四級銨化離子交換薄膜製備與反應分析

Preparation and Reaction Analysis Quaternary Ammonium Membrane

力健中(Chang-Chung Li)

指導教授 ： 吳和生

元智大學/工程學院/化學工程與材料科學學系/碩士(2006年)

摘要

氯甲基苯乙烯與二乙烯苯利用塗附法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(三甲基胺、三乙基胺、三丙基胺、三丁基胺、三戊基胺)，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。根據Volhard method 與元素分析儀測定離子交換容量，含水率、膜厚與膨潤形變率等數值也被測定，在型態學方面利用掃描式電子顯微鏡來觀察薄膜。結果顯示減少陰離子交換膜上固定化的胺基碳數，會增加薄膜的離子交換容積與薄膜的含水率。

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。
利用四級胺化離子交換薄膜進行丙烯化反應，可將有毒物質酚反應製造成為有經濟價值的酚基丙烯基醚，在批次反應器中，反應溫度338k，轉速400rpm，水相酚濃度為5000ppm，油相的溴丙烯濃度為水相酚的20倍，此反應的產率可達到趨近100%，且可將5000ppm的酚濃度降到低於2ppm。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。

關鍵字

陰離子交換薄膜 ； 相間轉移催化技術 ； 丙烯化 ； 酚的資源化

並列摘要

An anion exchange membrane was made from polymerizing chloromethylstyrene crosslinking with divinylbenzene by the “paste method” to form the insoluble base membrane, and immobilized with tertiary amines (tri-methylamine, triethylamine, tripropylamine, tri-n-butylamine, and tri-n-hexylamine) in the quaternarization process. The base membrane would be swollen in the quaternarization process. The ion-exchange capacity in the membrane was determined by means of Volhard method and Elemental analysis. The water content, thickness and volume ratio of the membrane was also determined. The morphology of the membrane was observation using the SEM. Increasing the carbon number of teritary amines decreased the ion exchange capacity (IEC) and water content.

Up to now, many research have successfully used anion exchange membrane in seawater desalination and used in the recovery of metal ions from wastewater and in electro-dialysis experiments. Because quaternary ammonium membranes have catalytic effect in a two-phase reaction system, the purpose of this research is first to prepare poly (styrene- co- chloromethylstyrene) membranes with activating with tri-methylamine, triethylamine, tripropylamine, tri-n-butylamine, and tri-n-hexylamine, and then use them as phase-transfer catalysts for the allylation of phenol in a horizontal membrane reactor. The experiment results are then used to estimate the feasibility of using quaternary ammonium membrane in the phase-transfer catalytic system.

Phenol was reacted from the simulated wastewater in the form of useful product allyl phenyl ether using quaternary ammonium membrane. Initial phenol concentration in the aqueous phase was 5000 ppm, NaOH: Phenol=1.67:1(mole ratio) and the reaction was carried out in batch model at 338K (both organic and aqueous phase agitation rate =400rpm, allyl bromide in organic phase was 20 times (mole) phenol concentration, 1,2dichloroethane was used as organic solvent) and after reaction phenol concentration in the aqueous phase was found to be <2ppm and more than 99% of the phenol was recovered in the form of allyl phenyl ether. Effect of temperature and agitation rate of aqueous and organic phase was studied on yield of PhOR in organic phase and on phenol concentration in the aqueous phase after the reaction. Activation energy and turnover number of the reaction was also calculated.

並列關鍵字

Anion-exchange Membrane ； Phase-transfer Catalysis ； Allylation ； Phenol Recovery

參考文獻

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