超临界二氧化碳中组氨酸催化合成环状碳酸酯

研究了超临界二氧化碳中α-氨基酸催化二氧化碳与环氧化物环加成反应合成环状碳酸酯,发现组氨酸的催化活性最高.在二氧化碳压力为8MPa、反应温度130℃、反应时间48h、组氨酸加入量为0.8mol%的条件下,二氧化物可以顺利的与各种环氧化物反应,以高的选择性和产率生成相应的环状碳酸酯.     

氨基酸盐酸盐催化二氧化碳与环氧化物的环化反应

利用氨基酸盐酸盐作为催化剂,二氧化碳可以和环氧化物发生偶联反应,高产率和高选择性地生成环状碳酸酯,详细研究了反应条件如二氧化碳压力,反应温度,时间及催化剂用量对反应的影响。     

超临界二氧化碳中马来酸锌催化合成环状碳酸酯

在超临界二氧化碳中, 利用马来酸锌催化二氧化碳与环氧化物反应合成环状碳酸酯. 单独使用马来酸锌作为催化剂时, 对二氧化碳与环氧丙烷反应的催化活性较低, 而在DBU、DMAP、三乙胺、吡啶、咪唑或4-氨基吡啶等有机碱的存在下, 反应活性较高, 产物的收率得到明显提高. 有机碱作用的强弱顺序为DBU>Et3N>咪唑>4-氨基吡啶>DMAP>吡啶. 在压力为8 MPa, 温度110 ℃, 反应时间48 h条件下, 马来酸锌与DBU组成的二元催化系统可以催化二氧化碳与环氧丙烷反应, 得到83.4%产率的碳酸丙烯酯. 该二元系统也能催化其它环氧化物高产率地转化为相应的环状碳酸酯.     

SnCl4-organic base: Highly efficient catalyst system for coupling reaction of CO2 and epoxides

A simple and highly efficient catalyst system of SnCl₄-organic base was developed to catalyze the coupling reaction of carbon dioxide and epoxides in very mild condition to yield the cyclic carbonates. The proposed mechanism was described in terms of in situ ¹¹⁹Sn NMR investigations.     

Catalytic synthesis of cyclic carbonates from epoxides and carbon dioxide by magnetic UiO‐66 under mild conditions

The catalytic activity of UiO‐66@Fe₃O₄@SiO₂ catalyst was investigated in the fixation of carbon dioxide with epoxides under mild conditions. In this manner, a facile magnetization of UiO‐66 was achieved simultaneously by simply mixing this metal–organic framework and silica‐coated Fe₃O₄ nanoparticles in solution under sonication. The prepared catalyst was characterized using Fourier transform infrared and UV–visible spectroscopies, X‐ray diffraction, transmission and field emission scanning electron microscopies, N₂ adsorption and inductively coupled plasma atomic emission spectroscopy. This new heterogeneous catalyst was applied as a highly efficient catalyst in the coupling of carbon dioxide with epoxides at mild temperatures and pressures. Furthermore, it could be easily recovered with the assistance of an external magnetic field and reused three consecutive times without significant loss of activity and mass.     

Synthesis of Cyclic Carbonates Catalysed by Aluminium Heteroscorpionate Complexes

New aluminium scorpionate based complexes have been prepared and used for the synthesis of cyclic carbonates from epoxides and carbon dioxide. Bimetallic aluminium(heteroscorpionate) complexes 9 – 14 were synthesised in very high yields. The single‐crystal X‐ray structures of 12 and 13 confirm an asymmetric κ²‐NO‐μ‐O arrangement in a dinuclear molecular disposition. These bimetallic aluminium complexes were investigated as catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide in the presence of ammonium salts. Under the optimal reaction conditions, complex 9 in combination with tetrabutylammonium bromide acts as a very efficient catalyst system for the conversion of both monosubstituted and internal epoxides into the corresponding cyclic carbonates showing broad substrate scope. Complex 9 and tetrabutylammonium bromide is the second most efficient aluminium‐based catalyst system for the reaction of internal epoxides with carbon dioxide. A kinetic study has been carried out and showed that the reactions were first order in complex 9 and tetrabutylammonium bromide concentrations. Based on the kinetic study, a catalytic cycle is proposed.     

