摘要
“双碳”背景下,CO_(2)的综合利用迎来了挑战与机遇,将CO_(2)转化为高附加值化学品对于节能减排和碳循环利用具有重要意义。其中,将CO_(2)与环氧化合物经过环加成反应转化为环状碳酸酯是碳资源循环利用的重要方式之一。研究了环氧丙烷(PO)在以四丁基溴化铵(TBABr)为催化剂的均相体系中氢键供体效应对环加成反应的影响,探究了不同碳数醇类以及酚类极性对反应的影响。研究发现,在温和条件(100℃、2 h、1.5 MPa)下,以邻苯二酚为氢键供体时,PO的转化率可以达到99.8%,碳酸丙烯酯(PC)选择性可以达到99.51%,性能远远高于无氢键供体体系。此外,通过建立线性溶剂化能关系式以及Kamlet-Taft表达式,定量描述了氢键供体(醇类、酚类)极性参数对反应性能的影响,阐明了氢键供体对提高CO_(2)-PO环加成反应效率的影响。
Under the background of“carbon peaking and carbon neutrality goals”,the comprehensive utilization of CO_(2) meets great challenges and opportunities.Furthermore,the conversion of CO_(2) into high value-added chemicals is of great significance for energy conservation,emission reduction and carbon recycling.The conversion of CO_(2) and epoxides into cyclic carbonates through cycloaddition reaction is one of the important ways of carbon resource recycling.The effects of hydrogen bond donor on cycloaddition reaction of propylene oxide(PO)in homogeneous system with tetrabutylammonium bromide(TBABr)as catalyst were explored in detail.In addition,the polarity of linear alcohols and phenols were investigated for enhancing the catalytic performance,respectively.It was found that the conversion of PO shows significantly increased propylene epoxide conversion from 49.8%to 99.8%while maintaining high propylene carbonate selectivity(99.51%)under the mild conditions(100℃,2 h,1.5 MPa),which is much higher than that of non-hydrogen bond donor system. In addition, this study quantitatively described the impact of the polar parameters of hydrogen bond donors (alcohols, phenols) on reaction performance by establishing a linear solvation energy relationship and a Kamlet-Taft expression. Meanwhile, the reaction mechanism of the hydrogen bond donor was elucidated.
作者
张广宇
付然飞
孙冰
袁俊聪
冯翔
杨朝合
徐伟
ZHANG Guangyu;FU Ranfei;SUN Bing;YUAN Juncong;FENG Xiang;YANG Chaohe;XU Wei(National Key Laboratory of Chemical Safety,SINOPEC Research Institute of Safety Engineering Co.,Ltd.,Qingdao 266000,Shandong,China;State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Qingdao 266580,Shandong,China)
出处
《化工学报》
EI
CSCD
北大核心
2024年第6期2243-2251,共9页
CIESC Journal
基金
国家自然科学基金项目(22208383,21978325)。
