氮杂环有机催化CO2环加成反应：咪唑环的弱协同效应

doi:10.11949/0438-1157.20210051

摘要/Abstract

摘要：

稳定的CO₂ 需要高能分子的活化，如环氧化物。而亲核试剂有助于诱发三元氧环的开环，进而实现CO₂的插入活化。针对聚苯乙烯负载的有机催化剂，考察不同含氮杂环材料在催化CO₂环加成中的活性差异，发现五元氮杂环显示出了高于六元氮杂环的催化活性，五元氮杂环对底物间弱的协同效应是诱发环氧丙烷开环和活化CO₂插入的关键。进而与引入ZnCl₂、烷基胺的聚苯乙烯负载型催化剂作对比，虽然后两者反应速率得以提高，但也造成了选择性的下降。在无金属、无卤素、无添加剂、无溶剂下，PS-Im这种简单、廉价、稳定且可回收利用的聚苯乙烯负载氮杂环材料适合于工业推广。

关键词: CO₂, 催化, 活性, 氮杂环, 咪唑, 协同效应

Abstract:

Stable CO₂ has to be activated by high-energy chemicals, such as epoxide. Nucleophilic reagents are acted as the trigger for the ring-opening of epoxides and CO₂ insertion. In this work, a series of polystyrene-supported N-heterocycles were tested for their difference on CO₂ cycloaddition. It is found that five-membered heterocyclic compounds exhibited higher activity than six-membered ones. A weak interaction between five-membered heterocycles and substrates is the key point to promote the ring-opening of epoxide and the activation of CO₂ insertion. By comparison, the introduction of ZnCl₂ and_{alkyl amine boosted the reaction rate, but decreased the selectivity. As a simple, cost-effective, stable and reusable material, polystyrene-supported imidazole without metal, halide, co-catalyst and solvent, is considered as a suitable catalyst for industrial application.}

Key words: CO₂, catalysis, reactivity, N-heterocycle, imidazole, synergistic effect

中图分类号:

O 643.36

王结祥, 关磊, 叶松寿, 郑进保, 陈秉辉. 氮杂环有机催化CO₂环加成反应：咪唑环的弱协同效应[J]. 化工学报, 2021, 72(7): 3696-3705.

WANG Jiexiang, GUAN Lei, YE Songshou, ZHENG Jinbao, CHEN Binghui. N-Heterocyclic organocatalyst for carbon dioxide cycloaddition: weak synergistic effect of imidazolium[J]. CIESC Journal, 2021, 72(7): 3696-3705.

图/表 14

图1 PS-N的合成

Fig.1 Synthesis of polystyrene-supported N-heterocycles

图2 PS-Mim-ZnCl2和PS-Im-Ep-TEPA的合成路线

Fig.2 Synthesis routes of PS-Mim-ZnCl2 and PS-Im-Ep-TEPA

图3 PS-N的定性与定量分析

Fig.3 Qualitative and quantitative analysis for PS-N heterocycle series

图4 CO2环加成反应

Fig.4 CO2 cycloaddition reaction

图5 PS-N应用于CO2环加成反应[反应条件:PO 15ml,PCO2 4 MPa(初始压力),催化剂 1.5 g(其中,Mim 0.5 g,约为PS-Mim活性组分用量的3倍),T=100℃, t=10 h]

Fig.5 CO2 cycloaddition catalyzed by PS-N series

表1 PS-Im用于CO2环加成反应的条件优化

Table 1 Reaction condition optimization for PS-Im to catalyzed CO2 cycloaddition

Entry	Temp./℃	Cat.∶PO	Initial pressure/MPa	Time/h	PC yield/%	PC selectivity/%
1	80	1.5 g∶15 ml	4	10	59.2	98.8
2	100	1.5 g∶15 ml	4	10	81.3	99.0
3	120	1.5 g∶15 ml	4	10	97.4	99.5
4	140	1.5 g∶15 ml	4	10	99.8	99.3
5	120	3.0 g∶30 ml	4	10	95.3	99.5
6	120	0.5 g∶15 ml	4	10	96.6	99.6
7	120	0.5 g∶15 ml	4	10	96.1	99.8

图6 PS-Im在CO2环加成中的重复性测试[反应条件:PO 15 ml,PCO2 3 MPa(初始压力),催化剂 0.5 g,T=120℃, t=10 h]

Fig.6 Recycling test for PS-Im to catalyzed CO2 cycloaddition

图7 PS-N系列的孔结构性质及对CO2的吸附性能

Fig.7 CO2 adsorption for PS-N heterocycle series

图8 组分间的相互作用示意图

Fig.8 The diagram for the interaction of components

图9 PC-Pz、PC-Mim两种混合液的1H NMR比较

Fig.9 1H NMR comparison for PC-Pz and PC-Mim

图10 PC-Mim混合液的ATR-IR

Fig.10 ATR-IR for PC-Mim mixture

图11 PS-Im上咪唑环对反应底物CO2和PO间可能的弱协同催化示意图

Fig.11 Plausible schematic diagram of a weak cooperative catalysis between imidazole and substrates (CO2 and propylene oxide) on PS-Im

图12 改性PS-N的定性分析

Fig.12 Qualitative analysis for the modified polystyrene-supported imidazoles

表2 聚苯乙烯负载系列用于CO2环加成反应

Table 2 CO2 cycloaddition catalyzed by PS-supported series

Catalyst	Reaction time/h	Yield/%	Selectivity/%
PS-Mim	10	62.5	98.1
PS-Mim-ZnCl₂	7	97.1	92.5
PS-Im	10	97.4	99.0
PS-Im-Ep-TEPA	8	98.7	94.6

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氮杂环有机催化CO₂环加成反应：咪唑环的弱协同效应

N-Heterocyclic organocatalyst for carbon dioxide cycloaddition: weak synergistic effect of imidazolium

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