苯胺衍生高分子之製備及其應用研究

Preparation, Characterization and Application Studies of Aniline-derivating Polymers

許昌隆(Chang-lung Shiu)

指導教授 ： 葉瑞銘

中原大學/理學院/化學研究所/碩士(2008年)

https://doi.org/10.6840/cycu200800465

摘要

本研究內容分為兩大部分，第一部分是製備與探討苯胺與含氟苯胺之共聚物，分析其薄膜在氣體分離上的應用及物性研究；而第二部分是製備與探討不同比例之苯胺三聚體在其衍生之電活性環氧樹脂中，對防腐蝕及其它物性的影響。
在第一部份，利用導入天然氯化鈣/氯化氫水溶液，使不同比例之鄰氟苯胺單體與苯胺單體經由氧化聚合，成功地合成出一系列高分子量之聚鄰氟苯胺及其衍生共聚物之導電高分子薄膜。先以衰減式全反射傅立葉轉換紅外光譜儀(ATR-FTIR)鑑定材料的結構，紫外-可見光譜儀（UV-vis）初步探討分子量的變化，再藉由凝膠滲透層析儀(GPC)，可得知當高分子中的鄰氟苯胺單體成分愈多，分子量有逐漸下降的趨勢，利用導電度分析儀進行偵測，導電度隨著分子量的下降而遞減；氣體穿透分析儀（GPA）探討不同比例組成對滲透率與選擇率的影響，當鄰氟苯胺單體成分愈多時，對O2、N2、CO2、氣體滲透率逐漸遞增，而O2/N2的選擇率都維持在10左右，以聚苯胺最佳；再以熱失重分析儀(TGA)和動態機械熱分析儀(DMA)進行量測，探討其熱裂解溫度、碳渣殘餘量與儲存模數的變化，以聚苯胺所呈現出來的效果最好。
在第二部份，首先將對苯二胺與苯胺單體進行氧化反應合成電活性的苯胺三聚體(ACAT)，再以苯胺三聚體和聚氧化丙烯三醇胺(T-403)不同添加比例與4,4′-四縮水甘油基二氨基二苯基甲烷(TGDDM)行開環反應聚合成具有電活性鏈段之環氧樹脂。並進一步利用衰減式全反射傅立葉轉換紅外光譜儀(ATR-FTIR)、核磁共振儀(NMR)、質譜儀(MASS)進行結構鑑定，在電化學的研究方面，藉由循環伏安儀(CV)探討環氧樹脂之電活性與相對應之腐蝕行為，結果顯示當高分子中含有較多之苯胺三聚體時具有較明顯之電活性，在冷軋鋼上塗佈時呈現較佳之防腐蝕效果。此外以交流阻抗圖譜分析儀(EIS)進一步地佐證防腐蝕效果；在性質之檢測方面，由熱失重分析儀(TGA)、微差掃描式熱分析儀(DSC)及動態機械分析儀(DMA)的量測結果顯示，苯胺三聚體含量愈多，在所合成的環氧樹脂中具有最佳的熱穩定性與機械性質。

關鍵字

防腐蝕 ； 氣體分離 ； 苯胺三聚體 ； 聚苯胺

並列摘要

The studies divide into two major parts, one is that preparation and characterization different-proportion of poly(aniline-co-fluoroaniline), besides, discussions of gas separation and other properties. The other is to prepare and character ratio-change aniline trimer in the electroactive epoxy resins, furthermore, investigate the influence of anticorrosion and physical properties.
In the first, the copolymerization of aniline and 2-fluoroaniline was carried out by chemical oxidation in CaCl2/HCl medium. The materials were characterized by Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy and identified the molecular weight by UV-visible and gel permeation chromatography (GPC). Furthermore, the gas permeability and selectivity were measured by the gas permeability analyzer (GPA), conductivity of poly(aniline-co-fluoroaniline)s run by a four-points-probe conductivity method, thermal and mechanical properties were investigated using thermogravimetric Analysis (TGA) and dynamic mechanical analysis (DMA). Polyaniline exhibit well properties for all tests.
The second part, a series of electroactive epoxy thermosets (EETs) containing redox catalytic segments of amino-capped aniline trimer (ACAT) were successfully prepared. First of all, ACAT was synthesized by oxidative coupling of 1, 4-phenylenediamine and 2 eq. aniline with ammonium persulfate as oxidant. Subsequently, series of EET materials were prepared by performing thermal ring-opening polymerization reactions between different feeding ratio of ACAT/T-403 and 4, 4'-tetraglycidyldiaminodiphenyl methane (TGDDM) and subsequently characterized by Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy. Furthermore, the redox behavior of as-prepared EET materials was identified by the electrochemical cyclic voltammetry (CV) studies.
It should be noted that the anticorrosive efficiency of as-prepared EETs, in the form of coating, was found to increase as the content of ACAT increased in the EETs on cold-rolled steel (CRS) electrode based on a series of electrochemical corrosion measurements such as corrosion potential, polarization resistance, corrosion current and corrosion rate in 5 wt-% NaCl supporting electrolyte. Effect of material composition on the thermal stability and mechanical strength of EETs was also investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA), respectively.

並列關鍵字

gas separation ； polyaniline ； ACAT ； anticorrosion

參考文獻

1. H. Naarnann,Angew. Chem. Int. Ed., 8, 915 ( 1969).

2. T. Ito, H. Shirakawa, S. Ikeda, J. Polym. Sci., Polym. Chem. Ed., 12, 11 ( 1971).

4. A. F. Diaz, K. K. Kanazdwd in “Extended Linear Chain Compounds“（G. S. Miller ed.）, Plenum, New York, p3 (1982).

5. R. M. Baughman, J. L. Bredas, R. L. Elsenbaumer, L. W. Shacklette, “Structural basis for semiconducting and metallic polymer dopant systems“ Chem. Rev., 82, 209 (1982).

6. K. Kaneto, S. Ura, K. Yoshino, Y. Inuishi, “Optical and Electrical Properties of Electrochemically Doped n- and p-Type Polythiophenes“ Jap. J. App. Phys., 23, 189 (1984).