Polystyrene-supported Phenol/DMAP： an Efficient Binary Catalyst System for CO2 Fixation to Give Cyclic Carbonates

Polystyrene-supported phenol （PS-PhOH） was successfully synthesized by alkylation reaction of phenol with 2% DVB cross-linked chloromethylated polystyrene and characterized by IR spectra and elemental analysis. In conjunction with an organic base such as DMAP, DBU, triethylamine （Et3N）, diethylamine （Et2NH） or pyridine, the PS-PhOH could effectively catalyze the coupling reaction of carbon dioxide with epoxides to give cyclic carbonates in high yield and selectivity under mild conditions. The binary catalyst system of the PS-PhOH/DMAP was found to be the most active. The influence of reaction temperature, carbon dioxide pressure and reaction time on the yield of product was carefully investigated. The PS-PhOH could be recycled by simple filtration for at least up to ten times without loss of catalytic activity.     

Cyclic carbonate synthesis from epoxides and CO2 over cyanocobalamin/n‐Bu4NI

The synthesis of cyclic carbonates from epoxides and carbon dioxide catalyzed by cyanocobalamin and n‐Bu₄NI system was achieved under 0.8 MPa CO₂ pressure at 140°C without organic solvents. Propylene carbonate was obtained in 99% yield within 6 h under the optimized reaction conditions. The cyanocobalamin catalyst could be recycled with water and retained moderate catalytic activity. Copyright © 2012 John Wiley & Sons, Ltd.     

Differences in Reactivity of Epoxides in the Copolymerisation with Carbon Dioxide by Zinc-Based Catalysts: Propylene Oxide versus Cyclohexene Oxide

The homogeneous dinuclear zinc catalyst going back to the work of Williams et al. is to date the most active catalyst for the copolymerisation of cyclohexene oxide and CO₂ at one atmosphere of carbon dioxide. However, this catalyst shows no copolymer formation in the copolymerisation reaction of propylene oxide and carbon dioxide, instead only cyclic carbonate is found. This behaviour is known for many zinc‐based catalysts, although the reasons are still unidentified. Within our studies, we focus on the parameters that are responsible for this typical behaviour. A deactivation of the catalyst due to a reaction with propylene oxide turns out to be negligible. Furthermore, the catalyst still shows poly(cyclohexene carbonate) formation in the presence of cyclic propylene carbonate, but the catalyst activity is dramatically reduced. In terpolymerisation reactions of CO₂ with different ratios of cyclohexene oxide to propylene oxide, no incorporation of propylene oxide can be detected, which can only be explained by a very fast back‐biting reaction. Kinetic investigations indicate a complex reaction network, which can be manifested by theoretical investigations. DFT calculations show that the ring strains of both epoxides are comparable and the kinetic barriers for the chain propagation even favour the poly(propylene carbonate) over the poly(cyclohexene carbonate) formation. Therefore, the crucial step in the copolymerisation of propylene oxide and carbon dioxide is the back‐biting reaction in the case of the studied zinc catalyst. The depolymerisation is several orders of magnitude faster for poly(propylene carbonate) than for poly(cyclohexene carbonate).     

二氧化碳与环氧化物共聚催化剂研究进展

二氧化碳是主要的温室气体,也是最丰富的C1资源.利用二氧化碳与环氧化物共聚生成可生物降解的聚碳酸酯是目前研究的热点之一.就目前的研究情况而言,二氧化碳与环氧化物共聚反应存在的主要问题是催化效率低、催化剂成本高、反应条件苛刻、共聚物产率较低以及催化剂分离复杂等.我们分类综述了二氧化碳与环氧化物共聚的新型催化体系,并探讨了各类催化体系的优缺点,对二氧化碳的资源化利用具有重要的应用价值.     

