臺灣博碩士論文加值系統

使用苯胺單體與其寡聚體，如雙體、四聚體等為起始物，化學合成掌性的聚苯胺奈米纖維。其反應最佳條件是樟腦磺酸10 M、苯胺雙體1.06 M、分五次加入過硫酸胺2.13 M、在室溫且反應時間兩小時。由苯胺單體、雙體及四聚體所產生的聚苯胺其g-factor分別為-8.9*10-5、-8.4*10-3和-1.6*10-3；導電度分別是6.4*10-8、1.0*10-5和3.1*10-6，由此可得知使用苯胺雙體聚合可得到最好的掌性聚苯胺。另外加入微量苯胺寡聚體如p-phenylenediamine和4,4’-diaminodiphenylamine，作為促進劑（promoter）進行聚合，，其g-factor及導電度都下降。由掃描式電子顯微鏡可以發現，苯胺雙體聚合出的聚苯胺為直徑100nm的掌性奈米纖維，而苯胺雙體所產生的聚苯胺，無論是左旋或右旋的奈米纖維皆可以利用氨水進行去摻雜（dedoping）與再摻雜（redoping）。
使用苯胺雙體進行兩相介面聚合，也可以產生掌性的聚苯胺奈米纖維，且產生的聚苯胺結構也隨著反應時間不同而改變。值得注意的是，使用樟腦磺酸S-CSA反應時，在4℃與15℃分別為兩種相反的旋光結構。

摘要……………………………………………………………………Ⅰ
目錄……………………………………………………………………Ⅱ
圖目錄…………………………………………………………………Ⅵ
表目錄…………………………………………………………………Ⅸ

1、緒論……………………………………………………………………1
1.1、導電高分子發展…………………………………………………..1
1.1.1、聚苯胺簡介與發展近況…………………………………….1
1.1.2、聚苯胺的聚合機制………………………………………….2
1.1.3、聚苯胺的氧化還原態……………………………………….2
1.1.4、聚苯胺的結構與紫外光-可見光光譜（UV-Vis）…………4
1.2、圓二色極化光譜（circular dichroism，CD）…………………6
1.2.1、g-factor………………………………………………………9
1.3、聚苯胺的合成方法………………………………………………10
1.3.1、電化學聚合…………………………………………………10
1.3.2、生物催化聚合法……………………………………………10
1.3.3、化學聚合法…………………………………………………11
1.3.3.1、兩相介面聚合法……………………………………11
1.3.3.2、傳統化學聚合法……………………………………12
1.4、掌性聚苯胺…………………………………………...…………..15
1.4.1、傳統化學法聚合掌性聚苯胺………………………………15
1.4.2、電化學法聚合掌性聚苯胺…………………………………17
1.5、溫度效應……………………………………………….….……..19
1.6、研究動機與目的……………………………………….….……..21
2、實驗部分…………………………………………………………….23
2.1、試藥……………………………………………………………..23
2.1.1、試藥……………………………………………………….23
2.1.2、試藥結構………………………………………………….24
2.2、儀器設備………………………………………………………..26
2.3、實驗步驟………………………………………………………..27
2.3.1、傳統聚合方法……………………………………………27
2.3.1.1、加入氧化劑的方式………………………………27
2.3.1.2、摻雜酸濃度影響………………………………….27
2.3.1.3、苯胺雙體與氧化劑的比例……………………....28
2.3.1.4、苯胺雙體濃度對摻雜酸的影響………………….28
2.3.1.5、溫度效應以及反應時間…………………………28
2.3.1.6、使用不同種類的苯胺寡聚體……………………28
2.3.2、兩相介面聚合法…………………………………………30
2.3.2.1、摻雜酸濃度影響…………………………………30
2.3.2.2、聚合反應時間……………………………………31
2.3.2.3、反應環境溫度……………………………………31
2.3.3、去摻雜與再摻雜聚苯胺…………………………………31
2.3.4、製備SEM、FT-IR所需的聚苯胺試片…………………31
2.3.5、聚苯胺溶液的CD與UV光譜分析……………………32
2.3.6、分子量測定……………………………………………...33
2.3.7、導電度測量………………………………………………33
3、結果與討論
3.1、加入氧化劑的方式……………………………………………...34
3.2、摻雜酸濃度影響………………………………………………..37
3.3、苯胺雙體與氧化劑的比例……………………………………..37
3.4、苯胺雙體濃度對摻雜酸的影響………………………………..40
3.5、溫度效應………………………………………………………..40
3.6、使用不同種類的苯胺寡聚體…………………………………..42
3.6.1、苯胺寡聚體自身聚合…………………………………….42
3.6.2、苯胺寡聚體作為催化劑聚合………………………..……47

3.7、去摻雜與再摻雜聚苯胺………………………………………..53
3.8、掃描式電子顯微鏡觀察聚合物分子結構……………………..55
3.9、分子量及導電度………………………………………………..58
4、兩相聚合…………………………………………………………….62
4.1、摻雜酸濃度影響………………………………………………..62
4.2、聚合反應時間…………………………………………………..63
