CAJ | 학술논문

为了提高乙醇氧化羰基化合成碳酸二乙酯(DEC)催化反应性能，考察了不同配体、催化剂配比、催化剂浓度、反应温度、反应时间等条件对乙醇转化率和DEC选择性的影响，并利用气相色谱-质谱联用(GC-MS)和气相色谱(GC)对反应产物进行了定性和定量分析。结果表明，当以4-二甲氨基吡啶(DMAP)为配体，CuBr：DMAP=1：2，在合适的反应条件下(催化剂浓度0.25 mol?L-1，反应压力3.5 MPa，反应温度100℃，40 mL N,N-二甲基乙酰胺(DMA))，乙醇转化率为28.6%，DEC选择性为99.9%。通过探讨反应机理，认为CuBr/DMAP/DMA催化体系不仅有利于主反应控制步骤CO的插入反应，有助于中间体的形成，缩短了反应的诱导期，反应时间由180 min减至90 min，也抑制了副产物乙酸乙酯中间体的形成，提高了反应的选择性。
위료제고을순양화탄기화합성탄산이을지(DEC)최화반응성능，고찰료불동배체、최화제배비、최화제농도、반응온도、반응시간등조건대을순전화솔화DEC선택성적영향，병이용기상색보-질보련용(GC-MS)화기상색보(GC)대반응산물진행료정성화정량분석。결과표명，당이4-이갑안기필정(DMAP)위배체，CuBr：DMAP=1：2，재합괄적반응조건하(최화제농도0.25 mol?L-1，반응압력3.5 MPa，반응온도100℃，40 mL N,N-이갑기을선알(DMA))，을순전화솔위28.6%，DEC선택성위99.9%。통과탐토반응궤리，인위CuBr/DMAP/DMA최화체계불부유리우주반응공제보취CO적삽입반응，유조우중간체적형성，축단료반응적유도기，반응시간유180 min감지90 min，야억제료부산물을산을지중간체적형성，제고료반응적선택성。
In order to improve the diethyl carbonate (DEC) synthesis using oxidative carbonylation of ethanol, the effects of ligands, catalyst composition and concentration, reaction temperature and time on the ethanol conversion rate and DEC selectivity were investigated. Gas chromatography-mass spectroscopy (GC-MS) and gas chromatography (GC) were used to identify and quantify the reaction products. The results show that when 4-dimethylaminopyridine (DMAP) is used as the ligand with the CuBr/DMAP molar ratio of 1/2, the ethanol conversion rate can reach 28.6%and the selectivity of DEC is 99.9%under suitable reaction conditions (catalyst concentration:0.25 mol?L-1, pressure:3.5 MPa, temperature:100℃, 40 mL N,N-dimethylacetamide ). Reaction mechanism study shows that the CuBr/DMAP/DMA catalytic system prefers the insertion of CO (the rate-controlling step) and the formation of intermediate, which reduces the induction period. The reaction time decreases from 180 min to 90 min and the formation of the byproduct ethyl acetate intermediate is suppressed. The reaction selectivity is also enhanced.