乙烯路线制备甲基丙烯酸甲酯研究进展

甲基丙烯酸甲酯（MMA）是一种重要的基础有机化工原料,主要用于生产有机玻璃、塑料改性剂及表面涂料等诸多行业,具有非常广阔的发展前景,MMA 合成路线众多。本文综述了以乙烯为起始原料,经过羰基化反应制备丙醛、丙酸和丙酸甲酯等中间产物,然后经羟醛缩合反应制备MMA的研究进展。概述了乙烯制备MMA的3条工艺路线及其发展趋势,指出中间产物与甲醛的缩合反应是乙烯路线的关键步骤,重点介绍了羟醛缩合反应及其催化剂的研究现状。目前用于气相催化羟醛缩合反应的催化剂主要有V、Si、P酸性催化剂和K、Cs碱性催化剂,其中以Cs为主活性组分的碱性催化剂研究最为广泛,载体种类、助剂、制备方法、反应条件等对催化剂的活性、选择性和寿命等具有较大影响。为进一步改善催化剂的性能,需加强对羟醛缩合反应催化机理的研究,具有酸碱两性的复合催化剂是今后重点研究方向。

Progress in preparation of methyl methacrylate by ethylene route

Methyl methacrylate (MMA) is an important raw material in organic industry. It is widely used in the production of organic glass (PMMA), plastic modifier and surface coating and so on. It has a very broad development prospect and many synthetic routes have been adopted for its production. This paper reviews the development of the ethylene route for the preparation MMA. Ethylene is used as the starting material the intermediates such as propionaldehyde, propionic acid and methyl propionate may be obtained through the carboxylation reaction. Therefore, there are three routes to prepare MMA by the aldol condensation reaction based on these intermediates, and their development trend is also summarized. The aldol condensation reaction of these intermediates with formaldehyde is the key step of ethylene route, so the research status of aldol condensation reaction and its catalysts are emphasized in this paper. At present, V, Si, P based acid catalysts and K, Cs based basic catalysts are often used in the gas phase catalytic aldol condensation reaction. Among them, the Cs-based catalysts are the most widely studied. The activity, selectivity, stability of the catalysts are affected by the supports, promoters, preparations and process conditions. To improve the performance of the catalysts, it is necessary to strengthen the basic researches on the mechanism for aldol condensation reaction, and the acid-base composite catalysts are also the key research direction in the future.