多位点离子液体聚合物催化CO2环加成反应研究

CO₂与环氧化物环加成反应制备环状碳酸酯是一条绿色经济的CO₂利用途径。针对现有CO₂与环氧化物环加成反应中非均相离子液体催化剂活性低和活性组分易流失等问题,设计制备了系列多位点离子液体超交联聚合物HCPs-[DmPhe]Br,研究了多位点协同作用、超交联聚合物组成和结构等因素对其催化CO₂与环氧化物环加成反应性能的影响。其中,同时含有双季铵-卤素离子对、羟基和叔胺结构的HCP-[DmPhe]Br-DCX离子液体超交联聚合物催化剂,在1.3 MPa, 130℃,8 h的条件下,可实现94%的碳酸丁烯酯收率,且催化剂循环稳定性好,重复使用5次,催化活性没有明显降低。另外,超交联聚合物的多孔结构以及大比表面积促进了离子液体的较好分散,使其与离子液体单体具有相当的活性。该工作对CO₂与环氧化物环加成反应高效非均相离子液体催化剂的开发与优化具有一定的借鉴意义。     

多孔有机聚合物催化二氧化碳合成环状碳酸酯研究进展

二氧化碳（CO₂）捕集、利用和储存（CCUS）在全球能源结构转型中是一种极具潜力的策略,能够实现能源供给、基础原料产出以及限制气候变化。多孔有机聚合物（POPs）具有高CO₂吸附容量和吸附选择性、突出的结构特性以及优异的化学可调控性,其作为极具潜力的材料广泛应用于催化CO₂参与的有机反应中。其中,CO₂与环氧化物环加成生成环状碳酸酯的反应具有100%的原子经济性,且其产物也极具工业价值。本文基于CO₂环加成反应催化机制,从催化剂的合成方法、结构性质与组成特性角度出发,综述了POPs在CO₂/环氧化物环加成反应的研究进展,包括金属配合物类、氢键供体类、离子液体类、金属配合物/离子液体和氢键供体/离子液体等有机多孔聚合物体系。通过阐述POPs在催化CO₂制备高附加值环状碳酸酯反应中的研究现状和发展趋势,为POPs的开发与应用以及CO₂综合利用的工业化探索提供具有建设性的指导意见。     

均相体系中酸碱协同催化二氧化碳与环氧化物的环加成反应

基于“可持续发展”和“绿色化学”的概念,近年来CO₂的捕获、储存及资源化利用在工业上和学术上一直备受关注。通过具有100%原子经济性特点的CO₂与环氧化物环加成反应合成五元环状碳酸酯是最有前景的方法之一。基于均相催化剂的设计思想与方法,以CO₂和环氧化物的活化本质出发,从催化剂结构的角度综述了均相体系中酸碱协同催化CO₂与环氧化物环加成反应合成环状碳酸酯的研究进展,包括简单二元催化体系、功能型一元催化体系和金属配合物催化体系等。     

季铵型多孔超交联离子聚合物催化二氧化碳环加成合成环状碳酸酯

以双(三苯基膦)氯化铵为单体，通过傅-克烷基化反应制备一种季铵型多孔超交联离子聚合物(QA-PHIP)。采用傅里叶变换红外光谱、扫描电镜和N₂吸附-脱附等对QA-PHIP进行表征。结果表明，QA-PHIP的比表面积为903.7 m²·g^-1,在0.1 MPa和0℃条件下CO₂的吸附量为52.1 cm³·g^-1。将QA-PHIP应用于催化CO₂与环氧化物合成环状碳酸酯的反应，考察反应温度和催化剂用量等因素对催化性能的影响。QA-PHIP表现出良好的催化性能，在120℃和1.0 MPa条件下反应12 h,可获得99.6%的环氧氯丙烷转化率和97.3%的氯甲基二氧杂戊环酮收率。QA-PHIP表现出良好的底物扩展性和重复使用性。     