Salen-decorated Periodic Mesoporous Organosilica: From Metal-assisted Epoxidation to Metal-free CO2 Insertion

We clicked a salen ligand onto a thiol-ethane bridged periodic mesoporous organosilica (Salen-PMO) using a photo-initiated thiol-ene click reaction. This process resulted in a covalently bonded salen ligand on the PMO material. The final BET surface area amounts 511 m²/g and the pore size diameter is approximately 7 nm. The functionalized PMO material showed an excellent carbon dioxide uptake capacity of 1.29 mmol/g at 273 K and 1 bar. More importantly, by coordinating a MoO₂²⁺ complex onto the Salen-PMO material, we obtained a heterogeneous catalyst with a good catalytic performance for the epoxidation of cyclohexene. The catalyst was highly reusable, as no decrease in its activity was observed for at least four runs (99% conversion). Finally, the metal-free Salen-PMO showed an exceptional catalytic performance in the cycloaddition of CO₂ to epoxides. The obtained results clearly demonstrate the versatility of the Salen-PMO material not only as metal-free catalyst but also as a support material to anchor metal complexes for specific catalytic applications. With the same catalytic platform, we were able to firstly create epoxides out of alkenes, and subsequently turn these epoxides into cyclic carbonates, consuming CO₂.     

Electrochemical activation of carbon dioxide in ionic liquid: synthesis of cyclic carbonates at mild reaction conditions

Electrocatalytic cycloaddition of carbon dioxide to epoxides in room temperature ionic liquids as reaction media without any additional supporting electrolyte and catalyst could be conducted with high to excellent performances under mild conditions.     

Mg(OH)Cl/KI as a Highly Active Heterogeneous Catalyst for the Synthesis of Cyclic Carbonates from CO2 and Epoxides under Solvent‐Free Conditions

The combination of magnesium hydroxyl chloride [Mg(OH)Cl] with KI could efficiently catalyze the coupling reaction of carbon dioxide with epoxides to give the corresponding cyclic carbonates in good to excellent yields (75.0% –98.3%) and high selectivity (99.6%) in the absence of organic solvents. The heterogeneous catalyst Mg(OH)Cl/KI could be reused at least six times almost without loss of the catalytic activity. The influence of some key factors (such as molar ratio of Mg(OH)Cl to KI, temperature, reaction time and CO₂ pressure) on the reaction was also discussed.     

Biodegradable Polycarbonate Synthesis by Copolymerization of Carbon Dioxide with Epoxides Using a Heterogeneous Zinc Complex

As a means for the chemical fixation of carbon dioxide and the synthesis of biodegradable polycarbonates, copolymerizations of carbon dioxide with various epoxides such as cyclohexene oxide (CHO), cyclopetene oxide, 4-vinyl-1-cyclohexene-1,2epoxide, phenyl glycidyl ether, allyl glycidyl ether, propylene oxide, butene oxide, hexene oxide, octene oxide, and 1-chloro-2,3-epoxypropane were investigated in the presence of a double metal cyanide catalyst (DMC). The DMC catalyst was prepared by reacting K₃Co(CN)₆ with ZnCl₂, together with tertiary butyl alcohol and poly(tetramethylene ether glycol) as complexing reagents and was characterized by various spectroscopic methods. The DMC catalyst showed high activity (526.2 g-polymer/g-Zn atom) for CHO/CO₂ (P_CO2 = 140 psi) copolymerization at 80 °C, to yield biodegradable aliphatic polycarbonates of narrow polydispersity (M_w/M_n = 1.67) and moderate molecular weight (M_n = 8900). The DMC catalyst also showed high activities with different CO₂ reactivities for other epoxides to yield various aliphatic polycarbonates with narrow polydispersity.     

