以乳液融合法製備導電核殼型奈米顆粒及其性質研究

Abstract

本研究聚焦於開發可撓式生質導電複合薄膜，並透過本實驗所研發之新型乳化融合法，將兩種不同乳液直接混合形成核殼型複合乳膠顆粒。本論文分為兩部分，其中第一部分為利用格林那合成法聚合聚噻吩(P3HT)導電高分子，作為生質複合薄膜之導電高分子的來源。第二部份則利用十二烷基硫酸鈉(SDS)將高分子P3HT/甲苯混合物分散於水中形成P3HT水乳液，並結合本實驗室自行開發之生質乳液，製備成核殼型複合乳膠顆粒，並探討其塗佈成膜後之光電特性。 於本研究之第一部份中，我們從分子設計、聚合技術和反應條件等方面，合成了正規序列的聚噻吩，並使用格林那合成法進行末端官能化反應，接著再以核磁共振儀來計算高分子之規整度以及確認其分子結構、凝膠滲透層析儀以及基質輔助雷射脫附游離/飛行時間質譜儀分析來鑑定合成高分子之分子量及其末端官能基團，接著再透過差示掃描分析儀、X光繞射儀來分析高分子之結晶情形。 於第二部份複合膜製備實驗研究上，我們開發了將兩種不同乳液直接混合之乳液融合方法，從穿透式電子顯微鏡可以清楚觀察到P3HT借助甲苯之作用使得高分子吸附於乳膠顆粒之表面，因此形成P3HT在殼層，生質乳膠在核層之核殼型結構。本研究發現，此過程中只需添加固含量5%之P3HT即可形成連續之導電網路結構，並藉由DMSO溶劑處理之過程，使得複合膜內部之P3HT得以重新排列，進而使導電度得到提升，而後續透過紫外線/可見光分光光譜儀及差示掃描量熱儀之結果得到證實。於動態機械分析儀表明P3HT之添加可以使得複合膜之機械性質提升，且透過複合薄膜之負重摺疊實驗，發現經折疊後薄膜表面電阻之恢復，顯示此複合膜具有柔軟及自我修復之特性。 本研究將導電高分子引入材料中，並借助高分子本身獨特之光電性質，使複合膜具有導電特性，並透過對複合材料性質的深入探討，期許為開發具有優異性能和多功能性的複合膜奠定基礎，開啟複合材料領域的新可能性。

This research focuses on the development of flexible bio-based conductive composite films, and through the new emulsion fusion method developed in this experiment, two different emulsions are directly mixed to form core-shell composite emulsion particles. This thesis is divided into two parts, the first part of which is to use the Grignard Metathesis method to polymerize polythiophene (P3HT) conductive polymers as the source of conductive polymers for bio-based composite films. The second part uses SDS to disperse the polymer P3HT/toluene mixture in water to form a P3HT emulsion, and combines the bio-based emulsion developed by our laboratory to prepare core-shell composite latex particles, and discusses the photoelectric characteristics of composite films. In the first part of this study, we synthesized polythiophenes with regular sequences from the aspects of molecular design, polymerization techniques, and reaction conditions, and used the Grignard Metathesis method for terminal functionalization reactions. Then use nuclear magnetic resonance to calculate the regularity of the polymer and confirm its molecular structure, gel permeation chromatography and matrix-assisted laser desorption/time-of-flight mass spectrometer analysis to identify the molecular weight and terminal function of the synthesized polymer group. Then, analyze the crystallization of the polymer through differential scanning analyzer and X-ray diffractometer. In the second part of the experimental research on the preparation of composite membranes, we developed an emulsion fusion method that directly mixes two different emulsions. From the transmission electron microscope, it can be clearly observed that P3HT makes polymers adsorb on the surface of latex particles through the action of toluene. Therefore, a core-shell structure is formed in which P3HT is in the shell layer and biomass latex is in the core layer. This study found that a continuous conductive network structure can be formed only by adding P3HT with a solid content of 5% in this process. And through the process of DMSO solvent treatment, the P3HT inside the composite film can be rearranged, thereby improving the conductivity. The improvement was confirmed by the results of ultraviolet/visible light spectrometer and differential scanning calorimeter. The dynamic mechanical analyzer shows that the addition of P3HT can improve the mechanical properties of the composite film. And through the load folding experiment of the composite film, it is found that the surface resistance of the film after folding is restored, indicating that the composite film has softness and self-recovery properties. In this study, conductive polymers are introduced into the material, and the composite film has conductive properties by virtue of the unique photoelectric properties of the polymer itself. And through the in-depth discussion on the properties of composite materials, it is expected to lay the foundation for the development of composite membranes with excellent performance and multifunctionality, and open up new possibilities in the field of composite materials.