主链含3-吡啶基-2,5-二噻基噻吩的电化学聚合及其电致变色性能研究
Electrochemical Polymerization and Its Electrochromic Properties of Polymers Containing 3-Pyridinyl-2,5-Dithiathiophene in the Main Chain
DOI: 10.12677/MS.2019.96076, PDF,    国家自然科学基金支持
作者: 帕提古丽•艾散：新疆大学化学化工学院，石油天然气教育部重点实验室，新疆 乌鲁木齐；阿布都克尤木•阿布都热西提, 吐尼莎古丽•阿吾提*：新疆大学功能高分子重点实验室，新疆 乌鲁木齐
关键词: 吡啶基噻吩；电聚合；光谱电化学；电致变色性能；Pyridyl Thiophene； Electropolymerization； Spectroelectrochemistry； Electrochromic Performance
摘要: 本文以四丁基六氟磷酸铵(TBAPF6)为支持电解质，在二氯甲烷:乙腈(V:V = 1:19)溶剂中对单体3-吡啶基-2,5-二噻基噻吩(M3)进行电化学聚合获得了聚(2,5-二噻基-3-吡啶基噻吩)均聚物薄膜(P1)，并且分别以纯单体(M3)与3,4-乙撑二氧噻吩(EDOT)单体按照以(M3:EDOT = 1:1/1:3/3:1, c/c, (mmoL/L))为比例通过电化学聚合制备了聚(2,5-二噻基-3-吡啶基噻吩-3,4-乙撑二氧噻吩) P2 (1:1)、P3 (1:3)和P4 (3:1)等共聚物薄膜。使用核磁共振氢谱(1H-NMR)和傅里叶变换红外光谱(FT-IR)对单体M3进行了表征测试以及利用紫外-可见光谱(UV-Vis)对聚合物P1、P2、P3、P4薄膜的光学性能进行了研究。根据(UV-Vis)和(CV)分析所得的均聚物P1和共聚物P2、P3和P4的薄膜光学能隙依次为2.05 eV、2.02 eV、1.89 eV和2.06 eV，电化学能隙分别为3.56 eV、3.39 eV、3.77 eV和3.22eV。电化学均聚物P1薄膜和共轭聚合物P2、P3、P4薄膜均具有p-型掺杂和n-型掺杂行为。聚合物薄膜除了P2表现出(深紫灰色)以外P1、P3、P4由深棕色(还原)到浅灰色(氧化) (而P4为浅黄棕色)的电致变色转换。P2在440 nm处的光学对比度为42.9%，响应时间为1.1 s，具有良好的电致变色性能。
Abstract: The poly[3-pyridyl-2,5-bis-octyl thiophene]film (P1) and the copolymers of poly[3-pyridyl-2,5-bis- octyl thiophene-co-alt-3, 4-ethylenedioxythiophene] P2 (1:1), P3 (1:3) and P4 (3:1) films were obtained by electrochemical polymerization in equal proportions with the pure monomer of 3-pyridyl-2,5-bis-octyl thiophene (M3) and 3,4-ethylenedioxythiophene (EDOT) (M3:EDOT = 6:0/ 1:1/1:3/3:1, c/c, (mmoL/L)) in a solvent of dichloromethane:acetonitrile (V:V = 1:19) with tet-rabutylammonium hexafluorophosphate (TBAPF6) as a supporting electrolyte, respectively. The M3 was characterized by 1H-NMR, FT-IR and the optical properties of the polymers P1, P2, P3 and P4 films were observed by UV-Vis. Then the optical energy gap values of the homopolymer (P1) flim and the three copolymers (P2, P3, P4) films according to UV-Vis and cyclic voltammetry (CV) were 2.05 eV, 2.02 eV, 1.89 eV and 2.06 eV, and the electrochemical energy gap values were 3.56 eV, 3.39 eV, 3.77 eV, and 3.22 eV, respectively. The polymers of P1, P2, P3, and P4 films had p-type doping and n-type doping behavior. Spectroelectrochemical analysis showed that the polymer films showed electrochromic conversion of P1, P3, and P4 from dark brown (reduced) to light gray (oxidized) (P4 was light yellowish brown) except that P2 exhibited (dark purple). The polymer P2 has a good electrochromic behavior and its optical contrast at 440 nm is 42.9%, the response time is 1.1 s.
文章引用：帕提古丽•艾散, 阿布都克尤木•阿布都热西提, 吐尼莎古丽•阿吾提. 主链含3-吡啶基-2,5-二噻基噻吩的电化学聚合及其电致变色性能研究[J]. 材料科学, 2019, 9(6): 600-611. https://doi.org/10.12677/MS.2019.96076

