Metal catalyst of esterification of adipic acid and C14-15 alcohol

本研究為客製化客戶所需求之製品，規格要求為酸價0.1KOH mg/g以下；氫氧價3.0KOH mg/g以下和水分0.05%以下；該製品為己二酸和C14-15醇完全反應所得製品，審視現場實際生產該製品發現耗時費力，除了反應時間很長外，以及酸價無法達到要求與顏色過深，而利用純化工程，又會因不確定因素之干擾亦導致曠日費時。由於客戶要求低酸價(0.1mg KOH/g以下)以及低色度(APHA 50以下)，而低酸價的要求勢必需添加觸媒且高溫反應才勉強可達到要求。本實驗用了鈦酸四丁酯(TnBT)以及草酸亞錫兩種觸媒，觸媒加入的比例為250ppm以及500ppm，而在草酸亞錫的實驗中則多做了添加了次亞磷酸鈉做為抑色劑的試驗。實驗結果顯示，草酸亞錫與鈦酸四丁酯兩種觸媒皆有降低反應時間的效果。而草酸亞錫在不添加抑色劑的反應相較於TNBT有更佳的反應速率，而觸媒量添加500ppm，相較於250ppm均會提高反應時間，250ppm為較佳的觸媒添加量。結論是在添加250ppm的草酸亞錫相較於250ppm TnBT觸媒添加量更能顯著的降低反應時間，雖然草酸亞錫的反應會有著色的現象，但仍可達到客戶要求之低色度APHA 50與低酸價0.1 (mg·KOH/g)以下。This research is about customizing product of esterification that client needed,and the client asked for the specification of product less than Acid Value 0.1(mg·KOH/g),Hydroxyl Value 3.0 (mg·KOH/g) and Moisture 0.05%.This esterification is reacted by adipic acid and Isalchem145(C14-C15 alcohol). Examining the actual production situation of the factory,we found that besides reactions spending too much time,acid value and color can’t reach the specification. If by using the purification,there are some uncertain reasons lead to take much more time. As the specification that low acid value and light color that client required,adding catalyst and react at high temperature can reach low acid value reluctantly. This research is about comparing TnBT and Stannous oxalate as metal catalyst of esterification,the proportion of the catalyst adding is 250 ppm and 500 ppm. In the reaction of stannous oxalate, the addition of sodium hypophosphite as color-inhibition agent. The result is shown that two kinds of catalyst that TnBT and stannous oxalate for reducing the reaction time are both effective,and the reaction of stannous oxalate without color inhibition agent is more effective than the reaction of TnBT. The proportion of the addition of catalyst 500 ppm take much more time than 250ppm,so 250ppm is the better proportion that addition of catalyst for this ester reaction. The conclusion is that adding 250 ppm of stannous oxalate is more effective than the same proportion of TnBT for reducing reaction time. Although the color of production that stannous oxalate as catalyst is darker,it still can reach the specification that less than Acid Value 0.1 (mg·KOH/g) and Color APHA 50 that client ordered.第一章 前言 1 第二章 文獻回顧 3 2.1 酯化反應 3 2.2 觸媒反應 6 2.3 TnBT鈦酸丁酯 9 2.4 草酸亞錫 10 2.5 次亞磷酸鈉 11 2.6 研究動機 12 第三章 實驗設備與方法 14 3.1 實驗設計與步驟 14 3.2 試驗材料 15 3.3 分析儀器 16 3.4 分析方法 16 3.4.1 含水量(Karl Fischer)檢驗法 16 3.4.2 酸價(Acid Value)檢驗法 17 3.4.3 皂化價(Saponification Value)檢驗法 20 3.4.4 氫氧價(Hydroxyl value)檢驗法 22 3.4.5 比重(Specific Gravity)檢驗法 24 3.4.6 動黏度(Viscosity,cst)檢驗法 25 3.4.7 核磁共振光譜(Nuclear Magnetic Resonance Spectroscopy,NMR) 27 3.4.8 傅立葉轉換紅外線光譜儀(Fourier transform infrared spectroscopy,FTIR) 29 3.4.9 MALDI-TOF 質譜儀(Matrix-Assisted Laser Desorption/ Ionization Time of Flight Mass Spectrometry) 31 第四章 結果與討論 33 4.1 成品之水份 33 4.2 成品之酸價 34 4.3 成品之皂化價 35 4.4 成品之氫氧價 36 4.5 成品之色相 38 4.6 成品之反應時間 39 4.7 分析數據總表 40 4.8 傅立葉轉換紅外線光譜圖 43 4.9 核磁共振光譜圖 47 4.11 MALDI-TOF 質譜儀 50 第五章 結論 53 參考文獻 5