為了建立更完整相間轉移觸媒的平衡資料,本研究針對常用的四級鹽類及自行合成的油溶性四級鹽類(TBA-TBPO及TBA-BPO)分別測定其兩相平衡分佈。從實驗數據中分析得相關熱力學參數,有系統的探討觸媒在兩相平衡分佈情形,提供了解利用相間轉移觸媒催化技術合成有機化合物的化學反應之催化系統各種現象。藉著數學模式的建立,求得相關之熱力學參數,由熱力學參數瞭解觸媒在兩相的分佈對兩相反應的影響。 (1)四級鹽類在兩相平衡分佈: 本實驗採四級鹽類(Aliquat336、TBAI、TBPB、TBAB、TBAC、TBA-TBPO、TBA-BPO)在油相初始濃度範圍為0.00625kmol/m3 ~ 0.1kmol/m3做油/水兩相及油/鹼性水溶液兩相之平衡實驗。其中油相溶劑包括氯仿、二氯甲烷、二氯乙烷及氯苯。分別加以探討四級鹽類用量、鹼量、溫度、不同有機溶劑、油相的含水量變化及觸媒攜水至油相的能力對兩相平衡分佈的影響。 (2)求得相關之熱力學參數: 本文在(i)四級鹽類在油相中只有單一離子對存在及(ii)四級鹽類在油相存在多種形態兩種假設得到描述系統及數學模式,求得相關之熱力學參數,如:分配係數m、萃取係數ETQX、解離常數Kd、平均活性係數值 等。由結果可發現四級鹽類在油相存在多種形態之假設所求得的熱力學參數較為準確。 (3)利用本實驗提出的HLB計算式,如下: 由此式計算出四級鹽類之HLB值,並由此推知其親水親油關係,合理的描述反應結果。 [註] Aliquat336:tricaprylmethylammonium chloride TBA-BPO : tetra-n-butylammonium 4-bromophenoxide TBA-TBPO : tetra-n-butylammonium 2,4,6-tribromophenoxide TBPB : tetra-n-butylphosphonium bromide TBAI:tetra-n-butylammonium iodide TBAB:tetra-n-butylammonium bromid TBAC:tetra-n-butylammonium chloroide HLB : hydrophile-lipophile balance : 烷基的碳數 MT : 總分子量 MH : 親水基部分的分子量 MNX : 離子基的分子量 MTBAB : TBAB的分子量
In this study , the thermodynamic properties of equilibrium of quaternary salts in an organic solvent and alkaline solution was investigated. The thermodynamic parameters were calculated systematically , such as diffusion coefficient , extraction coefficient , dissociation coefficient , mean activity coefficient and the value of Hydrophilic-Lipophile-Balance(HLB) etc. A new definition of HLB was set up . A correlation relationship of HLB and extraction coefficient was built up to offer to choose proper quaternary salts in a phase-transfer catalyzed reaction. Seven kinds of quaternary salts(Aliquat336、TBAI、TBPB、TBAB、TBAC、TBA-TBPO、TBA-BPO) and four kinds organic solvents(CHCl3、C2H4Cl2、CH2Cl2、C6H5Cl) were employed in measuring the extractive properties of quaternary salts between the organic phase and the aqueous phase. In addition , amount of quaternary salts , temperature , concentration of base , kinds of salts ware conducted to understand the thermodynamic phenomenon of quaternary salts between two phase. Two numerical modeling was employed to calculate the distribution coefficient , extraction coefficient , dissociation coefficient , mean activity coefficient. According to the numerical and experimental results. The two types of quaternary salts existing in the organic phase are free ion and ion-pair. [Notation] Aliquat336:tricaprylmethylammonium chloride TBA-BPO : tetra-n-butylammonium 4-bromophenoxide TBA-TBPO : tetra-n-butylammonium 2,4,6-tribromophenoxide TBPB : tetra-n-butylphosphonium bromide TBAI:tetra-n-butylammonium iodide TBAB:tetra-n-butylammonium bromid TBAC:tetra-n-butylammonium chloroide HLB : hydrophile-lipophile balance : number of carbons MT : total molecular weight of the molecule MH : molecular weight of the hydrophilic molecule MNX : molecular weight of the ion NX MTBAB : molecular weight of the TBAB