摘要
三聚氯氰与4,4'-联苯二甲酸二酰肼和三(4-苯甲酰肼基)胺通过无过渡金属参与的亲核取代反应,构筑了两种酰肼桥联共价三嗪基聚合物(HB-CTP-1和HB-CTP-2)。采用FTIR、SSNMR、XRD、SEM、TEM、TGA、BET对HB-CTP-1和HB-CTP-2的结构组成、微观形貌、热性能和孔隙特性进行了表征和测试,通过N_(2)和CO_(2)吸附-脱附实验,测定了HB-CTP-1和HB-CTP-2对CO_(2)/N_(2)的吸附选择性,考察了HB-CTP-1和HB-CTP-2作为吸附剂和催化剂的CO_(2)吸附和合成环状碳酸酯性能。结果表明,HB-CTP-1和HB-CTP-2具有良好的CO_(2)吸附性能,273 K、0.1 MPa下吸附量分别为1.61和1.63 mmol/g;313 K、6 MPa下吸附量分别为3.55和5.55 mmol/g;两者因为酰肼桥联基团对N_(2)的排斥作用而表现出较高的CO_(2)/N_(2)吸附选择性(90和119);两者的极限吸附热分别为43.5和30.7 kJ/mol,均属于物理吸附的范畴,表明结构中存在的三嗪单元能够通过偶极-四极作用,增强材料的CO_(2)吸附驱动力。在以HB-CTP-2(100 mg)为主催化剂、四丁基溴化铵为助催化剂(其用量占环氧化物物质的量的5%)、CO_(2)压力2 MPa、温度80℃、反应时间12 h、无溶剂的最优反应条件下,带有多种取代基团的环氧化物均可以较高的收率(60%~99%)被转化为环状碳酸酯类精细化学品,且催化剂循环使用5次后活性无明显下降。
Two acylhydrazine-bridged covalent triazinyl polymers(HB-CTP-1 and HB-CTP-2)were constructed by nucleophilic substitution reaction between cyanuric chloride and 4,4'-bisbenzhydrazide as well as tris(4-benzoylhydrazyl)amine without any transition metal catalyst,respectively.The structural composition,microstructure,thermal properties and pore characteristics of HB-CTP-1 and HB-CTP-2 were characterized and analyzed by FTIR,SSNMR,XRD,SEM,TEM,TGA and BET.The adsorption selectivity of HB-CTP-1 and HB-CTP-2 for CO_(2)/N_(2) was measured,while the performance of HB-CTP-1 and HB-CTP-2 in CO_(2) adsorption and synthesis of cyclic carbonates as adsorbents and catalysts was investigated through adsorption-desorption experiments of N_(2) and CO_(2).The results showed that both HB-CTP-1 and HB-CTP-2 exhibited good CO_(2) capture performance under atmospheric and high pressures(1.61 and 1.63 mmol/g at 273 K and 0.1 MPa,3.55 and 5.55 mmol/g at 313 K and 6 MPa).Based on their reversible adsorption-desorption isotherms at 273 K and 0.1 MPa,the CO_(2)/N_(2) selectivity of HB-CTP-1 and HB-CTP-2 were calculated as 90 and 119 due to the repulsive effect of the acylhydrazine bridging group on N_(2).The ultimate adsorption heat of the two was 43.5 and 30.7 kJ/mol respectively,both belonging to the category of physical adsorption,indicating that the triazine units could enhance the CO_(2) adsorption driving force of the material through dipole-quadrupole interaction.Under the optimal reaction conditions of HB-CTP-2(100 mg)as main catalyst,tetrabutylammonium bromide as co-catalyst(its dosage accounting for 5%of the amount of substance of epoxide),CO_(2) pressure 2 MPa,temperature 80℃,reaction time 12 h,and solvent-free,epoxides with multiple substituent groups could all be converted into cyclic carbonate fine chemicals in a relatively high yield(60%~99%),and the activity of the catalyst did not show significant decrease after being recycled 5 times.
作者
闫秋宇
高燕飞
纪烈勇
刘安华
YAN Qiuyu;GAO Yanfei;JI Lieyong;LIU Anhua(State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Liaoning,China;Shanghai Triumph Energy Conservation Engineering Co.,Ltd.,Shanghai 200333,China)
出处
《精细化工》
北大核心
2026年第3期586-595,共10页
Fine Chemicals
基金
中国建材集团攻关专项资助项目(2021HX0102)
大连理工大学基本科研业务费项目(DUT20LK17)。