溴代甲基咪唑修饰的蜜勒胺低聚物催化CO2环加成反应性能

采用两步法合成了溴代甲基咪唑修饰的蜜勒胺低聚物(CN-MIm),利用FTIR、XRD、SEM、TG和XPS对其结构、形貌和热稳定性进行了表征。考察了反应工艺条件对环氧氯丙烷(ECH)和CO₂环加成反应的影响。结果表明,咪唑基离子液体成功负载在蜜勒胺低聚物上,且具有较好的热稳定性。以CN-MIm为催化剂,在反应温度为120℃、反应时间为1.5 h,CO₂压力为2.0 MPa、催化剂(0.1 g)与ECH质量比为0.036∶1条件下,ECH转化率和氯代碳酸丙烯酯产率分别为99%和98%。CN-MIm对不同环氧化物均具有良好的普适性。此外,提出了蜜勒胺低聚物中含有的羟基、氨基及咪唑基离子液体中Br^–对环氧化物和CO₂环加成的协同催化反应机理。     

离子液体和低共熔溶剂催化二氧化碳合成有机碳酸酯的研究进展

离子液体和低共熔溶剂因其良好的溶解与催化能力,可催化CO₂转化为高附加值化学品。本文综述了离子液体和低共熔溶剂催化CO₂转化为有机碳酸酯的研究进展,分析了CO₂与醇生成直链碳酸酯以及与环氧化物生成环状碳酸酯的反应机理;介绍了传统型、质子型、功能化离子液体以及由氯化胆碱、季铵盐与季膦盐、有机碱等作为氢键受体组成的低共熔溶剂,及其在CO₂转化为直链和环状碳酸酯反应中的催化性能;总结了此两类反应中离子液体和低共熔溶剂设计的基本规律;指出了CO₂转化反应中离子液体与低共熔溶剂存在的催化效率低、稳定性不高、后续分离困难等问题,后续研究可结合计算机辅助设计方法,探索更合适的阴阳离子/氢键供受体组合,获得更高效的催化体系。     

固载氨基化离子液体的制备及其对CO2的吸附性能

利用浸渍法将[NH₃P-mim][BF₄]和[MEA]L两种离子液体负载到AC、Al₂O₃和MCM-41上,考察了对CO₂的吸附性能,确定了[NH₃P-mim][BF₄]/AC对CO₂的吸附性能最优。并对[NH₃P-mim][BF₄]/AC考察了不同负载量、不同温度下对CO₂的吸附性能,确定了固载离子液体对CO₂的吸附容量随着负载量的增加而增加,且30℃是固载离子液体吸附CO₂的最佳温度,吸附容量达到0.063 mmol CO₂·(g SILP)^-1。对[NH₃P-mim][BF₄]/AC进行红外和热重两种表征,确定了负载离子液体的结构以及在50℃以下优良的热稳定性。     

离子液体在CO_2环加成反应中的应用

离子液体作为一种新型的“绿色溶剂”,因其具有热稳定性好、挥发性低、结构可设计性等优点被广泛应用在CO2环加成反应中。综述了由离子液体催化CO2与环氧化物的环加成反应制备环状碳酸酯的研究进展,从反应相态的角度将离子液体催化剂分为普通离子液体催化剂和负载离子液体催化剂,分别阐述了其催化性能。简要分析了离子液体催化剂目前存在的主要问题,并对离子液体在CO2环加成反应中的应用进行了展望。     

离子液体在CO_2环加成反应中的应用

离子液体作为一种新型的“绿色溶剂”,因其具有热稳定性好、挥发性低、结构可设计性等优点被广泛应用在CO2环加成反应中。综述了由离子液体催化CO2与环氧化物的环加成反应制备环状碳酸酯的研究进展,从反应相态的角度将离子液体催化剂分为普通离子液体催化剂和负载离子液体催化剂,分别阐述了其催化性能。简要分析了离子液体催化剂目前存在的主要问题,并对离子液体在CO2环加成反应中的应用进行了展望。     

