氧代氮代苯并環己烷與苯胺三聚體共聚物之合成及應用於抗腐蝕材料之研究

Preparation of copolymers of benzoxazine and aniline trimer and their application for anticorrosion

林信辰(Shin-Chen Lin)

指導教授 ： 劉英麟

國立清華大學/工學院/化學工程學系/碩士(2014年)

摘要

本研究以帶有馬來醯胺官能基的氧代氮代苯并環己烷化合物(NHMI-Bz)與苯胺三聚體(ACAT)為單體，利用紅外光譜儀(FTIR)和微差掃描卡計(DSC)探討其混合物的共聚合行為和反應機構，以及共聚合物的防腐蝕效能。在NHMI-Bz與ACAT的熱共聚合的過程中，苯胺三聚體先進行quinoid crosslinking，緊接著是苯胺三聚體末端的一級胺與馬來醯胺上的碳碳雙鍵進行Michael addition反應，隨後苯胺三聚體末端的一級胺催化了氧代氮代苯并環己烷的開環反應，並與開環後的中間體產生反應，最後是苯胺三聚體之間進行聚合為聚苯胺與碳碳雙鍵的加成反應。
透過熱重損失分析儀分析NHMI-Bz/ACAT共聚合物的熱穩定性質，發現其共聚物在氮氣環境下，800 °C時的殘碳量達到50 wt%以上，5 wt%的重量損失溫度皆在320 °C以上，顯示其共聚物具有良好的熱穩定性以及難燃性。
防腐蝕實驗結果顯示，加入33 wt%的ACAT於NHMI-Bz/ACAT共聚合物中時，塗佈此共聚合物的冷軋鋼之腐蝕速率為4.8 μm/year，明顯低於使用純NHMI-Bz或是ACAT所量得的腐蝕速率，顯示NHMI-Bz和ACAT具有防腐蝕的協同效應，主要原因為氧代氮代苯并環己烷提供良好的水氣阻隔性，以及苯胺三聚體本身所具有的電活性，在這兩個因素的影響下產生了協同效應，而達到良好的防腐蝕效果。

關鍵字

氧代氮代苯并環己烷 ； 苯胺三聚體 ； 防腐蝕

並列摘要

This work studies reactive blends of a maleimide-containing benzoxazine (NHMI-Bz) and an amine-capped aniline trimer (ACAT) compounds. The first part is the investigation on the reaction mechanism with Fourier Transform Infrared and Differential Scanning Calorimmetry. At the initial heating stage, the quinoid crosslinking reaction of ACAT occurs first. The Michael-addition reaction between the amine groups of ACAT and maleimide groups of NHMI-Bz follows at higher temperatures. The amine groups of ACAT catalyze the ring-poening reaction of the benzoxazine groups of NHMI-Bz to generate the reaction intermediate bearing iminium moieties, which might react toward both another benzoxazine groups of NHMI-Bz and the amine groups of ACAT. Moreover, self-polymerization of the maleimide groups of NHMI-Bz and the aniline groups of ACAT results in highly crosslinked products. The fully cured NHMI-Bz-ACAT resins show good thermal stability and sufficient flame retardancy.
The cured NHMI-Bz-ACAT resins have been used for anticorrosion application. The corrosion rate of the cured samples with 33wt% ACAT is much slower than the values recorded with the cured neat NHMI-Bz resin and the neat ACAT polymer. This result indicates that NHMI-Bz and ACAT could play a synergistic effect on anticorrosion, as NHMI-Bz contributes the water resistance and ACAT provides the electroactivity.

並列關鍵字

benzoxazine ； aniline trimer ； anticorrosion

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