参考文献

[1] Waltman, R.J., Bargon, J. and Diaz, A.F. (1983) Electrochemical Studies of Some Conducting Polythiophene Films. The Journal of Physical Chemistry, 8, 1459-1463. [Google Scholar] [CrossRef] 
[2] Pouwer, K.L., Vries, T.R., Havinga, E.E., Meijer, E.W. and Wynberg, H. (1988) Poly-1,4-diketones Obtained by the Stetter Reaction: A New Route to Conducting Heterocyclic Poly-mers. Journal of the Chemical Society, Chemical Communications, 21, 1432. [Google Scholar] [CrossRef] 
[3] Roncali, J., Garreau, R. and Lemaire, M. (1990) Electrosynthesis of Conducting Poly-Pseudo-Crown Ethers from Substituted Thiophenes. Journal of Electroanalytical Chemistry, 278, 373-378. [Google Scholar] [CrossRef] 
[4] Lee, K. and Sotzing, G.A. (2001) Poly(thieno[3,4-b]thiophene) a New Stable Low Band Gap Conducting Polymer. Macromolecules, 34, 5746-5747. [Google Scholar] [CrossRef] 
[5] Kumar, S.R.C. (1998) Advances in Conductive Polymers. European Polymer Journal, 34, 1053-1060. [Google Scholar] [CrossRef] 
[6] Li, Y. and Zou, Y. (2010) Conjugated Polymer Photovoltaic Materials with Broad Absorption Band and High Charge Carrier Mobility. Advanced Materials, 20, 2952-2958. [Google Scholar] [CrossRef] 
[7] Groenendaal, L., Zotti, G., Aubert, P.H., Waybright, S.M. and Reynolds, J.R. (2010) Electrochemistry of poly(3,4-al- kylenedioxythiophene) Derivatives. Advanced Materials, 15, 855-879. [Google Scholar] [CrossRef] 
[8] Rousseau, T., Cravino, A., Bura, T., Ulrich, G., Ziessel, R. and Roncali, J. (2009) Bodipy Derivatives as Donor Materials for Bulk Heterojunction Solar Cells. Chemical Communications, 13, 1673. [Google Scholar] [CrossRef] [PubMed]
[9] Chen, H., Lu, Y., Ong, T.T. and Ng, S.C. (2009) Synthesis, Characterization, and Prop-erties of Regioregular Conjugated Polymers Containing Quaterthiophene and an Acceptor Repeating Units. Journal of Polymer Science, Part A: Polymer Chemistry, 47, 2163-2171. [Google Scholar] [CrossRef] 
[10] Hong, K.H., Oh, K.W. and Kang, T.J. (2010) Preparation and Properties of Electrically Conducting Textiles by in Situ Polymerization of poly(3,4-ethylenedioxythiophene). Journal of Applied Polymer Science, 97, 1326-1332. [Google Scholar] [CrossRef] 
[11] Abdiryim, T., Jamal, R., Zhao, C., Awut, T. and Nurulla, I. (2010) Structure and Properties of Solid-State Synthesized Poly(3’,4’-ethylenedioxy-2,2’:5’,2’-terthiophene). Synthetic Metals, 160, 325-332. [Google Scholar] [CrossRef] 
[12] Roncali, J., Blanchard, P. and Frere, P. (2005) 3,4-ethylenedioxythiophene(edot) as a Versatile Building Block for Advanced Functional Pi-Conjugated Systems. Journal of Materials Chemistry, 15, 1589-1610. [Google Scholar] [CrossRef] 
[13] Shuai, D., Ahmat, A., Ruxangul, J., Ling, X., Ziping, Z. and Tursun, A. (2018) An Electro-chemical Sensor of Poly(edot-pyridine-edot)/Graphitic Carbon Nitride Composite for Simultaneous Detection of cd2+ and pb2+. Ma-terials, 11, 702. [Google Scholar] [CrossRef] [PubMed]
[14] Gunbas, G. and Toppare, L. (2012) Electrochromic Conjugated Pol-yheterocycles and Derivatives-Highlights from the Last Decade towards Realization of Long Lived Aspirations. Chemical Commu-nications, 48, 1083-1101. [Google Scholar] [CrossRef] 
[15] Abdurashid, A., Ahat, B., Mirzehmet, A., Awut, T. and Nurulla, I. (2016) New Soluble π-Conjugated Polymers Containing 2-Diisopropylamino-1,3,5-Triazine Unit: Synthesis, Characterization and Optical Properties. Journal of Polymer Research, 23, 92. [Google Scholar] [CrossRef] 
[16] Baran, D., Balan, A., Celebi, S., Meana Esteban, B., Neugebauer, H., Sariciftci, N.S., et al. (2010) Processable Multipurpose Conjugated Polymer for Electrochromic and Photovoltaic Applications. Chemistry of Materials, 22, 2978-2987. [Google Scholar] [CrossRef] 
[17] Beaujuge, P.M. and Reynolds, J.R. (2010) Color Control in Pi-Conjugated Organic Polymers for Use in Electrochromic Devices. Chemical Reviews, 110, 268-320. [Google Scholar] [CrossRef] [PubMed]
[18] 张国兵. 低能带隙、低HOMO能级的给/受体聚合物太阳能电池材料的设计、合成及光伏性能[D]: [硕士学位论文]. 上海: 上海交通大学, 2011.
[19] Heinze, J. (2010) Cyclic Voltammetry—“Electrochemical Spectroscopy”. New Analytical Methods (25). Angewandte Chemie International Edition, 23, 831-847. [Google Scholar] [CrossRef] 
[20] Ming, S., Zhen, S., Lin, K., Zhao, L., Xu, J. and Lu, B. (2015) Thiadiazolo[3,4-\r, c\r, ]pyridine as an Acceptor toward Fast-Switching Green Donor-Acceptor-Type Elec-trochromic Polymer with Low Bandgap. ACS Applied Materials and Interfaces, 7, 11089-11098. [Google Scholar] [CrossRef] [PubMed]
[21] Jian, N., Gu, H., Zhang, S., Liu, H., Qu, K., Chen, S., et al. (2018) Synthesis and Electrochromic Performances of Donor-Acceptor-Type Polymers from Chalcogenodiazolo [3,4-c]pyridine and Alkyl Prodots. Elec-trochimica Acta, 266, 263-275. [Google Scholar] [CrossRef] 

为你推荐