4.3、反應環境溫度…………………………………………………..64
5、結論與未來展望…………………………………………………….66
6、參考文獻…………………………………………………………….67

(1) T. Ito, Hideki Shirakawa, S. Ikeda, Simultaneous polymerization and formation of polyacetylene film on the surface of concentrated soluble Ziegler-type catalyst solution.
(2) H. Shirakawa, E. J. Louis, S. C. Gau and A.G. MacDiarmid. Electrical conductivity in doped polyacetylene. Phys. Rev. Lett. 39 (1977) 1098–1101
(3) H.L. Wang, A.G.MacDiarmid, Y.Zwang, D.D.Gebler, A.J.Epstein. Application of polyaniline (emeraldin base, EB) in polymer light-emitting devices. Synthetic Metals 78 (1996) 33-37.
(4) S.A. Chen, K.R. Chuang, C.I. Chao, H.T. Lee. White-light emission from electroluminescence diode with polyaniline as the emitting layer. Synthetic Metals 78 (1996) 207-210.
(5) W.K. Lu, R.L.Elsenbaumer and B. Wessling. Corrosion protection of mild steel by coatings containing polyaniline. Synthetic Metals 71 (1995) 2163-2166
(6) X. Li, Ming Ju, Xingwei Li. Chlorine ion sensor based on polyaniline film electrode. Sensors and Actuators 97 (2004) 144–147
(7) A.L. Kukia, Yu.M.Shirshov, S.A.Piletsky . Ammonia sensor based on sensitive polyaniline films. Sensors and Actuators 97 (1996) 135–140.
(8) Y. Shao, Y. Jin, S. Dong. DNA-templated assembly and electropolymerization of aniline on gold surface. Electrochemistry Communications 4 (2002) 773–779
(9) P. J. O’Connell, C. Gormally, M. Pravda, G.G. Guilbault. Development of an amperometric l-ascorbic acid (Vitamin C) sensor based on electropolymerised aniline for pharmaceutical and food analysis . Analytica Chimica Acta 431 (2001) 239–247
(10) Y. Yang, S. Mu . Bioelectrochemical responses of the polyaniline horseradish peroxidase electrodes. Journal of Electroanalytical Chemistry 432(1997)71-78
(11) P.C. Pandey, G. Singh. Tetraphenylborate doped polyaniline based novel pH sensor and solid-state urea biosensor. Talanta 55 (2001) 773–782
(12) A. Talaie. Conducting polymer based pH detector: a new outlook to pH sensing technology. Polymer 38 (1997) 1145-1150.
(13) P.C. Pandey, A.P. Mishra Novel potentiometric sensing of creatinine. Sensors and Actuators B 99 (2004) 230–235
(14) A. Eftekhari. Glycerol biosensor based on glycerol dehydrogenase incorporated into polyaniline modified aluminum electrode using hexacyanoferrate as mediator. Sensors and Actuators B 80 (2001) 283–289
(15) A.A. Karyakin, O.A. Bobrova, L.V. Lukachova, E.E. Karyakina. Potentiometric biosensors based on polyaniline semiconductor films. Sensors and Actuators B 33 (1996) 34–38.
