- 學位論文
以胺基封端苯胺三聚體及五聚體來合成電活性聚亞醯胺及其性質之系統性比較研究
Systematically Comparative Studies on the Preparation and Properties of Electroactive Polyimide Containing Amino-Capped Aniline Pentamer and Trimer
摘要
本論文內容主要是研究電活性聚亞醯胺高分子材料之製備及其特性研究，並且著重於導入共軛鏈段之胺基封端之苯胺三聚體(amine-capped aniline trimer; ACAT)與胺基封端之苯胺五聚體(amine-capped aniline pentamer; ACAP)並系統性比較不同共軛鏈段長度對於電活性聚亞醯胺在物性與化性的影響效益。 本論文內容主要分為五個部份。第一章為緒論，文章內容以導論及文獻回顧為主。第二章，為實驗儀器以及實驗藥品與實驗條件的部份。第三章，為改善傳統聚合電活性聚亞醯胺之繁瑣步驟，且增加其加工性，本實驗中，利用氧化偶合一步法合成ACAT，並進一步將ACAT與N-phenyl-1,4-phenylene diamine利用氧化偶合一步法合成ACAP，之後以立體障礙結構較大之二酸酐(2,2-bis[4-(dicarboxyphenoxy)phenyl]propane dianhydride，BSAA)為單體，分別以ACAT與ACAP經二階段法製備電活性聚亞醯胺高分子薄膜(EPI-3與EPI-5)。第四章，進一步探討具電活性之EPI-3與EPI-5對材料在熱性質、機械性質、電性質、電活性與防腐蝕之變化，並利用二階段熱縮合法製備出電活性聚亞醯胺緻密膜，首次探討以胺基封端之苯胺五聚體(ACAP)作為電活性共軛鏈段之電活性聚亞醯胺緻密膜對氧氣、氮氣、二氧化碳、甲烷在不同溫度下氣體滲透率與氣體選擇率之變化，以及探討經過無機酸(HCl)摻雜前後對氣體滲透率與氣體選擇率之影響，並分析活化能，了解結構與分離效能之關係。第五章為結論及參考文獻。 本研究中，此系列新型具電活性之苯胺三聚體及苯胺五聚體於主鏈之芳香族聚亞醯胺高分子之合成與基本特性，做一系列之研究與比較，並克服以往不易成膜之缺陷，成功製備出具出色的薄膜成型能力，良好機械性質，且對其氣體分離特性作一系列之比較與探討。
並列摘要
This study has been separated into five chapters. Chapter 1 is general introduction. Chapter 2 is the experimentions. In chapter 3, 2,2-bis[4-(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA) were first reacted with emeraldine base (EB) form of amine-capped aniline trimer (ACAT) and amine-capped aniline pentamer (ACAP) units through chemical imidization to give series of electroactive polyimides (EPIs) by thermal and chemical imidization. In chapter 4 ,we compared the preparation and properties of electroactive polyimide containing amino-capped aniline trimer and pentamer systematically.EPI free-standing film was exhibited toughness and flexibility simultaneously in new experimental conditions (e.g., short reaction time, lower temperature, and solvent). EPI to investigate concentration effect of conjugated diamine segment, (i.e., ACAT and ACAP) on the physical (e.g., mechanical, and thermal) properties of as-prepared corresponding EPIs was incorporated into EPI (EPI-3 and EPI-5) for systematically comparative studies. It should be noted that the higher benzene rings units of conjugated segments existed, the remarkable enhancement in mechanical and thermal properties, respectively. Subsequently, EPIs consisting of ACAT or ACAP have been choosed to evaluate corrosion protection efficiency on cold-rolled steel (CRS) electrodes based on a series of electrochemical measurements. It was noticed that the as-prepared EPI-5 shows excellent anti-corrosion properties. It might probably be attributed to the redox catalytic property of as-prepared electroactive polyimide coatings inducing the formation of passive layer of metal oxide. The first evaluation of gas transport properties of dense EPIs membranes prepared by thermal imidization were presented. The results for gas transport properties of these membranes revealed that the gas permeation properties significantly decreased as the HCl doped of EPI-5 and the selectivity of gas pairs, such as O2/N2, and CO2/CH4 slightly increased. The temperature dependence of permeability was also investigated by an Arrhenius-type equation. Chapter 5 is conclusions. The synthesis, basic characterization, electrochemical, gas separation, and anti-corrosion properties of series of novel electroactive aromatic polyimides were investigated and compared. And it reveals that mechanical and thermal properties, electrochemical, anti-corrosion properties and gas separation of EPI-5 is better than EPI-3 All polymers had good solubility in many polar aprotic solvents, and exhibited excellent thin-film-forming ability, good thermal stability and mechanical properties. Thus, all the obtained polymers these electroactive polyimide may be widely applied in the future due to their unique properties.