四級銨化苯乙烯-氯甲基苯乙烯樹脂在油水兩相中性質測定

Characterization of Quaternary Ammonium Styrene Chlomethylstyrene resin in an organic solvent/water system

李俊昇(Chun-Shen Lee)

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(1998年)

摘要

本文主要研究對-甲氧基苯基乙酸和正溴基丁烷反應物在兩不相溶之界面合成對甲氧基苯基乙酸丁酯。運用的三相觸媒是利用苯乙烯，氯甲基苯乙烯為聚合反應物，加入二乙烯苯當交聯劑，利用懸浮共聚合法合成觸媒擔體。再將具有催化性質之三丁基胺、三辛基胺固定於高分子固體擔體上，另外和商業化的季銨鹽型觸媒加以比較。
擔體結構會影響到觸媒性質，進而影響取代反應的效率。因此首先測定合成出來的觸媒結構，結果與預先配製的相近。再測量不同結構擔體所合成出的觸媒其本身的交聯度、環取代數及外在的鹽類水溶液、有機溶劑等對每克觸媒的吸收溶劑組成。再與醚酯類反應結果互相比較其中的關係。
結果發現觸媒的吸收溶劑組成量和油、水所佔的比例對反應的影響很大。外在的鹼性溶液氫氧化鉀、氫氧化鈉量等，對於吸入量皆有不同影響，其中在氫氧化鈉下平均的吸油、吸水性較在氫氧化鉀佳。但因在氫氧化鈉比氫氧化鉀下的水合作用大，故在氫氧化鈉反應速率較在氫氧化鉀下慢。商業化觸媒上的三甲基胺使得觸媒較為親水，水合作用大，反應效果差。三辛基胺使得觸媒極親油，水相反應物在觸媒內的量減少，反應效果也不好。三丁基胺吸油、吸水性相近，約1/1,在反應上較前兩者佳。
觸媒的使用壽命也是本文討論的重點之一，將使用過的觸媒以元素分析及熱重分析來比較活性基座上三級銨的損失情況。
觀察發現，四級銨化苯乙烯-氯甲基苯乙烯的抗鹼性不錯，但其 耐熱性並不佳。故在選用反應及觸媒時需對其使用效率及經濟效益做一審慎的評估。

關鍵字

三相觸媒 ； 環取代數 ； 溶劑吸收組成

並列摘要

The synthesize of 4-methoxy-phenylactic acid butyl ester by reacting 4-methoxyphenyl acetic acid with n-bromobutane in an organic solvent and alkaline solution was investigated by triphase catalysis .Triphase catalyst was synthesized with styrene ,vinyl chlorobenzyl and divinyl benzene (crosslinkage agent) by suspension polymerization . Then, tri-n-butylamine ,tri-n-octanylamine moberlized on polymer particle.The char-acterization of poly-support catalyst compared to that of commercial quarternary ammoniun catalyst.
The polymer support structure affect catalytic properties and the substitution reaction of ether. The ratio of styrene, vinyl chlorobenyl and divinylbenzene was closed to that of our prepare. The catalystic structures
of crosslinkage and ring substitution , and imbibed solvent composition were measured to achieve a optimum condition . The result corresponds to that of the substitution reaction of ether.
According to experimental result, imbibed solvent composition and extraparticle base concentration play crucial role in promoting the re-action rate .The imbibed amount of water and organic solvent for NaOH solution was larger then that for KOH solution. However, because the solvation ability of reactant and water in polymer particle for NaOH solution is much than for KOH solution ,the reaction rate for NaOH is slower than that for KOH solution. The imbibed ratio of water to organic solvent is too large in a commercial ammonium catalyst of tri-methyl amine. The tri-octylamine has imbibed less solvent and reactant in cata-lyst so that the reaction rate is solw .The catalyst of tri-butylamine has proper imbibed solvent composition ,may 1/1 .Hence, the reaction rate for tri-butylamine is rapid than those of two catalysts as mentioned above.
The catalyst degradation and reuse are also conducted in the study. Element analysis and thermal gravity analysis were employed to char-acterize the properties of polymer resins.The antialkaline property for producted ammonium resin of tributylamine is good ,however thermal property is bad .Hence, the efficacy and economic of the catalyst had to be considered before reaction.

並列關鍵字

tri-phase catalysis ； ring substitution ； imbibed solvent composition

參考文獻

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