近代高分子科学聚苯胺简介.pptVIP

导电高分子材料聚苯胺研究进展, 工程 ,1,目录,OUTLINE,聚苯胺发展历史,聚苯胺合成方法,聚苯胺应用领域,聚苯胺发展前景,1,2,3,4,2,聚苯胺发展历史,aniline black emeraldine,non-greening aniline black,1947年，Brown 首次在文章中提及polyamine,3,H. Letheby, Journal of the Chemical Society 15 (1862) 161. E. Noelting, Scientific and Industrial History of Aniline Black, WM. J. Matheson & Co, 1889,4,深蓝色 部分氧化 导体,绿色 部分氧化 质子导体,绿色 部分氧化 质子导体,无色 全还原 绝缘,A.G. MacDiarmid, J.C. Chiang, A.F. Richter, A.J. Epstein, Synthetic Metals 18 (1987) 285,5,还原单元,氧化单元,结构单元可表示为,其中y 表示氧化-还原程度。氧化度不同的聚苯胺表现不同的组分、结构、颜色及电导特性。如从完全还原态(Leucoemeraldiline , LB y = 1) 向完全氧化态( Pernigraniline , PB y = 0) 转化的过程中,随氧化度的提高聚苯胺依次表现为黄色、绿色、深蓝、深紫色和黑色。,6,聚苯胺合成方法,Scheme 3. Monomeric and dimeric products of aniline oxidation: 1) nitrobenzene, 2) phenazine, 3) 2-aminodiphenylamine, 4) hydrazobenzene, 5) azobenzene, 6) azoxybenzene, 7) potassium orthoaminophenyl sulfate, 8) benzidine, 9) 4-aminodiphenylamine, 10) N-phenyl-1,4-benzoquinonediimine, 11) indophenol, 12) 1,4-benzoquinone, 13) 1,4-benzoquinoneimine, 14) 4-aminophenol, 15) phenylhydroxylamine, and 16) nitrozobenzene.,G.A. Planes, J.L. Rodrguez, M.C. Miras, G. Garca, E. Pastor, C.A. Barbero, Physical Chemistry Chemical Physics 12 (2010) 10584,7,Scheme 4. Single-electron oxidations of aniline (C), anilinium cation (A), aniline cation radical (D) and aniline neutral radical (F), accompanied with corresponding acid/base equilibria: anilinium cation/aniline, anilinium dication radical (B)/aniline cation radical, aniline cation radical/aniline neutral radical, aniline dication (E)/aniline nitrenium cation (G), and aniline nitrenium cation/aniline nitrene(H singlet nitrene).,8,Scheme 5. Major products of possible aniline oxidative dimerization reactions (A 138, B 138, C 139, D 115,122,139, E 138) determined computationally by using AM1/COSMO 115,122,138,139 and PM3/COSMO 122,138,139 semiempirical quantum chemical methods.,9,Scheme 7. Redox reactions versus Michael addition reactions of N-phenyl-1,4-benzoquinonediimine and/or higher iminoquinonid oligoanilines with aniline in highly acidic (pH 2), respectively.,Scheme 6. The reactions of aniline nitrenium cation with aniline and sulfate anion,giving 4-ADPA and ortho-aminophenyl sulfate, respectively.,10,Fig. 1. Molecular structures of low-molecular-weight OANIs formed/precipitated in APS/aniline system in buffer solutions at pH 2.510.0 or under falling-pH conditions, proposed by several research groups on the basis of structural characterization (elemental analysis, FTIR, Raman, UVvis, and 1H/13C/15N NMR spectroscopies, GCMS, ESI-MSand MALDI-TOF MS) and semiempirical quantum chemical predictions of oligomerization mechanism:,1 化学氧化聚合法 聚苯胺的化学氧化聚合法，是在酸性水溶液中用氧化剂使苯胺单体氧化聚合。化学氧化法能够制备大批量的聚苯胺，也是最常用的一种制备聚苯胺的方法。 质子酸是影响苯胺氧化聚合的重要因素，它主要起两方面的作用：提供反应介质所需要的pH值和以掺杂剂的形式进入聚苯胺骨架赋予其一定的导电性。 苯胺化学氧化聚合常用的氧化剂有：过氧化氢、重铬酸盐、过硫酸盐、 氯化铁等，所得聚苯胺性质基本相同。,11,2 电化学聚合法 电化学法制备聚苯胺是在含苯胺的电解质溶液中，选择适当的电化学条件，使苯胺在阳极上发生氧化聚合反应，生成粘附于电极表面的聚苯胺薄膜或是沉积在电极表面的聚苯胺粉末。 主要的电化学聚合法有：动电位扫描法、恒电位法、恒电流法和脉冲极化 电化学方法合成的聚苯胺纯度高，反应条件简单且易于控制。但电化学法只适宜于合成小批量的聚苯胺。,12,13,聚苯胺应用领域,防腐蚀涂料,抗静电和电磁屏蔽材料,其它材料,特殊分离膜,二次电池的电极材料,选择电极,应用,14,Fig. 2. (a) Partially protonated PANI-NF: zig-zag lines and the green dots represent PANI chains and Cl ions, respectively; the grain feature of protonated regimes is implicated. (b) An illustration ofentangled PANI-NFs; the internanotubular contacts are marked in blue and an inset shows a close view of the red rectangle area. The 3D green regimes in the inset illustrate protonated grain structures in a single PANI NF. (c) SEM image of PANI nanodevice.(For interpretation of the references to color in this figure legend, the reader is referred to the web version of the article.),15,Fig. 3. Top: Scheme of the formation for nitrogen-doped graphene sheets derived from PANI and Co precursors using multiwalled CNTs (MWCNTs) as a template. Bottom: SEM (a) and HR-TEM (bd) images of the graphene-rich nanocomposites observed in Co-N-MWCNT catalysts.,G. Wu, N.H. Mack, W. Gao, S. Ma, R. Zhong, J. Han, J.K. Baldwin, P. Zelenay, ACS Nano 6 (2012) 9764,16,S. Liu, J. Wang, D. Zhang, P. Zhang, J. Ou, B. Liu, S. Yang, Applied Surface Science 256 (2010) 3427 J. Yang, J. Choi, D. Bang, E. Kim, E.-K. Lim, H. Park, J.-S. Suh, K. Lee, K.-H. Yoo, E.K. Kim, Y.-M. Huh, S. Haam, Angewandte Chemie International Edition 50 (2011) 441,Fig. 4. Schematic illustration of the preparation of organic photothermal agents based on PANI-NPs and their appl