具電活性鏈段之LED光硬化型乙烯基化環氧樹脂之合成、鑑定及其在金屬抗腐蝕之應用研究

本碩士論文之研究主軸為乙烯基苯胺三聚體之合成、鑑定及其應用於UV-LED高分子塗料固化抗腐蝕之研究，並以電化學方法探討其應用於金屬防腐蝕塗料之成效。首先，利用二苯胺(或鄰磺酸對苯二胺)與苯胺進行化學氧化偶合法，以合成胺基封端苯胺三聚體(Amine-Capped Aniline Trimer ； ACAT)，再進一步合成 (Amine-Capped Vinyl Aniline Trimer； V-ACAT)。以核磁共振光譜儀(1H-NMR)、傅立葉紅外光譜儀(FTIR)及質譜儀(MS)對所合成之ACAT/V-ACAT進行化學結構鑑定與比較。由研究數據顯示: V-ACAT的導入可有效加強環氧丙烯酸的抗腐蝕能力。將先前所合成之ACAT加入環氧丙烯酸樹脂中，發現ACAT在環氧丙烯酸中之物理分散性不好。因此衍生以化學合成乙烯基苯胺三聚體導入環氧丙烯酸，而且其電活性具有強化環氧丙烯酸抗腐蝕能力的特性。 V-ACAT在UV-LED固化系統中具有加強環氧丙烯酸抗腐蝕的效果是利用電化學方式來評估。由研究的數據顯示: UV-LED固化系統中有添加V-ACAT的環氧丙烯酸樹酯的抗腐蝕效果比起未添加的樹酯來的有效。在電化學防蝕能力的評估方面，探討所合成的高分子塗料以塔伏(Tafel)曲線、涅斯特(Nyquist)曲線及博德(Bode)曲線測試之後的結果。由所做的數據資料顯示: 添加V-ACAT的環氧丙烯酸塗料較未添加的環氧丙烯酸塗料呈現較佳的金屬(如:冷扎鋼)防蝕效果。此防蝕效果提升的原因可解釋如下: 添加V-ACAT的塗層具有電催化能力，可在金屬表面產生緻密的鈍性金屬氧化層以保護下層未受腐蝕之金屬，因此會比傳統環氧丙烯酸樹酯塗料呈現較佳的抗腐蝕效果。關鍵字：電活性、防腐蝕、苯胺三聚體、UV-LED

關鍵字

電活性；防腐蝕；苯胺三聚體； UV-LED

並列摘要

The main motivation of this master thesis is to synthesize, characterization of the UV-LED curable electroactive epoxy-acrylate coating and applied in the anticorrosion field. First, amine-capped aniline trimer (ACAT) was synthesized by the chemical oxidative coupling reaction between diphenylamine and aniline. Subsequently, vinyl-modified ACAT (denoted V-ACAT) was synthesized by reacting methacryloyl chloride with ACAT. The as-prepared ACAT and V-ACAT were then characterized by nuclear magnetic resonance spectroscopy (1H-NMR), Fourier transform infrared (FTIR) spectroscopy and mass spectrometry. (MS) The feeding ratio of 0.5 wt-% as-prepared V-ACAT was then mixing with commercial epoxy acrylate under stirring for 30 minutes, followed by UV-LED curing. ( radiation time: 20 second; radiation distance: 2 cm, wavelength of radiation: 395 nm). Redox capability of epoxy acrylate was also investigated by electrochemical cyclic voltammetry (CV) studies. In corrosion measurements, a series of electrochemical methods such as Tafel plots, Nyquist plots and Bode plots were used to evaluate the performance of as-prepared materials. It should be noted that the V-ACAT epoxy acrylate coating containing 0.5 wt-% of V-ACAT was found to exhibit better anticorrosion as compared to that of epoxy acrylate without V-ACAT. The possible reason for the enhancement of anticorrosion performance of epoxy acrylate coating containing of V-ACAT may be related to the appearance of electroactive V-ACAT, which lead to the formation of densely passive metal oxide layer (i.e., Fe2O3 and Fe3O4) to protect the underlying metal surface. Keywords: electroactive，corrosion，aniline trimer， UV-LED