臺灣博碩士論文加值系統

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。

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.

目錄
中文摘要 I
英文摘要 III
目錄 V
圖索引 VIII
表索引 X

第一章 緒 論 1
1-1 前言 1
1-2 導電高分子之發展史 2
1-3 聚苯胺之簡介 4
1-4 聚苯胺之結構與物性 5
1-4-1 聚苯胺之合成與機構 5
1-4-2 聚苯胺之摻雜 8
1-4-3 自身摻雜態聚苯胺 9
1-4-4 二次摻雜態聚苯胺 9
1-4-5聚苯胺之電化學現象 11
1-5 聚苯胺衍生物的研究 11
1-5-1 環上取代聚苯胺衍生物 11
1-5-2 氮上取代聚苯胺衍生物 12
1-5-3 聚苯胺共聚合物 13
1-5-4 聚苯胺寡聚體的研究 15
1-5-5 苯胺寡聚體衍生之電活性高分子 15
1-6 環氧樹脂簡介 16
1-6-1 環氧樹脂之硬化 17
1-6-2 環氧樹脂官能基數的表示 18
1-6-3 環氧樹脂的特性 18
1-7 高分子之應用 19
1-7-1 氣體分離薄膜 19
1-7-2 防腐蝕塗料 26
1-8 研究動機 34
第二章 實驗藥品及量測條件 36
2-1 藥品 36
2-2 儀器設備 37
2-3 氣體部分 40
2-4 輔助儀器 40
2-5 儀器分析原理與實驗方法 41
第三章 聚鄰氟苯胺及其共聚物氣體分離薄膜之製備與物性探討 51
3-1 實驗部份 51
3-1-1 聚苯胺、聚鄰氟苯胺及其共聚物之合成 51
3-1-2聚苯胺、聚鄰氟苯胺及其共聚物之成膜 52
3-2 結果與討論 53
3-2-1 基本鑑定 53
3-2-2 氣體選擇之探討 57
3-2-3 導電度之探討 64
3-2-4 熱性質之探討 65
3-2-5 機械性質之探討 66
第四章 苯胺三聚體衍生之電活性環氧樹脂防蝕塗料上之製備與物性探討 68
4-1 實驗部分 68
4-1-1 苯胺三聚體之合成 68
4-1-2 環氧樹脂之固化反應 68
4-2 結果與討論 70
4-2-1 苯胺三聚體之鑑定 70
4-2-2 環氧樹脂之結構分析 73
4-3 電活性之測試 75
4-4 防腐蝕行為之探討 76
4-5 熱性質分析 85
4-6 機械性質 87
第五章 總結與未來展望 89
第六章 參考文獻 91

圖索引
Fig.1-1常見之導電高分子的化學結構 3
Fig.1-2 Polymerization mechanism of aniline 6
Fig.1-3 Interconversion of different forms of polyaniline 8
Fig.1-4 聚苯胺的二次摻雜效應 10
Fig.1-5 poly(aniline-co-ethylaniline)取代基含量與導電度的關係圖 14
Fig.1-6 薄膜之兩相分離示意圖 20
Fig.1-7 高分子薄膜之氣體分離示意圖 23
Fig.2-1 氣體穿透分析儀裝置 43
Fig.2-2 Electrochemical cyclic voltammetric test cell equipped with platinum foil counter electrode, SCE reference electrode and working electrode 45
Fig.2-3 工作電極示意圖 46
Fig.2-4 Electrochemical corrosion test cell equipped with graphite rod counter electrode, SCE reference electrode, working electrode and an operational temperature controller 46
Fig.2-5 四點探針 48
Fig.2-6 四點探針側導電度示意圖 48
Fig.3-1 聚苯胺、聚鄰氟苯胺和其共聚物之合成步驟 52
Fig.3-2 ATR of aniline- derivative polymer membranes 54
Fig.3-3 UV-vis of aniline- derivative polymer solutions 56
Fig.3-4 GPA of aniline- derivative polymer membranes (O2) 59
Fig.3-5 GPA of aniline- derivative polymer membranes (N2) 60
Fig. 3-6 GPA of aniline- derivative polymer membranes (CO2) 60
Fig.3-7 TGA cures of aniline- derivative polymers 65
Fig.3-8 DMA of aniline- derivative polymer membranes 66
Fig.4-1 Flow chart for the synthesis of electroactive epoxy thermosets 69
Fig.4-2 (a) Mass spectrum of ACAT (b) FTIR spectrum of ACAT (c) 1H-NMR spectrum of ACAT. 72
Fig.4-3 ATR of electroactive-epoxy-thermoset films 73
Fig.4-4 Redox behavior of EET40、EET10 and EET0-coated Pt foil electrode measured in 1.0 M H2SO4 aqueous solution 76
Fig.4-5 Tafel plots of electroactive-epoxy-thermoset coatings and bare CRS electrodes measured in 5 wt-% NaCl aqueous solution 77
Fig.4-6 交流電壓與電流的變化示意圖 79
Fig.4-7 複數平面之阻抗示意圖 79
Fig.4-8 電極之等效電路圖 80
Fig.4-9 電極之等效電路圖 81
Fig.4-10 Nyquist plots of electroactive-epoxy-thermoset coatings and bare CRS electrodes measured in 5 wt-% NaCl aqueous solution 82
Fig.4-11 Bode plots of electroactive-epoxy-thermoset coatings and bare CRS electrodes measured in 5 wt-% NaCl aqueous solution 84
Fig.4-12 TGA cures of electroactive-epoxy-thermoset materials 86
Fig.4-13 DMA cures of electroactive-epoxy-thermoset films 87

表索引
Table 3-1 Band assignments and detail data of aniline- derivative polymers 54
Table 3-2 density and FFV of aniline- derivative polymer membranes 58
Table 3-3 GPA of aniline- derivative polymer membranes (O2) 61
Table 3-4 GPA of aniline- derivative polymer membranes (N2) 61
Table 3-5 GPA of aniline- derivative polymer membranes (CO2) 62
Table 3-6 selectivity of aniline- derivative polymer membranes 62
Table 3-7 active energy of aniline- derivative polymer membranes 63
Table 3-8 Mw and conductivity of aniline- derivative polymers 64
Table 3-9 Thermal properties of aniline- derivative polymers 67
Table 4-1 Band assignments and detail data of epoxy resin 74
Table4-2 Relations of electroactive-epoxy-thermoset materials with the Ecorr, Rp, Icorr, and Rcorr measured from electrochemical methods 78
Table 4-3 Thermal properties of electroactive-epoxy-thermoset materials 88

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