基于EDOT和二溴代物的新型导电聚合物制备及其电致变色性能

发布时间：2018-03-23 08:11

本文选题：导电聚合物　切入点：5　出处：《青岛科技大学》2017年硕士论文　论文类型：学位论文

【摘要】：导电聚合物由于其独特的性能优势而引起了人们的广泛关注,这些优势包括合成工艺简单,加工性能优异,多色彩显示。目前,导电聚合物的研究主要集中在新型聚合物单体的设计和合成上。3,4-二氧乙撑噻吩(EDOT)由于其特点鲜明,性能优异,被广泛应用在新型导电聚合物单体中,用来改善相应导电聚合物的电致变色性能。本论文主要研究了以EDOT为原料,经过分子设计,分别和5,7-二溴吲哚、2,7-二溴-9,9螺二芴、4,7-双(2-溴-5-噻吩基)-2,1,3苯并噻二唑,通过Stille偶联反应合成了三种新型单体,并基于相应的聚合物膜制备了电致变色器件,研究了其电致变色性能。1、以EDOT和5,7-二溴吲哚为原料,通过偶联反应生成了新型单体5,7-双(2-(3,4-亚乙二氧基)噻吩基)-吲哚,即5,7-bis(2-(3,4-ethylenedioxy)thienyl)-indole(ETI)。在乙睛体系中,基于ETI单体制备了高性能的、具有自支撑性质的导电聚合物PETI。研究表明该聚合物膜具有优良的电化学活性和稳定可逆的氧化还原性质。利用红外光谱、核磁氢谱等分析法探讨了该聚合物聚合反应机理。光谱电化学研究表明,PETI具有良好的电致变色性质,显示出两种不同颜色:棕色和蓝色,并且具有高的光对比度(ΔT%)和着色效率。基于PETI和聚(3,4-二氧乙撑噻吩)(PEDOT)研制了电致变色器件,该器件具有快速的响应时间,较高的着色效率,良好的光学记忆和稳定性。2、以EDOT和2,7-二溴-9,9’螺二芴为原料,合成了新的化合物2,7-双(2-(3,4-亚乙二氧基)噻吩基)-螺二芴,2,7-bis(2-(3,4-ethylenedioxy)thienyl)-spirobifluorene(ETS),制备了相应的聚合物PETS。该聚合物薄膜具有良好的电化学活性,电致变色性能良好,能够在粉红色和天蓝色之间相互转换。以PEDOT和PETS制备了电致变色器件,通过光谱电化学方法研究了其电致变色性能。研究表明,该器件能够在黄绿色和深蓝色之间反复转换,转换时间快,变色稳定性好,器件在600nm处的着色效率为290 cm2 C-1。3、以EDO T和4,7-双(2-溴-5-噻吩基)-2,1,3苯并噻二唑为原料,经过Stille反应制备了单体4,7-双(2-(3,4-亚乙二氧基)-5-噻吩基)-2,1,3-苯并噻二唑,即4,7-Bis(2-(3,4-ethylenedioxy)-5-thienyl)-2,1,3-benzothiadiazole(ETB)。该单体通过电化学聚合制备了相应的聚合物PETB,其氧化电位为0.75 V,光谱电化学研究表明,PETB可以在深绿色和深蓝色之间可逆转化,并且显示出了良好的电致变色性能,具有较高的着色效率,在电致变色智能窗方面具有潜在的应用。
[Abstract]:Conductive polymers have attracted wide attention due to their unique performance advantages, including simple synthesis process, excellent processing performance, multi-color display. The research of conductive polymer is mainly focused on the design and synthesis of novel polymer monomers. Due to its distinctive characteristics and excellent properties, it has been widely used in novel conductive polymer monomers. In this paper, the electrochromic properties of the corresponding conductive polymers were studied by using EDOT as the raw material, and the molecular design was carried out, respectively, with 5o 7- dibromoindole 2, dibromoindole 9, spirofluorene 4, 7, bis-2-bromo-5-thiophene-1-tribenzothiadiazole-1-3-benzothiadiazole, respectively, and 5-dibromoindole and 5-dibromoindole-2-dibromoindole-9-difluorofluorene. Three new monomers were synthesized by Stille coupling reaction, and electrochromic devices were prepared based on the corresponding polymer films. The electrochromic properties of the devices were studied. The electrochromic properties of the devices were studied by using EDOT and 5-dibromoindole as raw materials. By coupling reaction, a new monomer, 5o 7- dioxy (2-dimethylidene) thienyl) -indoleindole (57-biso 2-ethylenedioxythienylthienyl chloride-indoleurane) was synthesized by coupling reaction. High performance ETI monomers were prepared in the system of ethylenedioxythienedioxythienyl-indoledoxylic acid (ETI). A self-supporting conductive polymer PETI.The study shows that the polymer film has excellent electrochemical activity and stable and reversible redox properties. The polymerization mechanism of the polymer was investigated by nuclear magnetic hydrogen spectroscopy and other methods. Spectroelectrochemical studies showed that PETI had good electrochromic properties and showed two different colors: Brown and blue. Based on PETI and PEDOT, an electrochromic device has been developed. The device has fast response time and high coloring efficiency. Good optical memory and stability, using EDOT and 2-dibromo-9 '-spirodifluorene as raw materials, A new compound 2H _ 7- Bis _ 2-N _ 3H _ 3H _ 3H _ 3H _ 2O _ 2H _ 2H _ 2H _ 2H _ 2H _ 2H _ 7-biso _ 2-H _ 3N _ 4-ethylenedioxybutadiene thienyl-spirobifluoreorene-ETSN was synthesized and the corresponding polymer PETSs was prepared. The film has good electrochemical activity and good electrochromic properties, and its electrochromic properties are good. The electrochromic device was prepared by PEDOT and PETS. The electrochromic properties of the device were studied by spectroelectrochemical method. The results show that the device can be converted repeatedly between yellowish green and dark blue. The conversion time is fast and the stability of discoloration is good. The coloring efficiency of the device at 600nm is 290 cm2 C-1.3. The raw materials of the device are EDO T and 4o 7-bis-2-bromo-5-thiophene 2-bromo-5-thiophene 1-tribenzo-thiadiazole. The monomer 4H _ 7- Bis _ 2-N _ 3N _ 4-ethylene dioxy _ 2-thiophene _ (2) N _ (1) C _ (3) -benzothiadiazole was prepared by Stille reaction. The corresponding polymer PETB was prepared by electrochemical polymerization. The oxidation potential of PETB was 0.75 V. Spectral and electrochemical studies showed that PETB could be reversible converted between dark green and dark blue, and showed good electrochromic properties. It has high coloring efficiency and potential application in electrochromic intelligent windows.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O633.5;TB34

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