对苯二甲基二甲醚的合成工艺进展  

Research progress in synthesis of 1,4-bis(methoxymethyl) benzene

作　　者：陈婷婷[1,2] 林涨 佟子睿 方明哲 胡予缤 陈新志 CHEN Ting-ting;LIN Zhang;TONG Zi-rui;FANG Ming-zhe;HU Yu-bin;CHEN Xin-zhi(College of Chemical and Biological Engineering,Zhejiang University,Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology,Hangzhou 310027,China;Institute of Zhejiang University-Quzhou,Quzhou 324000,China)

机构地区：[1]浙江大学化学工程与生物工程学院,浙江省化工高效制造技术重点实验室,浙江杭州310027 [2]浙江大学衢州研究院,浙江衢州324000

出　　处：《应用化工》2022年第6期1713-1718,1728,共7页Applied Chemical Industry

摘　　要：对苯二甲基二甲醚是重要的精细化工原料和合成中间体,主要用于合成高分子树脂。对其合成方法进行分类,并归纳了这些方法的优缺点,其中对二卤苄路线具有原料易得、操作简便、产率高等优点,但卤素会转化成卤盐,原子经济性差,后处理成本高。对二苄醇路线中,以硫酸二甲酯为醚化试剂,副产物主要是硫酸和硫酸甲酯,具有强烈的刺激性和腐蚀性,对设备要求较高;以碳酸二甲酯为醚化试剂,催化剂易得,副产物主要是甲醇和CO_(2),但反应需高温高压,反应条件苛刻。对苯二甲酸二甲酯直接加氢制备对苯二甲基二甲醚,反应步骤简单,但使用贵金属催化剂,价格昂贵,且反应需高温高压。综合来看,以碳酸二甲酯为醚化试剂与对二苄醇酯交换脱羧生成对苯二甲基二甲醚,无需引入卤素,环境污染程度低,且释放CO_(2)有利于推动反应正向进行,产物产率高,有实现绿色工业化生产的前景。1,4-Bis(methoxymethyl)benzene is an important fine chemical raw material and synthesis intermediate,mainly used for the synthesis of polymer resins.This paper classifies the synthetic methods of 1,4-bis(methoxymethyl)benzene and summarizes the advantages and disadvantages of these methods.The 1,4-bis(chloromethyl)benzene route has the advantages of easy availability of raw materials,simple operation and high yield,but halogens will be converted into halide salts,which results in poor atomic economy and high post-processing costs.In the 1,4-benzenedimethanol route,when dimethyl sulfate is used as the etherificating reagent,the by-products are mainly sulfuric acid and methyl sulfate,which are strongly irritating and corrosive,requiring suitable equipment;while dimethyl carbonate is used as the etherificating reagent,the catalyst is easily available and the by-products are mainly methanol and CO_(2),but the reaction conditions are harsh,requiring high temperature and high pressure.Dimethyl terephthalate is directly hydrogenated to prepare 1,4-bis(methoxymethyl)benzene route has the simple reaction steps,but it requires expensive catalysts,high temperature and high pressure.On the whole,dimethyl carbonate used as etherificating reagent reacts with 1,4-benzenedimethanol to transesterify and decarboxylate to produce 1,4-bis(methoxymethyl)benzene,doesn’t introduce halogens,with low contamination degree.And the release of CO_(2) is conducive to promoting the positive reaction,bringing high product yield.This route has the prospect of realizing green industrialized production.

关 键 词：对苯二甲基二甲醚 合成树脂 对二卤苄 碳酸二甲酯 有机化合物 

分 类 号：TQ32[化学工程—合成树脂塑料工业]