基于噻吩-蒽单元的无规共聚物电化学制备及其电致变色性能研究  

Electrochemical preparation and electrochromic properties of random copolymer based on thiophene anthracene unit

作　　者：郭亚飞 陶益杰 梁高勇 董梦杰 王美慧 郝新敏 GUO Yafei;TAO Yijie;LIANG Gaoyong;DONG Mengjie;WANG Meihui;HAO Xinmin(Institute of Quartermaster Engineering&Technology,Academy of System Engineering Academy of Military Science,Beijing 100010,China;College of Materials Science and Engineering,Hunan University,Changsha 410082,China)

机构地区：[1]军事科学院系统工程研究院军需工程技术研究所,北京100010 [2]湖南大学材料科学与工程学院,长沙410082

出　　处：《材料工程》2022年第11期165-172,共8页Journal of Materials Engineering

摘　　要：蒽单元嵌入聚噻吩主链能显著调控聚合物的变色性能,但其聚合电位偏高易导致聚合物的成膜质量和性能较差。为降低含蒽单元的单体电聚合电位,通过Stille偶联反应合成了9,10-二(2-噻吩基)蒽单体(Th-An-Th),并分别在BFEE,BFEE+CF_(3)COOH,LiClO_(4)/ACN和LiClO_(4)/PC等聚合媒介中进行电化学聚合。结果表明:Th-An-Th难以通过电化学反应共聚,但可以作为共单体与噻吩(Th),3-甲基噻吩(MeTh),3,4-亚乙基二氧噻吩(EDOT)和硒酸(SePh)在低电位下进行无规共聚,得到系列无规共聚薄膜P1,P2,P3,P4。循环伏安和FTIR测试证实了聚合过程和共聚物的特征结构,光谱电化学测试结果表明,系列共聚物均具有丰富的颜色变换性能,在-0.6 V到1.0 V扫描下,P1,P3,P4膜可实现4种颜色的变化,且表现出良好的近红外变色能力。共聚物薄膜具有较快的开关响应速度和良好的电化学稳定性,P4膜在521 nm处漂白和着色响应时间分别为1.9 s和3.4 s,光学对比度为35.6%,在210次循环变色后,共聚物光学对比度仅损失2.3%,电化学循环400次仍保持82%的电化学活性。The intercalation of anthracene units into polythiophene backbone can significantly regulate the discoloration properties of polymers,but the high polymerization potential leads to poor film-forming quality and properties of polymers.In order to reduce the oxidation potential of monomers containing anthracene units,a monomer 9,10-bis(2-thiophenyl)anthracene(Th-An-Th)was synthesized by Stille coupling reaction and electrochemically polymerized in polymerization solvent BFEE,BFEE+CF_(3)COOH,LiClO_(4)/ACN and LiClO_(4)/PC,respectively.The results show that th an th is difficult to copolymerize by electrochemical reaction.However,it can be a good comonomer to obtain copolymers with other monomers such as thiophene(Th),3-methylthiophene(MeTh),3,4-ethylenethiophene(EDOT)and selenophone(SePh)via electrochemical copolymerization.The copolymerized films are named as P1,P2,P3 and P4.Cyclic voltammetry and FTIR tests confirm the polymerization process and the characteristic structure of the copolymers.The spectroelectrochemical test results show that the series of copolymers have rich color conversion properties.P1,P3 and P4 films can change four colors under-0.6 V to 1.0 V scanning,and show good near-infrared discoloration ability.The copolymer film has fast switching response rate and good electrochemical stability.The bleaching and coloring response times of P4 film at 521 nm are 1.9 s and 3.4 s,respectively,and the optical contrast is 35.6%.After 210 switching cycles,the optical contrast of the copolymer is only lost by 2.3%,and the electrochemical activity of the copolymer remains 82%after 400 cycles.

关 键 词：噻吩 蒽 电化学共聚 电致变色 

分 类 号：TQ15[化学工程—电化学工业]