(16) H. Guo, R.B. Kaner. Achiral recognition polymer based on polyaniline. Synthetic Metals 101 (1999) 44-47.
(17) X. Zhang , V. Chechik , D.K. Smith, P.H. Walton , Anne-Kathrin Duhme-Klair , Y. Luo . Nanocomposite hydrogels-controlled synthesis of chiral polyaniline nanofibers and their inclusion in agarose. Synthetic Metals 159 (2009) 2135-2140
(18) Y. Li, B. Wang, W. Feng. Chiral polyaniline with flaky, spherical and urchin-like morphologies synthesized in the L-phenylalanine saturated solution. Synthetic Metals 159 (2009) 1597-1602
(19) P. Rannou, M. Nechtschein. Aging studies on polyaniline: conductivity and thermal stability. Synthetic Metals 84 (1997) 755-756.
(20) S. Kobayashi, H. Uyama and S. Kimura. Enzymatic Polymerization. Chem. Rev. 2001, 101, 3793-3818.
(21) J. Huang and R.B. Kaner. A general chemical route to polyaniline nanofibers. J. AM. CHEM. SOC. 126 (2004) 851-855
(22) J. Huang and R.B. Kaner. The intrinsic nanofibrillar morphology of polyaniline. Chem Commun (2006) 367-376
(23) S. Liu, K. Zhu, Y. Zang, J. Xu. Cyclic polyaniline nanostructures from aqueous/organic interfacial polymerization induce by polyacrylic acid. Polymer 47 (2006) 7680-7683
(24) Y. He, J. Lu. Synthesis of polyaniline nanostructures with controlled morphology by two-phase strategy. Reactive ＆ Functional polymers 67 (2007) 476-480
(25) M.V. Kulkarni, A.K. Viswanath. Comparative studies of chemically synthesized polyaniline and poly(o-toluidine) doped with p-toluene sulphonic acid . European Polymer Journal 40 (2004) 379–384
(26) N. Ballav. High-conducting polyaniline via oxidative polymerization of aniline by MnO2, PbO2 and NH4VO3. Materials Letters 58 (2004) 3257–3260
(27) N. Gospodinova, L. Terlemezyan. Conductingpolymers prepared by oxidative polymerization: polyaniline. Prog. Polym. Sci 23 (1998) 1443-1484
(28) J. Li, H. Tang, A. Zhang, X. Shen, L. Zhu. A new strategy for the synthesis of polyaniline nanostructures: From nanofibers to nanowires. Macromol. Rapid Commun. 2007, 28, 740–745
(29) L. Zhang, M. Wan, Y. Wei. Nanoscaled polyaniline fibers prepared by ferric chloride as an oxidant. Macromol. Rapid Commun. 27 (2006) 366–371
(30) M. Rezajidi, L.A.P. Kane-Maguire and G.G. Wallace. Chemical generation of optically active polyaniline via the doping of emeraldine with (+)-or(-)-camphorsulfonic acid . Polymer. 36 (1995) 3597-3599
(31) I.D. Norris, G.G. Wallace, W. Zheng. Facile preparation of optically active polyanilines via the in situ chemical oxidative polymerisation of aniline. Synthetic Metals 106 (1999) 171-176.