溴化锌-季(鎓)三溴盐催化二氧化碳和环氧化合物偶联反应

研究了溴化锌-季鎓三溴盐催化二氧化碳和环氧化合物偶联反应,考察了反应温度、压力和不同金属盐对反应的影响以及催化剂的循环使用性能.结果表明,在413 K和1.0 MPa条件下,以溴化锌为催化剂,苯基三甲基三溴化铵为共催化剂,无需加入任何溶剂就可以使二氧化碳和环氧化合物发生偶联反应,并以很高的收率得到环碳酸酯.     

A poly(ethylene glycol)-supported quaternary ammonium salt for highly efficient and environmentally friendly chemical fixation of CO2 with epoxides under supercritical conditions

A PEG-supported quaternary ammonium salt is proved to be an efficient and recyclable homogeneous catalyst for solvent-free synthesis of cyclic carbonates from carbon dioxide and epoxides under supercritical conditions. Supporting Bu₄NBr on soluble polymer PEG6000 enhances the catalytic activity. The workup procedure is straightforward, and the catalyst can be reused over five times with no appreciable loss of catalytic activity and selectivity.     

脂肪族聚碳酸酯共聚物的研究进展

脂肪族聚碳酸酯共聚物是一类可完全生物降解的新型材料,自1969年井上祥平等首次通过二氧化碳与环氧化合物反应合成脂肪族聚碳酸酯以来,人们在将二氧化碳固定为全降解聚合物这一研究领域取得了大量研究成果.本文综述了用于二氧化碳和环氧化合物共聚合成脂肪族聚碳酸酯的各类催化剂及反应机理,讨论了脂肪族聚碳酸酯结构/性能关系,并简要介绍了其在不同领域的应用.     

Restrictive Regulation of Ionic Liquid Quaternary Ammonium Salt in SBA-15 Pore Channel for Efficient Carbon Dioxide Conversion

Herein, the synthesis of a new type of catalyst, SBA−M (Schiff complex of different metal types grafted on SBA-15) based on a quaternization reaction, is described. Various amounts of ionic liquid were grafted into the pore channels of SBA-15 using the post-grafting method, which allowed the ionic liquid to be grafted into the pore channels restrictively. Notably, over six cycles, SBA−Mn (0.2) has been shown to maintain its catalytic activity and stability. In addition, a reaction mechanism for the cycloaddition of CO₂ with epoxides based on density-functional theory is proposed. The cycloaddition reaction of CO₂ and epoxides is an efficient way of carbon fixation. It is demonstrated that the metal coordinated with the oxygen atom of the epoxides and that a halogen attacked the carbon of epoxides. Moreover, theoretical calculations and synthesis strategy provide a new approach for CO₂ conversion.     

Bifunctional Onium and Potassium Iodides as Nucleophilic Catalysts for the Solvent-Free Syntheses of Carbonates,Thiocarbonates, and Oxazolidinones from Epoxides

The catalytic potential of organo-onium iodides as nucleophilic catalysts is aptly demonstrated in the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO₂), as a representative CO₂ utilization reaction. Although organo-onium iodide nucleophilic catalysts are metal-free environmentally benign catalysts, harsh reaction conditions are generally required to efficiently promote the coupling reactions of epoxides and CO₂. To solve this problem and accomplish efficient CO₂ utilization reactions under mild conditions, bifunctional onium iodide nucleophilic catalysts bearing a hydrogen bond donor moiety were developed by our research group. Based on the successful bifunctional design of the onium iodide catalysts, nucleophilic catalysis using a potassium iodide (KI)-tetraethylene glycol complex was also investigated in coupling reactions of epoxides and CO₂ under mild reaction conditions. These effective bifunctional onium and potassium iodide nucleophilic catalysts were applied to the solvent-free syntheses of 2-oxazolidinones and cyclic thiocarbonates from epoxides.     

Development of a Halide‐Free Aluminium‐Based Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide

Kinetic studies of the synthesis of glycerol carbonate from glycidol and carbon dioxide have been carried out. These showed that under suitable reaction conditions, bimetallic aluminium(salen) complex 4 is able to catalyse the conversion of epoxides into the corresponding cyclic carbonates without the need for a co‐catalyst.