CAJ | 학술논문

苯氨基甲酸甲酯(MPC)是非光气法合成二苯甲烷二异氰酸酯的重要中间体。以苯胺、CO2和甲醇为原料催化合成MPC是一条绿色的工艺路线。为此重点研究了制备条件对Cu-Fe/ZrO2-SiO2催化性能的影响以及反应条件对MPC合成反应的影响。结果表明，采用机械混合法制备的金属负载量为10%(按氧化物计)的Cu-Fe/ZrO2-SiO2对MPC合成反应具有较好的催化效果。对不同方法制备的催化剂进行了 H2-TPR 实验测定，发现催化剂表面的金属活性位越多，金属与载体之间的作用越强，催化剂的活性越好。适宜的 MPC 合成反应条件为：溶剂乙腈/苯胺体积比为2：1，甲醇/苯胺摩尔比为1.2：1，催化剂用量为13%(wt)，CO2初压为2.0 MPa，反应温度为180℃和反应时间为11 h。在此条件下，苯胺的转化率为14.0%，MPC的收率及其选择性分别为9.2%及65.7%，远高于目前文献值。
분안기갑산갑지(MPC)시비광기법합성이분갑완이이청산지적중요중간체。이분알、CO2화갑순위원료최화합성MPC시일조록색적공예로선。위차중점연구료제비조건대Cu-Fe/ZrO2-SiO2최화성능적영향이급반응조건대MPC합성반응적영향。결과표명，채용궤계혼합법제비적금속부재량위10%(안양화물계)적Cu-Fe/ZrO2-SiO2대MPC합성반응구유교호적최화효과。대불동방법제비적최화제진행료 H2-TPR 실험측정，발현최화제표면적금속활성위월다，금속여재체지간적작용월강，최화제적활성월호。괄의적 MPC 합성반응조건위：용제을정/분알체적비위2：1，갑순/분알마이비위1.2：1，최화제용량위13%(wt)，CO2초압위2.0 MPa，반응온도위180℃화반응시간위11 h。재차조건하，분알적전화솔위14.0%，MPC적수솔급기선택성분별위9.2%급65.7%，원고우목전문헌치。
MethylN-phenyl carbamate (MPC) is an important intermediate for the manufacture of methylene diphenyl diisocyanate (MDI) via non-phosgene routes. A novel green process for the synthesis of MPC using aniline, carbon dioxide and methanol was studied, and the effects of preparation conditions on catalytic performance of Cu-Fe/ZrO2-SiO2 together with reaction condition effects on MPC synthesis was emphasized. The results indicate that Cu-Fe/ZrO2-SiO2 prepared by mechanical mixing with metal loading of 10%(wt) has better catalytic performance. H2-TPR results demonstrate that more metal active sites and stronger interaction between metal and support can result in better catalytic performance. The optimized reaction conditions were as follows: volume ratio of acetonitrile : aniline =2:1, molar ratio of methanol : aniline = 1.2:1, catalyst weight percentage =13%, CO2 initial pressure = 2.0 MPa, reaction temperature = 180℃, and reaction time = 11 h. The conversion of aniline, the yield and selectivity of MPC were 14%, 9.2% and 65.7%, respectively, which are much higher than the values reported.