(32) I.D. Norris, G.G. Wallace. Factor controlling the induction of optical activity in chiral polyaniline. Synthetic Metals 84 (1997) 115-116
(33) S.E. Moulton, G.G. Wallace, W.K. Maser. Optically activepolymer carbon nanotube composite. J. Phys. Chem. B 109 (2005) 22725-55729
(34) L.A.P. Kane-Maguire, G.G. Wallace. Chiral conducting polymers. Chem. Soc. Rev 39 (2010) 2545-2576
(35) H. Guo, C.M. Knobler and R.B. Kaner. A chiral recognition polymer based on Polyaniline. Synthetic Metals 101 (1999) 44-47
(36) L.A.P. Kane-Maguire, G.G. Wallace .The effect of added water on the conformation of optically active polyaniline in organic solvents. Synthetic Metals 135-136 (2003) 241-242
(37) V. Egan, R. Bernstein, L. Hohmann, T. Tran and R.B. Kaner. Influence of water on the chirality of camphorsulfonic acid-doped polyaniline. Chem. Commun., (2001) 801–802
(38) W. Li and H.L. Wang. Oligomer-assisted synthesis of chiral polyaniline nanofibers. J. AM. CHEM. SOC. 126 (2004) 2278-2279
(39) W. Li and H.L. Wang. Toward optimizing synthesis of nanostructured chiral polyaniline. Polymer 47 (2006) 3112-3118
(40) B.H. Weiller, R.B.Kaner. Polyaniline nanofibers: Facile synthesis and chemical sensor. J. AM. CHEM. SOC. 125 (2003) 314-315
(41) Y. Wang, H.D.Tran, X. Duan, R.B. Kaner .Nanoscale morphology, dimensional control, and electrical properties of oligoaniline. J. AM. CHEM. SOC. 132 (2010) 10365-10373.
(42) H.D. Tran, D. Li, R.B. Kaner. One-dimensional conducting polumer nanostructures: Bulk synthesis and applications. Adv. Mater 21(2009)1487-1499
(43) Y. Wang, H.D. Tran, R.B. Kaner. Applications of oligomers for nanostructured conducting polymers. Macromol. Rapid Commun. 32 (2011) 35-49
(44) X. Zhang, W. Song, P.J.F. Harris, Geoffrey R. Mitchell, Tam T. T. Bui, and Alex F. Drake. Chiral polymer-carbon-nanotube composite nanofibers. Adv. Mater. 19 (2007) 1079–1083
(45) M.R. Majidi, L.A.P. Kane-Maguire and G.G. Wallace. Enantioselective electropolymerization of aniline in the presence of (+)- or (−)-camphorsulfonate ion: a facile route to conducting polymers with preferred one-screw-sense helicity. Polymer, 36 (1994) 3113–3115
(46) E.E. Havinga, M.M. Bouman, E.W. Meijer, A. Pomp and M. M. J. Simenon. Large induced optical activity in the conduction band of polyaniline doped with (1S)-(+)-10-camphorsulfonic acid. Synth. Met., 66 (1994) 93-97
(47) D. Norris, L.A.P. Kane-Maguire, G.G. Wallace and L.H.C. Mattoso. Chiral induction in the acid doping of poly (o-methoxy aniline). J. Chem. 53 (2000) 89
(48) C.Boonchu, L A.P. Kane-Maguire and G.G. Wallace. Conformational changes in sulfonated polyaniline caused by metal salts and OH-. Synth. Met. 135–136 (2003) 241-242
(49) S.A. Ashraf, L.A.P. Kane-Maguire, M.R. Majidi, S.G. Pyne and G.G. Wallace. Influence of the chiral dopant anion on the generation of induced optical activity in polyanilines. Polymer 38 (1997) 2627-2631
(50) M. Bodner and M.P. Epse. Induced Optical Activity in Polyaniline: Solvent and Acid Dependence. Synth. Met. 135–136 (2002) 403
(51) Y. Pornputtkul, L. A. P. Kane-Maguire and G. G. Wallace. Influence of electrochemical polymerization temperature on the chiroptical properties of (+)-camphorsulfonic acid-doped polyaniline. Macromolecules 39 (2006) 5604-5610
(52) Zimmermann, U. Kunzelmann, L. Dunsch. Initial states in the electropolymerization of aniline and p-aminodiphenylamine as studied by in situ FT-IR and UV-Vis spectroenectrochemistry. Synthetic Metals, 17 (1998) 93
