磺胺嘧啶银/超强碱协同催化CO_(2)/醇耦合反应选择性制碳酸二甲酯  

Selective synthesis of dimethyl carbonate via the coupling reaction of CO_(2) and alcohols by the synergistic catalysis of silver sulfadiazine and superbase

作　　者：张福灿 刘平[1] 张侃[1] 吉可明[1] 张建利[3] 赵亮[2] 宋清文[1] ZHANG Fu-can;LIU Ping;ZHANG Kan;JI Ke-ming;ZHANG Jian-li;ZHAO Liang;SONG Qing-wen(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China;State Key Laboratory of Heavy Oil Processing,Chinese University of Petroleum(Beijing),Beijing 102249,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]中国石油大学(北京)重质油国家重点实验室,北京102249 [3]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3期304-313,共10页Journal of Fuel Chemistry and Technology

基　　金：山西省自然科学基金(20210302123002,202103021223460);潞安化工集团有限公司研发基金和省部共建煤炭高效利用与绿色化工国家重点实验室开放基金(2022-K20)资助。

摘　　要：甲醇、CO_(2)和炔丙醇三组分耦合反应为合成绿色化学品碳酸二甲酯(DMC)提供了一种热力学有利新路径。本工作针对该方法中存在的DMC收率低、中间产物转化速率慢的问题,研究了炔烃衍生物α-单取代炔丙醇在耦合反应中对DMC收率及选择性的影响。发展了磺胺嘧啶银与超强碱协同催化串联反应策略,进一步提升了反应效率。考察了催化剂、共催化剂、催化剂用量、溶剂、温度、原料比、压力和时间等因素的影响规律。最优的条件下,DMC选择性达89.5%,收率55.6%。研究表明,炔丙醇的结构会显著影响反应进程,同时,磺胺嘧啶银与1,8-二氮杂二环十一碳-7-烯(DBU)的协同催化作用是高收率、高选择性获得DMC的关键因素。The three-component coupling of methanol, CO_(2)and propargyl alcohol to manufacture dimethyl carbonate(DMC) provides a new, thermodynamic favorable and green chemical synthesis route. In this work, to overcome the problems of low DMC yield and slow conversion rate of intermediates, the synergistic catalytic strategy of silver sulfadiazine and superbase is developed to improve the reaction efficiency. The effect of various parameters i.e. catalyst and cocatalyst types, catalyst loading, solvent, temperature, proportion of raw materials,pressure and time on the coupling reactions is investigated in detail. Under the optimal conditions, the selectivity of DMC is 89.5% with the yield of 55.6%. And the effect of alkyne derivative α-monosubstituted propargyl alcohol on the efficiency and selectivity of DMC are also studied. The mechanism study shows that propargyl alcohols with different structures apparently affect the reaction process, and the synergistic catalysis of silver sulfadiazine/1,8-diazabicyclo[5.4.0]undec-7-ene(DBU) is the reason for the high yield and selectivity of DMC.

关 键 词：碳酸二甲酯 二氧化碳转化 耦合反应 协同催化 

分 类 号：O622.5[理学—有机化学]