四級銨化樹脂合成最佳化研究

Kinetic of Optimum Synthesis of Quaternary Ammonium Resin

林泓儒(Hung-Ju Lin)

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(2004年)

摘要

本文主要研究分為兩大部分，首先為觸媒擔體合成方式苯乙烯(styrene)為主要擔體結構藉由加入二乙烯苯(divinyl benzene)改變交聯度氯甲基苯乙烯(crosslinkage, CL)與加入vinylbenzyl chloride改變環取代數(ring substitution, RS)的比例，找出最佳化條件觸媒之結構。接著在固定化方面就以下變因進行探討，如固定化方式(攪拌式固定化與震盪式固定化)、固定化天數(0.125~4天)、三級胺濃度(0.1~2 kmol/m3)、固定化溶劑(甲醇、乙醇和二甲基甲醯胺(DMF))、固定化的三級胺類(三甲基胺、三乙基胺、三丙基胺、三丁基胺、三戊基胺、三己基胺、三辛基胺) 結論為當觸媒擔體之環取代數與交聯度比例為RS 10%, CL 2%，震盪式固定化一天，三己胺在甲醇溶液為最佳固定化程序條件。
另在反應分析方面，採用酚丙烯基化反應進行分析，轉速定為400rpm、溫度40℃，最後歸納以上兩部分得到結論：當利用溴丙烯的醚化反應做檢測反應時，可得到當觸媒擔體的環取代數為10%，交聯度為2%，並連結三己基胺所形成的季銨鹽為最具有催化效果的觸媒，並且固定化時間愈短，反應性愈好。並且可以得知，使用三丁基胺固定化之觸媒，可得知其turnover number為56.0452min-1;而使用三己基胺固定化之觸媒，可得知其turnover number為75.24035min-1。

關鍵字

相間轉移觸媒 ； 四級銨鹽 ； 液-固-液系統氧化反應 ； 最佳化研究 ； 懸浮聚合 ； 固定化 ； 反應動力學

並列摘要

The main study research divides into two major parts. The first part is the synthesis of ion-exchange resin. Added styrene for polymer-supported structure, induced divinyl benzene and vinylbenzyl chloride by changing the percentage of crosslinkage (CL) and ring substitution (RS) respectively. Next find out the best proportion of the structure for optimization condition of catalyst. Secondary changed the factors in immobilization as discussion below, e.g. the immobilized methods (by stirring or shaking), different times (0.125~4 days), the concentration of tertiary amine (0.1~2 kmol/m3), different solvents of immobilization (methyl alcohol, ethyl alcohol and DMF), different tertiary amines (trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, trioctylamine). The best immobilized effect was the proportion of ring substitution (RS) was 10% and crosslinkage (CL) was 2% for the catalyst, trihexylamine methanol solution in immobilization by shaking for one day.
The second part used the allylation of phenol for analysis, the agitation rate was 400rpm, and the temperature was 40 ℃. When uses the allylation of phenol for analysis, it could know when the catalyst was 10% of ring substitution and 2% of cross-linking linked trihexylamine to be the quaternary ammonium salt which has the best effect of the catalyst, and it’s immobilization time decreased, and reactivity was better. Immobilization by tributylamine methanol solution, that could get the turnover number is 56.0452min-1; immobilization by trihexylamine methanol solution, that also could get the turnover number is 75.24035min-1。

並列關鍵字

Phase-Transfer Catalyst ； Quaternary Ammonium Salt ； Liquid-Solid-Liquid System Oxidation Reaction ； the Optimum Research ； Suspension Polymerization ； Immobilization ； Reaction Kinetics

參考文獻

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