(53) W.C. Chen, T.C. Wen and A. Gopanlan. Electrochemical and Spectroelctrochemical Evidences for Copolymer, Formation between 2-Aminodiphenylamine and Aniline. Journal of The Electrochemical society, 148 (2001) E427-E434
(54) M.A. Cotarelo, F. Huerta, C. Quijada, R. Mallavia and J.L. Vazquez. Synthesis and characterization of electroactive films deposited from aniline dimers. Journal of the Electrochemical Society. 153 (2006) D114-112
(55) E.M. Sherif, S.M. Park. Inhibition of copper corrosion in acidic pickling solutions by N-phenyl-1,4-phenylenediamine. Electrochimica Acta, 51 (2006) 4665-4673
(56) G. Ciric-Marianovic, M. Trchova, E.N. Konyushenko, P. Holler and J. Stejskal. Chemical oxidative polymerization of aminodiphenylamins. J. Phys. Chem. B112 (2008) 6976- 6987
(57) J. Stejskal, A. Riede, M. Helmstedt, P. Holler. The effect of polymerization temperature on molecular weight, crystallinity, and electrical conductivity of polyaniline. Synthetic Metals 96 (1998) 55-61
(58) M. Trchova´, D. Hlavata´, J. Stejskal . Conductivity ageing in temperature-cycled polyaniline. Polymer Degradation and Stability 78 (2002) 393–401
(59) N.R. Chiou and A.J. Epstein. Polyaniline nanofibers prepared by dilute polymerization. Adv. Mater. 17 (2005) 1679-1683
(60) N.R. Chiou and A.J. Epstein. A simple approach to control the growth of polyaniline nanofibers. Synthetic Metals 153 (2005) 69-72
(61) J. Li, L. Zhu, W. Luo, Y. Liu, and H. Tang. Correlation between one-directional helical growth of polyaniline and its pptical activity. J. Phys. Chem. 111 (C2007) 8383-8388
(62) Y.Q. Zhang, W.L. Huang, D.E. Fennell. In situ chemical oxidation of aniline by persulfate with iron (II) activation at ambient temperature. Chinese Chemical Letters 21 (2010) 911–913
(63) H. Ma, J. Wang, S.Z. Abdel-Rahman, P.J. Boor, M.F. Khan. Oxidative DNA damage and its repair in rat spleen following subchronic exposure to aniline. Toxicology and Applied Pharmacology 233 (2008) 247–253
(64) F. DiGirolamo, L. Campanella, R. Samperi, A. Bachi. Mass spectrometric identification of hemoglobin modifications induced by nitrosobenzene. Ecotoxicology and Environmental Safety 72 (2009) 1601–1608
(65) T. Yamano and M. Shimizu. Skin sensitization potency and cross-reactivity of p-phenylenediamine and its derivatives evaluated by non-radioactive murine local lymph node assay and guinea-pig maximization test. Contact Dermatitis 60 (2009) 193-198
(66) W. Hemmer, M. Focke, N. Kriechbaumer, M.Gotz and R. Jarisch. Active sensitization to p-aminodiphenylamine. Contact Dermatitis 37 (1997) 238
(67) S.P. Surwade, S.R. Agnihotra, V. Dua, N. Manohar, S. Jain, S. Ammu, and S.K. Manohar. Catalyst-free synthesis of oligoanilines and polyaniline nanofibers uising H2O2. J. AM. CHEM. SOC.131 (2009) 12528–12529
(68) M.R. Majidi, L.A.P. Kane-Maguire and G. G. Wallace. Facile synthesis of optically active polyaniline and polytoluidine. Polymer 37 (1996) 359-362
(69) S.P. Surwade, N. Manohar and S.K. Manohar. Origin of bulk nanoscale morphology in conducting polymers. Macromolecules 42 (2009) 1792-1795
(70) H. Guan, Li-Zhen Fan, H. Zhang, X. Qu. Polyaniline nanofibers obtained by interfacial polymerization for high-rate supercapacitors. Electrochimica Acta 56 (2010) 964-968
(71) G. Shumakovich, A. Streltsov, E. Gorshina, T. Rusinova, V. Kurova, I. Vasil’eva, G. Otrokhov, O. Morozova, A. Yaropolov . Laccase-catalyzed oxidative polymerization of aniline dimer (N-phenyl-1,4-phenylenediamine) in aqueous micellar solution of sodium dodecylbenzenesulfonate. Jouranl of Molecular Catalysis B: Enzymatic 69 (2011) 83-88