A two-component supported catalyst, preparation method and application thereof

Abstract

The present invention provides a two-component supported catalyst having a structure of formula (I), which is composed of a carrier and an active component (including a Lewis acid and a Lewis base). The present application also provides a preparation method and application of the two-component supported catalyst. The two-component supported catalyst provided in the present application can catalyze the coupling reaction of carbon dioxide and epoxy compounds, and has high selectivity (>99%) and ultra-high activity (TOF=3*10 5 h ‑1 ) is used to prepare cyclic carbonates. After the reaction is completed, the catalyst is easy to separate and can be recycled for many times. It can be used for large-scale clean preparation of colorless cyclic carbonates, which meets the requirements of sustainable development strategies.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, and in particular to a two-component supported catalyst, a preparation method thereof and an application thereof. Background Art

[0002] In the face of the severe situation of global warming, carbon dioxide has attracted much attention as a major greenhouse gas. If it can be regarded as a non-toxic, low-cost and abundant natural C1 resource and utilized, it will meet the requirements of the sustainable development strategy. Therefore, it is of great significance to convert carbon dioxide into chemical products with industrial value. The preparation of cyclic carbonates by cycloaddition coupling reaction of epoxides and carbon dioxide is an effective strategy. On the one hand, the atom economy of the reaction is 100%, and on the other hand, cyclic carbonates can be used as electrolytes and cleaning solvents, and are widely used in terminal products such as lithium batteries, paints, degreasing, dyes and cosmetics.

[0003] In the reaction of carbon dioxide and epoxy compounds to prepare cyclic carbonates, the activation of carbon dioxide is a key issue. At present, a large number of catalysts have been developed and studied for the activation of carbon dioxide, including ionic liquids, organometallic materials, organic salts and alkali metal catalysts. In many literature surveys, the composition and design of the catalyst are crucial to its catalytic activity. Only when a catalytic system contains both Lewis acid and Lewis base can the activity of the catalyst be significantly improved. However, the high-activity formation of cyclic carbonates often requires the addition of a large amount of co-catalysts, which is difficult to separate and purify, and will also bring higher production costs and risk factors, which is not conducive to industrial production. The development and use of heterogeneous catalysts is undoubtedly an effective strategy to achieve clean and industrial preparation of cyclic carbonates.

[0004] Porous organic polymers (POPs) are heterogeneous catalysts containing Lewis acids and bases designed by this strategy. They have the highest activity (TOF = 15600h) in the reaction of carbon dioxide and epoxides to prepare cyclic carbonates. -1 ). However, the preparation of the catalyst is complicated, and the Lewis acid-base ratio in the structure cannot be clearly determined, making it difficult to conduct more in-depth regulation and analysis of the catalytic activity and mechanism of action of the catalyst. Therefore, it is of great significance to provide a new catalyst for cyclic carbonate. Summary of the invention

[0005] The technical problem solved by the present invention is to provide a two-component supported catalyst. The two-component supported catalyst provided by the present application has super high activity as a catalyst for preparing cyclic carbonates.

[0006] In view of this, the present application provides a two-component supported catalyst as shown in formula (I),

[0007]

[0008] Wherein, Carrier is an inorganic carrier, a polymer carrier or a composite carrier of an inorganic carrier and a polymer carrier;

[0009] The LA is a Lewis acid, and the LB is a Lewis base;

[0010] The x and y are load rates, 0<x<50%, y=1-x.

[0011] Preferably, the inorganic carrier is selected from SiO 2 、Al 2 O 3 , MgO, ZnO, TiO 2 , functionalized SiO 2 , functionalized Al 2 O 3 , functionalized MgO, functionalized ZnO and functionalized TiO 2 One or more of the functionalization methods are bromination, chloromethyl functionalization, amino functionalization, hydroxyl functionalization or thiol functionalization; the polymer carrier is selected from one or more of cross-linked polystyrene, polyamide, polyethylene-glycol resin, functionalized cross-linked polystyrene, functionalized polyamide and functionalized polyethylene-glycol resin, and the functionalization method is bromination, chloromethyl functionalization, amino functionalization, hydroxyl functionalization or thiol functionalization.

