Marcel Dekker,Inc.,1992. [5]Yamamoto H,Oshima M,Fukuda M,et al.Characteris-tics of aluminium solid electrolytic capacitors using aconducting polymer[J].J.Power Sources,996,60:173. [6]Yue J,Epstein A J,Zhong Z,et al.Thermal stabilitiesof polyanilines[J].Synth.Met.,1994,41:765. [7]Yue J,Wang Z H,Cromack KR,et al.Effect of sulfo-nic acid group on polyaniline backbone[J].J.Am.Chem.Soc.,1991,113:2 665. [8]Wei X L,Wang Y Z,Long S M,et al.Synthesis andphysical properties of highly sulfonated polyaniline[J].J.Am.Chem.Soc.,1996,118:2 545. [9]Hu C C,Lin J Y.Effects of the loading and polymeriza-tion temperature on the capacitive performance of polya-niline in NaNO3[J].Electrochim.Acta,2002,47:4055. [10]Hu C C,Chu C H.Electrochemical impedance charac-terization of polyaniline-coated graphite electrodes forelectrochemical capacitors-effects of film coverage/thickness and anions[J].J.Electroanal.Chem.,2001,503:105. [11]Lampert C M,Granqvist C G.Large-Area Chromoge-nics:Materials and Devices for Transmittance Control[M].Washington:SPIE Optical Engineering Press,1990. [12]Barbero C,Miras MC,Calvo E J,et al.A probe beamdeflection study of ion exchange at poly(vinylferro-cene)films in aqueous and nonaqueous electrolytes[J].Langmuir,2002,18:2756. [13]Hwang K S,Lee C W,Yoon T H,et al.Fabricationand characteristics of a composite cathode of sulfonatedpolyaniline and Ramsdellite MnO2for a new recharge-able lithium polymer battery[J].J.Power Sources,1999,79:225. [14]Ferreira M,Rubner M F.Molecular-level processingof conjugated polymers.1.layer-by-layer manipu-lation of conjugated polyions[J].Macromolecules,1995,28:7107. [15]Box G E P,Hunter W G,Hunter J S.Statistics for Ex-periments[M].New York:Wiley,1978.374. [16]Montgomery D C.Design and Analysis of Experiments,5th ed.,[M].Singapore:Wiley,2001.303. [17]Cornell J A.How to Apply Response Surface Methodo-logy,vol.8[M].Wisconsin:ASQC,1990.3. [18]Tsay P,Hu C C.Non-anomalous codeposition of iron-nickel alloys using pulse-reverse electroplatingthrough means of experimental strategies[J].J.Elec-trochem.Soc.,2002,149:C 492. [19]Hu C C,Tsay C H,Bai A.Optimization of the hydro-gen evolution activity of zinc-nickel deposits using ex-perimental strategies[J].Electrochim.Acta,2003,48:907. [20]Li Y J,Chang C C,Wen TC.Application of statisticalexperimental strategies to H2O2production on Au/graphite in alkaline solution[J].I&EC Research,1996,35:4 767. [21]Hsu C H,Peacock P M,Flippen R B,et al.Molecularweight of sulfonic acid ring-substituted polyaniline bylaser light scattering[J].Synth.Met.,1993,60:223. [22]Mu S,Kan J.Energy density and IR spectra of polyani-line synthesized electrochemically in the solutions ofstrong acids[J].Synth.Met.,1998,98:51. [23]Lim V W L,Kang E T,Neoh K G,et al.Determina-tion of pyrrole aniline copolymer compositions by X-ray photoelectron spectroscopy[J].Applied SurfaceScience,2001,181:317. [24]Trivedi D C.Handbook of Organic Conductive Mole-cules and Polymers,vol.2[M].New York:H.S.Nalwa,Wiley,1997.Chapter 12. [25]Anand J,Palaniappan S,Sathyanarayana D N.Hand-book of Organic Conductive Molecules and Polymers,vol.2[M].New York:H.S.Nalwa,Wiley,1997.Chapter 13. [26]Wang X H,Li J,Wang LX,et al.Structure and prop-erties of self-doped polyaniline[J].Synth.Met.,1995,69:149. [27]John McMurry.McMurry Organic Chemistry,4th ed.,[M].Brooks/Cole,1996.Chapter 16. [28]Kang E T,Neoh K G,Tan K L.Handbook of OrganicConductive Molecules and Polymers,vol.3[M].NewYork:H.S.Nalwa,Wiley,1997. [29]Yue J,Epstein A J.XPS study of self-doped conduc-ting polyaniline and parent systems[J].Macromole-cules,1991,24:4 441. [30]Wei X L,Fahlman M,Epstein AJ.XPS study of high-ly sulfonated polyaniline[J].Macromolecules,1999,32:3 114.