镍盐催化乙炔羰基化合成丙烯酸酯

摘要

采用一系列非卤素镍盐催化乙炔羰基化合成丙烯酸甲酯（MA）时发现，Ni（OAc）2·4H2O具有较高的催化活性。考察了溶剂的种类、反应温度、反应时间、催化剂用量、乙炔初始分压、CO初始分压及水对催化合成MA反应的影响。实验结果表明，在Ni（OAc）2·4H2O用量1.0 mmol、初始总压为4.6 MPa （n（乙炔）∶n（甲醇）∶n（CO）=1∶1.2∶4.5）、四氢呋喃为溶剂、220℃的条件下反应2 h，MA的收率为75.4%，选择性为96.2%。相同反应条件下，MA、丙烯酸乙酯和丙烯酸正丁酯的收率和选择性逐渐下降。在优化反应温度下，丙烯酸乙酯和正丁酯的选择性均超过94%。%The carbonylation of acetylene to acrylates over several non-halide nickel salt catalysts were studied,and Ni(OAc)2·4H2O exhibited a high catalytic activity in the carbonylation of acetylene to methyl acrylate. The influences of solvents,reaction temperature,reaction time, water,initial pressure of acetylene and initial pressure of carbon monoxide on the carbonylation reactions were investigated. It was showed that,under the conditions of tetrahydrofuran as solvent,initial pressure 4.6 MPa,220℃,n(C2H2)∶n(CH3OH)∶n(CO) 1∶1.2∶4.5, 1.0 mmol Ni(OAc)2·4H2O as catalyst and 2 h,the yield of methyl acrylate and the selectivity to methyl acrylate reached 75.4%and 96.2%,respectively. The yields and selectivities of acrylates decreased with increase of carbon atom number in the aliphatic alcohol molecules under the similar reaction conditions. The selectivities to both ethyl acrylate and n-butyl acrylate were more than 94%at optimal reaction temperature.