含酚吡啶基多孔离子聚合物催化CO_(2)合成环状碳酸酯  

Synthesis of cyclic carbonates from CO_(2) catalyzed by porous ionic polymers containing phenol pyridine

作　　者：陈亚举 梁晓道 林冬莹 郑梓帆 高兴 邱永健 雷琳 任清刚 纪红兵 CHEN Yaju;LIANG Xiaodao;LIN Dongying;ZHENG Zifan;GAO Xing;QIU Yongjian;LEI Lin;REN Qinggang;JI Hongbing(School of Chemistry,Guangdong University of Petrochemical Technology,Maoming 525000,Guangdong,China;Institute of Green Petroleum Processing and Light Hydrocarbon Conversion,College of Chemical Engineering,Zhejiang University of Technology,Hangzhou 310014,Zhejiang,China)

机构地区：[1]广东石油化工学院化学学院,广东茂名525000 [2]浙江工业大学化学工程学院浙江绿色石化与轻烃转化研究院,浙江杭州310014

出　　处：《精细化工》2024年第12期2693-2701,2736,共10页Fine Chemicals

基　　金：国家自然科学基金项目(22108046、21938001、21961160741);广东省普通高校重点领域专项项目(2022ZDZX2044);广东省普通高校青年创新人才类项目(2021KQNCX056);广东省科技创新战略专项资金项目(2023S007064、2021S0008);广东普通高校创新团队项目(2019KCXTD002)。

摘　　要：以1,4-二(溴甲基)苯、4-苯基吡啶、2,3-二萘酚为单体,通过Friedel-Crafts烷基化反应一步合成了含酚吡啶基多孔离子聚合物(Py-Pi P&OH),采用FTIR、XPS、SEM、XRD和TGA对其进行了表征。采用N_(2)和CO_(2)吸附-脱附分别对其孔道参数和CO_(2)吸附性能进行了测试。考察了Py-Pi P&OH催化环氧氯丙烷(ECH)与CO_(2)环加成反应的催化活性、最佳反应条件及循环使用稳定性。探究了Py-Pi P&OH在环氧化物与CO_(2)环加成反应中的底物普适性。结果表明,Py-Pi P&OH框架中富含酚羟基、吡啶离子液体单元和微孔结构,其比表面积为155.4 m^(2)/g,在273 K、0.1 MPa条件下,CO_(2)吸附量为37.1 cm^(3)/g。在25 mg Py-Pi P&OH、3.0 mmol ECH、0.05 m L N,N-二甲基甲酰胺、初始CO_(2)压力1.0 MPa、反应温度100℃、反应时间12 h的最佳反应条件下,ECH转化率为99.7%,氯甲基二氧杂戊环酮收率为96.3%;Py-Pi P&OH循环使用5次后,其催化活性和产物选择性没有明显下降;以模拟废气(CO_(2)和N_(2)体积分数分别为15%和85%)为CO_(2)源时,在100℃、3.0 MPa条件下反应24 h,氯甲基二氧杂戊环酮的收率仍可达90.3%。Py-Pi P&OH对催化环氧丙烷、环氧溴丙烷、1,2-环氧丁烷、1,2-环氧乙烷、1,2-环氧辛烷、烯丙基缩水甘油醚、环氧苯乙烷与CO_(2)的反应具有良好的普适性。Phenolated pyridine-based porous ionic polymer (Py-Pi P&OH) was synthesized from one step Friedel-Crafts alkylation reaction of 1,4-bis(bromomethyl)benzene,4-phenylpyridine and 2,3-dinaphthol,and characterized by FTIR,XPS,SEM,XRD and TGA.The catalyst obtained were evaluated by N_(2) and CO_(2) adsorption-desorption,respectively,for its pore parameters and CO_(2) adsorption properties,followed by analyses on its catalytic activity,optimal reaction conditions and recycling stability for catalysis on the cycloaddition reaction between epichlorohydrin (ECH) and CO_2.The substrate universality of Py-Pi P&OH for cycloaddition reaction of epoxide and CO_(2) was further investigated.The results showed that Py-Pi P&OH exhibited a microporous structure with abundant phenolic hydroxyl groups,pyridinium ionic liquid units.The catalyst showed a specific surface area of 155.4 m^(2)/g,and an adsorption capacity for CO_(2) of 37.1 cm^(3)/g at 273 K and 0.1 MPa.Under the optimal reaction conditions of 25 mg Py-Pi P&OH,3.0 mmol ECH,0.05 m L N,N-dimethylformamide,initial CO_(2) pressure 1.0 MPa,reaction temperature 100℃,reaction time 12 h,the ECH conversion was 99.7%,while the yield of 4-(chloromethyl)-1,3-dioxolan-2-one was 96.3%.Py-Pi P&OH could be reused for 5 times without significant loss in catalytic activity and selectivity.When simulated exhaust gas (15%CO_(2)+85%N_(2),volume fraction) was used as CO_(2) source,the yield of 4-(chloromethyl)-1,3-dioxolan-2-one could still reach 90.3% at 100℃and 3.0 MPa for 24 h.Moreover,Py-Pi P&OH displayed good universality in catalyzing reactions of propylene oxide,propylene oxide bromopropane,1,2-butane epoxide,1,2-hexane epoxide,1,2-octane epoxide,allyl glycidyl ether,phenylethane epoxide with CO_(2).

关 键 词：CO_(2) 环状碳酸酯 环氧化物 多孔离子聚合物 多相催化 

分 类 号：TQ23[化学工程—有机化工] TQ203.2