离子液体支撑液膜的CO2/CH4分离性能

由于离子液体对CO₂具有较好的溶解选择性,离子液体支撑液膜分离CO₂越来越受到关注。比较了含3种不同阴离子的常规离子液体([bmim][BF₄]、[bmim][PF₆]、[bmim][Tf₂N])作为支撑液膜的液膜相分离CO₂/CH₄的性能,考察了咪唑环上烷基链长对离子液体支撑液膜性能的影响。考虑向离子液体中引入胺基和羧基等亲CO₂基团,制备了1-丁基-3-甲基咪唑丙氨酸离子液体([bmim][β-Ala]),考察了 [bmim][β-Ala]支撑液膜分离CO₂/CH₄的性能,并对在CO₂渗透测试前后的支撑液膜进行了FT-IR分析,发现氨基酸离子液体中的-NH₂和CO₂的较强作用以及该离子液体的高黏性影响了CO₂的透过性,使[Bmim][β-Ala]支撑液膜的CO₂透过率低。     

A mini review on chemical fixation of CO 2 : Absorption and catalytic conversion into cyclic carbonates

In this article, we present our research results on chemical fixation of CO₂ using organobismuth compounds. We fabricated bismuth biphenoate complex, Zn-Mg-Al composite oxides, and SBA-15 or Al-SBA-15 immobilized hydroxyl ionic liquid for CO₂ cycloaddition onto epoxides. The hypervalent bismuth compounds show good ability for association and dissociation with CO₂. The bismuth biphenolate complexes are catalytically effective for the cycloaddition reaction. The heterogeneous catalysts, viz. Zn-Mg-Al oxides and SBA-15 or Al-SBA-15 immobilized ionic liquid, are efficient for the synthesis of cyclic carbonate from CO₂ and epoxide. It is found that the presence of a trace amount of water can improve the catalytic activity of the immobilized ionic liquid.     

Efficient homogenous catalysis of CO2 to generate cyclic carbonates by heterogenous and recyclable polypyrazoles

The cycloaddition between CO₂ and epoxides to produce cyclic carbonate is an attractive and efficiency pathway for the utilization of CO₂ as C1 source. The development of catalyst to mediate cycloaddition between CO₂ and epoxides at low temperature and pressure is still a challenge. Herein, a series of polypyrazoles with glass transition temperature (T_g) in the range of 42.3–52.5 ℃ were synthesized and served as catalyst to mediate the cycloaddition of CO₂ and epoxides by the assistant of tetrabutylammonium bromide. The catalytic behaviors of polypyrazole on the model cycloaddition of CO₂ to epichlorohydrin, including the reaction parameters optimization and versatility were investigated in detail, and excellent yield (99.9%) and selectivity (99%) were obtained under the optimized reaction conditions of 70 ℃ and 1.0 MPa for 6.0 h. Noteworthily, the polypyrazole acts as homogeneous catalyst during reaction (higher than T_g). And under room temperature, polypyrazoles can be easily separated and recovered, which is a promising feature of a heterogeneous catalyst. Furthermore, the reaction mechanism was proposed. The DFT calculation suggested that the formation of hydrogen bond between pyrazole and epoxide greatly reduced the energy barrier, which play an important role in promoting CO₂ cycloaddition.     

固载化BrФnsted酸离子液体催化合成环状碳酸酯的研究

制备了一系列聚苯乙烯树脂(PS)固载的系列BrФnsted酸性离子液体,并对其结构进行了表征。考察了固载化离子液体在二氧化碳与环氧化合物环加成反应中的催化性能,并对其反应条件进行了优化。在固载化离子液体PS-羧基异丁基-咪唑溴盐(PS-HBIMBr)的催化作用下,在反应温度为120℃、反应压力2.0 MPa的优化条件下反应3 h,碳酸丙烯酯的收率高达92.7%,该催化剂对二氧化碳与环氧化合物环加成反应具有良好的重复使用性能。     

Low-pressure CO2 sorption in ammonium-based poly(ionic liquid)s

Ammonium-based ionic liquid monomers and their corresponding polymers [poly(ionic liquid)s] are synthesized and characterized for CO₂ sorption. The polymers have much higher CO₂ sorption capacities than the room-temperature ionic liquids and imidazolium-based poly(ionic liquid)s. For example, P[VBTMA][PF₆] with polystyrene backbone has a CO₂ sorption capacity of 10.67 mol%. The CO₂ sorption is selective over N₂ and O₂. The effects of cation, backbone, substituent, anion and crosslinking on CO₂ sorption are discussed. The sorption mechanism study indicates that CO₂ sorption by the poly(ionic liquid)s is a bulk and surface phenomenon.     

