聚苯胺/二氧化矽界孔複合材料及有機酸摻雜聚亞醯胺薄膜之製備、鑑定與應用研究

Preparation, Characterization and Applications of Polyaniline/Silica Mesocomposites and Organic Acid-Doped Polyimide Membranes

徐健華(Chien-Hua Hsu)

指導教授 ： 葉瑞銘

中原大學/理學院/化學研究所/碩士(2013年)

https://doi.org/10.6840/cycu201300594

摘要

中文摘要
本論文分為兩部分，首先第一部分主要探討經製備、鑑定一系列不同比例之電活性聚苯胺/二氧化矽介孔複合材料，其對於熱傳導常數之變化，而第二部分則是以有機磺酸摻雜聚亞醯胺薄膜之製備與其性質之探討。
在本論文第一部分中，利用果糖作為模板以非界面活性劑模板法製備末端修飾N-[3-(trimethoxysilyl)-propyl]aniline 之中孔洞二氧化矽微球，以氮氣吸/脫附儀(BET)量測材料之表面積，並分別利用場效發射式掃描電子顯微鏡(FE-SEM)和穿透式電子顯微鏡(TEM)觀察中孔洞二氧化矽微球表面型態和內部結構。再以傅立葉轉換式紅外光譜儀(FT-IR)、固態核磁共振光譜儀(13C-NMR、29Si-NMR)分別做基本化學結構鑑定。
接著，將中孔洞二氧化矽微球導入聚苯胺製備成聚苯胺/二氧化矽介孔複合材料，並利用穿透式電子顯微鏡(TEM)觀察二氧化矽在聚苯胺中的分散型態；在性質研究部分，探討電活性聚苯胺/二氧化矽介孔複合材料在熱性質、熱傳導能力、機械性質、氣體滲透及表面接觸的特性變化分析。
本論文第二部分是利用氧化聚合一步合成法合成穩定的半氧化半還原態之胺基封端苯胺三聚體(amine-capped aniline trimer; ACAT)並選用非共平面之二酸酐(2,2-bis[4-(dicarboxyphenoxy)phenyl]propane dianhydride，BSAA)進行電活性聚亞醯胺的合成，並製備出非電活性聚亞醯胺 (PI)薄膜做比較，初步以傅立葉轉換式紅外光譜儀(FT-IR)、液態核磁共振光譜儀(1H-NMR)及質譜儀(Mass)分別做基本化學結構鑑定。
進一步以不同鏈長之有機磺酸摻雜之材料探討具電活性共軛鏈段之ACAT對於摻雜後之材料在熱性質、機械性質以及氣體滲透分離之趨勢；最後利用非電活性聚亞醯胺薄膜與電活性聚亞醯胺薄膜作系統性之比較，並突現具電活性之聚亞醯胺薄膜之電活性鏈端所帶來之影響。

關鍵字

聚苯胺 ； 苯胺三聚體 ； 電活性 ； 有機磺酸 ； 聚亞醯胺 ； 二氧化矽 ； 介孔 ； 非界面活性劑

並列摘要

Abstract
This study is divided in two parts , the first part mainly investigate the preparation, identification of different proportions of polyaniline / silica mesoporous composite material, its thermal conductivity change, while the second part is based on organic sulfur acid being doped polyimide film and explores their propertys.
In first part, we present the comparative studies for the effect of aniline-modified mesoporous silica (AMS), raw silica (ARS) and non-modified raw silica (NRS) particles on the physical properties of as-prepared polyaniline (PANI)-silica mesocomposite (PSM), nanocomposite (PSN) and PANI-raw silica (PRSN) membranes. First of all, the aniline-modified silica particles were synthesized by performing conventional base-catalyzed sol-gel reactions of TEOS in the presence/absence of PAPTMS molecules. The as-prepared aniline-modified silica particles were then characterized through Fourier Transform Infrared (FTIR), solid-state 13C-nuclear magnetic resonance (13C-NMR) and 29Si-NMR spectroscopy. Subsequently, the PSM and PSN materials were prepared through in-situ oxidation polymerization reactions of aniline monomers in the presence of AMS, ARS and NRS particles. The dispersion capability of silica particles in polymer matrix was further observed by transmission electron microscopy (TEM) studies. Gel permeation chromatography (GPC) was used to determine the molecular weights of as-prepared samples. Effect of material composition on the thermal, mechanical, surface and gas permeability properties of PSM and PSN membranes were investigated by thermal gravimetric analysis (TGA), transient plane source (TPS) technique, dynamic mechanical analysis (DMA), contact angle measurement and gas permeability analysis (GPA) technique, respectively.
Another part, we combine the amine-capped aniline trimer (ACAT) and 4,4’-(4,4’-Isopropylidene-diphenoxy)bis(phthalic anhydride) (BSAA) to prepare the Electroactive Polyimide (EPI) by using casting method, and conventional non-electroactive Polyimide (PI) membranes were also prepared for control experiments. Initial we identify chemical structure of Electroactive Polyimide (EPI) with Fourier transform infrared spectroscopy (FT-IR), the liquid NMR spectrometer (1H-NMR) and mass spectrometry (Mass).
Further explore a different chain lengths of the organic sulfonic acid doped membranes with electroactive conjugated segment ACAT in thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and permeability analysis (GPA) trend. Finaly, we use the Systematic comparison of non-electroactive Polyimide (PI) and Electroactive Polyimide (EPI) and emergent effective with the electroacitve segment of electroactive polyimide membrane.

並列關鍵字

Electroactive ； mesoporous ； polyaniline ； silica ； aniline trimer ； organic sulfonic acid ； Polyimide

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