- 學位論文
聚亞醯胺(ODA-BSAA)/二氧化矽及聚亞醯胺(BAPN-OPDA)/二氧化矽混成材料之製備 與性質研究
Preparation and Properties of Polyimide(ODA-BSAA)/silica and Polyimide(BAPN-OPDA)/silica Hybrid Materials
摘要
中文摘要 本研究可分為兩部份，第一部份為聚亞醯胺(1)/二氧化矽（Polyimide (1)/ SiO2）混成材料，主要是利用ODA/ BSAA等單體加入Ligand加強有機相（PI）及無機相（SiO2）之間的鍵結，並製備成一系列有機/無機混成聚亞醯胺(1)/二氧化矽混成材料，並探討有機/無機混成薄膜的特性與無機物二氧化矽在聚亞醯胺基材中的分散性。在本研究中，將討論此合成之混成材料其做為塗料應用時之金屬防蝕性。在腐蝕測試實驗中，將不同比例含量的聚亞醯胺(1)/二氧化矽塗布於冷軋鋼片（CRS）上時，將發現其金屬防腐蝕的性質會大大的提升。隨之進行一系列的電化學腐蝕模擬測試，以取得其腐蝕電位（Ecorr）、極化電阻（Rp）、腐蝕電流（Icorr）、阻抗之數據。並進一步探討所合成之混成材料的化學結構、耐熱性質、阻氣與阻水性質。其產物以FTIR、XRD、與TEM來進行分析鑑定；並利用GPC來量測評估混成材料中有機高分子聚合物的分子量大小；進一步將此材料製成自由立膜，以GPA及VPA測量其氣體穿透性和水氣穿透性；使用TGA與DSC來評估其熱性質，並以DMA量測其機械性質。 第二部份為聚亞醯胺(2)/二氧化矽奈米複合材料，主要是利用BAPN/OPDA等單體，以小分子有機鹼催化的方式導入無機的二氧化矽，並添加偶合劑（ATS）以加強有機相（PI）及無機相（SiO2）的相容性，因而製備出一系列新型有機/無機混成聚亞醯胺(2)/二氧化矽奈米複合材料。並進一步探討偶合劑對奈米複合材料的影響以及UV-vis 、FTIR、與TEM的性質和型態。其結果顯示，由於偶合劑的添加可有效縮小無機氧化物的粒徑而改善透光性質。隨之分別測試氣體穿透性質(GPA)、水氣穿透性質(VPA)、熱重分析(TGA)、微差掃描式熱分析(DSC)、機械性質(DMA)和吸水性(Water Up-Take)。
並列摘要
Abstract This thesis can be divided into two parts. For the first part, organic-inorganic hybrid materials based on SiO2 and polyimide derived from 4,4’-Oxydianiline（ODA）and 4,4′-(4,4′-Isopropylidene- diphenoxy ) bis (phthalic anhydride) （BSAA） were prepared. The structure and properties of the obtained Polyimide/silica（PI(1)/SiO2）hybrid materials were characterized in this study. PI(1)/SiO2 hybrid materials at low SiO2 loading up in the form of coating on cold-rolled steel (CRS) were found to exhibit much superior corrosion inhibition effect by performing a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and impedance spectroscopy in 5 wt% aqueous NaCl electrolyte. Furthermore, the synthesized PI(1)/SiO2 hybrid materials were subsequently characterized by Fourier-Transform infrared (FTIR) spectroscopy, wide-angle powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The molecular weights of PI(1)/SiO2 hybrid materials were determined by gel permeation chromatography (GPC). In the form of free-standing film, PI(1)/SiO2 hybrid materials were also studied by molecular permeability analysis. The gas permeability properties of the PI(1)/SiO2 hybrids were evaluated by GPA. The Water Vapor Permeability properties of the PI(1)/SiO2 hybrids were evaluated by VPA. Water absorption properties of the PI(1)/SiO2 hybrid materials were also examined. The thermal stability of PI(1)/SiO2 hybrid materials the were studied by TGA and DSC. The mechanical properties of PI(1)/SiO2 hybrid materials the were studied by DMA. For the second part, a new type of polyimide(2)/silica（PI(2)/SiO2）nanocomposite materials derived from BAPN（2,2-bis[4-(4- amionphenoxy)phenyl] norbornane）and OPDA（4,4- Oxydiphthalic anhydride）was prepared by base catalyze. The coupling agent ATS （3-Aminopropyl -trimethoxysilane）was chosen to enhance the compatibility between the polyimide (PI) and silica (SiO2). Furthermore, the effects of the coupling agent on the morphologies and properties of the PI(2)/SiO2 nanocomposite materials were investigated using UV-vis and FTIR spectroscopies and TEM. The results show that the size of the silica particle was reduced by the introduction of the coupling agent, which made the PI(2)/SiO2 nanocomposite materials film become transparent. In addition, free-standing films were also studied by molecular permeability analysis. (GPA), water vapor permeability measurements (VPA), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), water absorption properties, respectively.