四級銨化離子薄膜製備與性質分析

Characterization an Preparation of Quaternary Ammonium Membrane

吳玉凱(Yu-Kai Wu)

指導教授 ： 吳和生老師

元智大學/工程學院/化學工程與材料科學學系/碩士(2003年)

摘要

到目前為止，許多文獻將陰離子交換薄膜應用在海水淡化、回收金屬離子與電滲析實驗方面，由於四級銨化後的陰離子交換膜在兩相反應系統中亦具有催化的效果。本文旨在製備四級銨化陰離子交換薄膜並在薄膜反應器中使用陰離子交換薄膜當做相間轉移觸媒進行酚丙烯化反應，根據各項實驗結果來評估陰離子交換膜的可行性。
本文的第一部份是以親油性的氯甲基苯乙烯與二乙烯苯利用”Paste method”聚合方法將兩者單體共聚合交聯成不溶性的高分子骨架，再與不同種類三級胺進行四級銨化反應，即可得到具有催化效果的陰離子交換薄膜，研究結果發現共聚合後的基膜與三級胺進行四級銨化反應，會造成基膜不規則性膨潤，四級銨化後的薄膜平均厚度約為0.3mm，此外，根據volhard method 滴定氯離子含量結果顯示，三級胺烷基碳鏈增長以及基膜交聯度增加，明顯造成離子交換容量(IEC)與水含量減少，一般而言，IEC和水含量之間為正比關係。實驗結果顯示在40℃和24h的反應條件下用最短的三級胺烷基鏈，即可得到最大觸媒含量，其離子交換容量可高達2.9 meq/g。
第二部分，在酚丙烯化反應系統中以四級銨化三甲基膜做為相間轉移觸媒，研究的變因有攪拌速率、反應溫度、反應物莫耳濃度比例。實驗結果得知，加快攪拌速率對反應速率影響不大，隨著反應溫度的上升，亦加快反應的進行，當有機相反應物為過量(有機相：水相=15：1(0.06mol：0.004mol))時較利於反應進行，反應200min後產率可達80%，反應溫度為45℃，攪拌速率= 400 rpm。

關鍵字

陰離子交換薄膜 ； 相間轉移催化技術 ； 丙烯化

並列摘要

Up to now, many research have successfully used anion exchange membrane in seawater desalination、in the recovery of metal ions from waste water and in electrodialysis experiments.Because quaternary ammonium membranes have catalytic effect in two phase reaction systems,the purpose of this paper is first to prepare quaternary membranes,and them use them as transfer catalysts for the allylation of phenol in a vertical membrane recator.The experiment resoults are then used to estimate the feasibility of using quaternary ammonium membrane in the phase transfer catalytic system.
In this study firstly,an anion exchange membrane was made by using the “paste method” to copolymerize hydrophobic chloromethylstyrene and divinylbenzene to form the insoluble structure which by cross-linking and then immobilized with amines in the quaternarization process.The experimental results show that amines would make base membrane swell abnormally, quaternary membrane averages a thickness of 0.3mm.By titrating chloride ion content using volhard method ,resoults showed that increasing the allyl amines and degrees of crosslinking the base membrane would markedly decrease the content of ion exchange capacity (IEC) and water content.In generally, the relationship between IEC and water content are directly proportional.Besides,when base membrane reacted with tri-methylamine,the maximum catalyst activity can be obtained at 30℃in 24h with an ion exchange capacity of 2.9 meq/g if the shortest tertiary allyl amine was used.
In the system of allylation of phenol,using quaternary tri-methylamine membrane as phase-transfer catalyst ,the operating conditions for investigation include agitation rate,reaction temperature and the concentration ratio of reactants.It was found that increased reaction temperature raised the reaction rate,but the effect of agitation rate were not clear.Under excess organic phase condition,the yield of product could reach 80% under appropriate conditions after reacting for 200 minutes(molar ratio of water and organic phase is one fifteenths(W:O=1:15);reaction temperature=45℃,rpm=400).

並列關鍵字

Anion-exchange membrane ； Phase-transfer Catalysis ； Allylation

參考文獻

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