基于手性溶致液晶模板法制备螺旋型手性导电聚合物的研究

The chiral conducting polymer nanomaterials with helical structure which have the unique photical and electrical characterization have the significent application in the fields of the biological sensors, chiral recognition and separation, and invisible materials. And the research work on the induced preparation of the chiral conducting polymer nanomaterial made from the achiral monomers is an important scientific research. In this project, based on the lyotropic liquid crystal mixed of the ionic liquid and the polyoxyethylene-polyoxypropylene-polyoxyethylene amphiphilic triblock copolymer, a novel chiral lyotropic liquid crystal template will be induced by doping chiral molecules into the original lyotropic liquid crystal system. The nanostructured chiral conducting polymers with helical structure will be prepared from achiral monomers (thiophene, 3,4-ethylenedioxythiophene, pyrrole and aniline) by electrochemical method in the as-prepared chiral lyotropic liquid crystal template. The structure, morphology, thermal stability, conductivity, electrochemical and optical activities of the chiral conducting polymers will be characterized. The construction conditions of the novel chiral lyotropic liquid crystal template and the law of the structure of the product cotrolled by the template will be explored in order to provide an efficient method for the preparation of the functionalized chiral conducting polymer nanomaterials with the explicit structure cotrolled by the template. The relationship between the structure and the performance (such as conductivity, electrochemical and optical activities) of the conducting polymer nanomaterials will be clarified, which can provide the theoretical basis of the preparation of the goal product with the new fuction by designing its structure. The research work on whether the template is suitable for the monomers with the different structures will be explored in order to charify the specificity or the universality of the designed template. At the same time, this research is respected to charify the mechanism of the preparation of chiral conducting polymer nanomaterials with helical structure by the induction of the template.

螺旋型手性导电聚合物纳米材料具有独特的光电特性，在生物传感器、手性分离和识别及隐形材料等领域具有重要的应用价值，如何由非手性单体制备结构清晰的螺旋型手性导电聚合物纳米材料具有重要的科学研究价值。本项目基于离子液体与聚氧乙烯-聚氧丙烯-聚氧乙烯双亲三嵌段共聚物复合体系，通过掺杂手性分子构建新型手性溶致液晶作模板，诱导非手性单体（噻吩、3,4-乙撑二氧噻吩、吡咯和苯胺）电聚合为螺旋型手性导电聚合物，对产物结构、形貌进行表征，对其热稳定性、电学、电化学和光学性能进行测定。研究新型手性溶致液晶模板的构建条件及模板调控产物形貌的规律，为可控制备结构清晰的功能导电聚合物提供有效方法；阐明导电聚合物构效关系，为通过调控产物形貌实现制备具有特定功能的目标导电聚合物提供理论依据；探索模板法对不同结构单体的适用性，初步提出模板特异性或普适性规律, 并阐明模板法诱导制备螺旋型手性导电聚合物纳米材料的机理。

手性导电聚合物纳米材料具有独特的光电特性，在生物传感器、手性分离和识别及隐形材料等领域具有重要的应用价值，如何有效调控实验参数从而制备结构清晰的目标手性导电聚合物纳米材料具有重要的科学研究价值。本项目基于离子液体与聚氧乙烯-聚氧丙烯-聚氧乙烯双亲三嵌段共聚物复合体系，通过掺杂手性分子构建新型手性溶致液晶作模板，诱导非手性单体电聚合为手性导电聚合物。主要研究内容为：.（1）由1-丁基-3-甲基咪唑六氟磷酸盐和聚氧乙烯-聚氧丙烯-聚氧乙烯双亲三嵌段共聚物成功构建溶致液晶体系。表面活性剂浓度范围为40%-60%时可形成溶致液晶，继续掺杂浓度低于1%的樟脑磺酸手性小分子，不会改变原有的液晶织构。该新型溶致液晶体系为电化学方法制备手性导电聚合物纳米材料提供了新型的非对称聚合环境。.（2）以上述体系为模板采用电化学方法（恒电位法和循环伏安法）成功制备了聚噻吩、聚3,4-乙撑二氧噻吩、聚吡咯和聚苯胺系列聚合物纳米材料，实现了由非手性单体诱导电聚合为手性导电聚合物纳米材料。构建的新型溶致液晶在聚合过程中赋予产物特殊的手性结构，为手性功能材料的合成提供了一种模板制备新方法。.该研究成果具有的科学意义和应用价值在于，解决了现有手性单体种类有限、价格昂贵的问题。如果按照传统的方法先设计合成新型手性单体必须通过复杂的有机合成反应及繁琐的提纯过程，成本高操作复杂成功率低而难以推广。因此，该课题提供的方法可通过简单的模板诱导非手性单体在手性非对称反应环境中聚合为手性聚合产物，为模板法可控制备手性结构的聚合物材料提供了可能性。