二氧化碳高值利用合成苯氨基甲酸甲酯  

CO_(2)valorization through methyl N-phenylcarbamate synthesis

作　　者：荀家瑶 宋清文[1] 张乾霞 韩丽华 张侃[1] 张建利[2] 刘平[1] XUN Jia-yao;SONG Qing-wen;ZHANG Qian-xia;HAN Li-hua;ZHANG Kan;ZHANG Jian-li;LIU Ping(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China;State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering,Ningxia University,Yinchuan 750021,China)

机构地区：[1]中国科学院山西煤炭化学研究所煤转化国家重点实验室,山西太原030001 [2]宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室,宁夏银川750021

出　　处：《燃料化学学报（中英文）》2023年第4期415-427,共13页Journal of Fuel Chemistry and Technology

基　　金：supported by the Natural Science Foundation of Shanxi(20210302123002);Technical Research and Development Project from Lu'an Chemical Industry Group Co.,Ltd.(2021A0105005);the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(2022-K20).

摘　　要：苯氨基甲酸甲酯(MPC)是合成二苯甲烷二异氰酸酯(MDI)的关键原料。以二氧化碳(CO_(2))及其等价物或衍生物作为碳源合成MPC代表了绿色和可持续的精细化学品合成方法。基于该领域研究,概述了基于CO_(2)转化合成苯氨基甲酸甲酯的研究方法进展。合成路线包括研究较多的CO_(2)等价物(尿素或苯基脲)醇解法,碳酸二甲酯(DMC)氨解法以及二苯基脲和DMC耦合反应法。另外,最理想的合成方法是近几年发展的苯胺、CO_(2)和甲醇三组分“一锅”反应法,以及使用脂肪胺类原料构建氨基甲酸烷基酯类化合物,其代表了最有前景的CO_(2)利用途径之一。详细探讨了反应机理和催化剂选择等问题。研究进展将为进一步提升绿色催化和可持续化学过程效率提供重要理论支持。Methyl N-phenylcarbamate(MPC)is an important intermediate for the synthesis of diphenylmethane diisocyanate(MDI),and its preparation using CO_(2)or its equivalents/derivatives as carbon source represents a green and sustainable manner for fine chemicals synthesis.This review will highlight the development of MPC synthetic methods from the viewpoint of chemical fixation of CO_(2).The contents mainly include the introduction of MPC synthesis through CO_(2)equivalents(urea or phenyl urea)alcoholysis,dimethyl carbonate(DMC)aminolysis,and the coupling of DMC and diphenyl urea.Furthermore,one-pot synthesis of carbamates/MPC from aliphatic amines/aniline,CO_(2)and alcohols is highlighted which represents one of the most promising schemes in direct CO_(2)utilization.What is more,the reaction mechanisms and selection of catalysts are also discussed in detail.The advances will provide important theories on further improving the efficiency of green catalysis and sustainable chemical processes.

关 键 词：二氧化碳 CO_(2)等价物 苯氨基甲酸甲酯 催化 合成方法 

分 类 号：TQ217[化学工程—有机化工]