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导电聚合物PEDOT分散体的制备及其在抗静电涂料中的应用研究
Synthesis of Conducting Polymer Pedot Dispersion and Application in Antistatic Coating
【作者】 张莎；
【导师】 孙东成；
【作者基本信息】 华南理工大学 ， 应用化学， 2010， 硕士
【摘要】 导电聚合物聚3,4-乙撑二氧噻吩(简称PEDOT)由于具有高的电导率,较好的环境稳定性和薄膜透明性而受到广泛的关注,并在抗静电涂层、光电二极管、传感器等方面表现出了广阔的应用前景。但由于PEDOT的共轭长链带来的不溶不熔问题使其加工处理困难,从而限制了其商业应用,改善PEDOT的加工性能成为该领域重要且极具意义的研究。制备PEDOT分散体是解决其加工问题直接且重要的途径,本文围绕着探索改善PEDOT加工性能的方法展开,通过化学氧化聚合法成功制备了共聚磺酸掺杂型PEDOT分散体和基于聚氨酯乳胶粒子的PEDOT分散体两种不同类型的分散体,并研究了影响两种不同分散体稳定性的因素及其在抗静电涂料中的应用。本文从掺杂剂入手,以自制的苯乙烯磺酸钠(SSS)和乙烯磺酸钠(SVS)的共聚物PSS-VS为掺杂剂,制备了共聚磺酸掺杂型PEDOT/PSS-VS分散体,并研究了共聚磺酸的共聚比、分子量和用量、氧化剂用量以及理论固含量对分散体稳定性及电导率的影响。得出的最佳工艺条件为:SSS与SVS共聚摩尔比为5/5,磺酸根与单体摩尔比为2/1,氧化剂与单体摩尔比为1.5/1,理论固含量为2.8%。在该工艺条件下制备的PEDOT/PSS-VS电导率高达11.74S/cm,分散体平均粒径为447nm。本文从粒子形态结构入手,以自制的聚氨酯分散体(PUD)为基材,制备了基于聚氨酯乳胶粒子的PEDOT/PU分散体,并研究了不同合成条件和不同粒径大小的聚氨酯基材对分散体性能的影响。通过动态光散射和四探针测试表明,随着复合粒子中PEDOT含量的增加,PEDOT/PU分散体的粒径分布变宽,平均粒径和电导率均增加。综合考虑分散体稳定性和导电性,制备过程中EDOT/PU质量比选择1/10为宜。透射电镜分析表明,复合粒子呈核壳结构,聚氨酯乳胶基材的粒径大小对复合粒子的形貌有较大影响。以自制的两种PEDOT分散体为导电组分配制抗静电涂料,并应用于塑料基材,对涂膜进行了基本分析,结果表明,涂膜的附着力达到2级,透光性≧85%,耐水洗性能和稳定性好,表面电阻为108Ω,达到了抗静电涂料的要求。
【Abstract】 Conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) has obtained extensive attention because of its high conductivity, good environmental stability and transparency film, and showed broad application prospects in the fields of antistatic coating, photoelectric diode, sensors and so on. Unfortunately, highly conjugated backbones of PEDOT which cause insoluble and non-melt problems also lead to the material being rather intractable, thus the commercial application has been limited. To improve the processing performance of PEDOT has been important and meaningful in this field of research. A direct and important mean to solve the problem is preparing PEDOT dispersions. Around to explore ways to improve the processing property of PEDOT, this article has successfully prepared two different types of PEDOT dispersions, copolymer acid doped and based on polyurethane latex particle, by chemical oxidation polymerization. And studied the affecting factors of two different dispersions stability and application in antistatic coatings.Starting from the doping agent, the article has synthesized copolymer acid doped PEDOT/PSS-VS dispersion using copolymer PSS-VS of sodium p-styrenesulfonate (SSS) and sodium vinylsulfonate (SVS) as dopant. The stability and conductivity of dispersion affected by copolymeric ratio, molecular weight and amount of PSS-VS and other factors were investigated and the optimal oxidative polymerization conditions have been found: the copolymeric molar ratio of SSS/SVS is 5/5, molar ratio of SO3-/EDOT and oxidation/EDOT are 2/1 and 1.5/1, the solid content is 2.8wt%. Preparing under the conditions, the conductivity and average particle size of PEDOT/PSS-VS are 11.74S/cm and 447nm respectively.Starting from the particle morphology, the article has prepared PEDOT/PU dispersion based on home-made polyurethane(PU) latex particle, and the properties of dispersion affected by different synthetic conditions and particle sizes of PU substrate are researched. By dynamic light scattering and four-probe test, the particle size distribution of PEDOT/PU dispersion broadens, and the average particle size and conductivity increase. Comprehensive consideration of stability and conductivity, the quality ratio of EDOT/PU in preparation process is 1/10. TEM analysis indicates that the composite particles show a core-shell structure, and the particle sizes of PU substrate have great influence on the morphology of composite particles.Antistatic coatings have been prepared using two self-made PEDOT dispersions as conductive component and applied to plastic substrates. The results of basic analysis of the coating film show that the adhesion of coating achieves 2, light transmission is more than 85%, washing performance and stability are good, the surface resistance is 108Ω, which meet the requirements of antistatic coating.