Recent progress of green sorbents-based technologies for low concentration CO2 capture

The increased concentration of CO₂ due to continuous breathing and no discharge of human beings in the manned closed space, like spacecraft and submarines, can be a threat to health and safety. Effective removal of low concentration CO₂ from the manned closed space is essential to meet the requirements of long-term space or deep-sea exploration, which is an international frontier and trend. Ionic liquids (ILs), as a widespread and green solvent, already showed its excellent performance on CO₂ capture and absorption, indicating its potential application in low concentration CO₂ capture. In this review, we first summarized the current methods and strategies for direct capture from low concentration CO₂ in both the atmosphere and manned closed spaces. Then, the multi-scale simulation methods of CO₂ capture by ionic liquids are described in detail, including screening ionic liquids by COSMO-RS methods, capture mechanism by density functional theory and molecular dynamics simulation, and absorption process by computational fluid dynamics simulation. Lastly, some typical IL-based green technologies for low concentration CO₂ capture, such as functionalized ILs, co-solvent systems with ILs, and supported materials based on ILs, are introduced, and analyzed the subtle possibility in manned closed spaces. Finally, we look forward to the technology and development of low concentration CO₂ capture, which can meet the needs of human survival in closed space and proposed that supported materials with ionic liquids have great advantages and infinite possibilities in the vital area.     

负载[APMIm][Br]离子液体吸收CO2的性能

1-氨丙基-3-甲基咪唑溴盐（[APMIm][Br]）离子液体通过化学反应捕集CO₂。采用浸渍-蒸发将[APMIm][Br]离子液体负载在硅胶表面,通过比表面孔隙吸附测定仪、热重分析仪（TGA）对吸收剂的结构与性能进行研究,负载量为10%～50%,温度为303.15～323.15 K,CO₂浓度分别为10%、30%、50%。结果表明：硅胶表面的离子液体薄膜厚度达到86 nm（负载40%）时,具有最快的吸收速率,且受CO₂浓度和温度变化的影响较小,平衡吸收量在50% CO₂体系中达到理论吸收量的80%,随着温度的升高而降低,当负载量为50%时,膜厚增加到230 nm,导致吸收速率和平衡吸收量大幅度下降。值得注意的是：负载离子液体吸收剂在循环使用3次之后,结构与性能均保持不变,表现出一定的工业运用前景。     

Research on crosslinking of epichlorohydrin and ionic liquids

Ionic liquid supported liquid membranes have shown high CO₂ selective separation performance, but their low pressure resistance greatly limits their industrial applications. From the viewpoint of high cost and complex synthesis of crosslinkers used for crosslinking ILs, preparing IL-based gels by crosslinking diamino protic ionic liquids (PILs) with epichlorohydrin (ECH) was proposed in this work. The feasibility of this conception was confirmed via monitoring dynamical information of reaction system. The effects of protonation, reaction temperature and ECH-to-PIL molar ratio on the conversion of epoxy and chloride groups were systematically investigated. The gel transition property of these crosslinked PILs and the possible crosslinking mechanism were studied. Moreover, CO₂ permeation performance in crosslinked ILs was preliminarily tested.     

胆碱类低共融溶剂在CO2捕集与分离中的应用

胆碱类低共融溶剂是一种新型的离子液体。它不仅具有传统离子液体的优点,还具有价格低廉、低毒、生物可降解等优势。对胆碱类低共融溶剂在CO₂捕集与分离中所涉及的物理性质,如气体的溶解度、CO₂的吸收-解吸、密度、稳定性、黏度和表面张力等进行考察,并分析了胆碱类低共融溶剂的结构对各物性的影响。通过与传统离子液体的对比,胆碱类低共融溶剂在CO₂捕集与分离中的应用具有一定的优势,如CO₂溶解度高,黏度低。然而,胆碱类低共融溶剂在气体的选择性分离、表面张力等的研究还不足,且热稳定性方面还存在瓶颈,因此,其在CO₂捕集和分离中的应用还有待进一步探讨。