[0012] Preferably, the LA is selected from the metal porphyrin compound represented by formula a;

[0013]

[0014] Among them, R 1 ~R 19 Each is independently selected from hydrogen, halogen, amino, nitro, cyano, C1-C10 aliphatic group, C1-C10 substituted alkoxy group, C3-C10 substituted cycloalkyl group, C1-C10 heterocyclic group, C6-C12 substituted aryl or substituted C1-C12 heteroaryl;

[0015] The L 1 a functional group selected from amino, nitro, cyano or hydroxyl;

[0016] M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;

[0017] X is selected from halogen, -NO 3 , CH 3 COO-、CCl 3 COO-, CF 3COO-、ClO 4- , BF 4- BPh 4- 、-CN、-N 3 , p-toluenesulfonate, p-toluenesulfonate, o-nitrophenolate anion, p-nitrophenolate anion, m-nitrophenolate anion, 2,4-dinitrophenolate anion, 3,5-dinitrophenolate anion, 2,4,6-trinitrophenolate anion, 3,5-dichlorophenolate anion, 3,5-difluorophenolate anion, 3,5-di-trifluoromethylphenolate anion or pentafluorophenolate anion.

[0018] Preferably, the LB is one of the structures shown in formula b to formula d:

[0019]

[0020] Among them, o, p, q are the number of methylene groups, ranging from 1 to 7;

[0021] Y is selected from halogen, NO 3 - , CH 3 COO - , CCl 3 COO - CF 3 COO - , ClO 4- , BF 4- BPh 4- , CN - 、-N 3 , p-toluenesulfonate, p-toluenesulfonate, o-nitrophenolate anion, p-nitrophenolate anion, m-nitrophenolate anion, 2,4-dinitrophenolate anion, 3,5-dinitrophenolate anion, 2,4,6-trinitrophenolate anion, 3,5-dichlorophenolate anion, 3,5-difluorophenolate anion, 3,5-di-trifluoromethylphenolate anion or pentafluorophenolate anion.

[0022] Preferably, the LA is selected from the metalloporphyrin represented by formula a, and R 1 ~R 19 is selected from hydrogen, said L 1 is selected from amino, M is selected from Al, and X is selected from Cl;

[0023] The LB is selected from one of the structures shown in formulas b to d, Y is selected from halogen, and o, p, and q are selected from 1.

[0024] The present application also provides a method for preparing the dual-component supported catalyst, comprising:

[0025] The Lewis acid complex is reacted with some functional groups modified on the surface of the carrier compound, and the obtained Lewis acid supported compound is reacted with the Lewis base complex to obtain a two-component catalyst;

[0026] The carrier compound is selected from an inorganic carrier, a polymer carrier or a composite carrier of an inorganic carrier and a polymer carrier.

[0027] Preferably, the temperature of the reaction with the carrier compound is 50-100° C., and the time is 5-48 hours, and the temperature of the reaction with the Lewis base complex is 50-100° C., and the time is 5-48 hours.

[0028] The present application also provides a method for preparing a cyclic carbonate, comprising the following steps:

[0029] Carbon dioxide and epoxy compounds are reacted under the action of a two-component supported catalyst to obtain a cyclic carbonate, wherein the two-component supported catalyst is the two-component supported catalyst or the two-component supported catalyst prepared by the preparation method.

[0030] Preferably, the two-component supported catalyst is 10 -5 ~10 -1 mol%, the reaction pressure is 1-10 MPa, the reaction temperature is 25-200°C, and the reaction time is 0.5-24h.

[0031] Preferably, the epoxy compound is selected from one or more of ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-hexylene oxide, 1,2-octane oxide, styrene oxide, cyclohexene oxide, cyclopentane oxide, epichlorohydrin methacrylate glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether and styrene epoxy alkane.

[0032] The present application provides a two-component supported catalyst as shown in formula (I), which is composed of a carrier and active components, Lewis acid and Lewis base; the two-component supported catalyst provided by the present application has two active components, which can jointly promote the coupling reaction of carbon dioxide and epoxy compounds, so that it has ultra-high reaction activity as a catalyst, and can achieve high selectivity (>99%) and ultra-high activity (TOF=3*10 5 h -1 ) is used to prepare cyclic carbonates. After the reaction is completed, the catalyst is easy to separate and can be recycled for multiple times. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The reaction scheme for preparing the complex EL2 prepared in Example 1 of the present invention;

[0034] Figure 2 The H NMR spectra of the complexes EL1 and EL2 prepared in Example 1 of the present invention;

[0035] Figure 3 The preparation reaction route of the two-component supported catalyst prepared in Example 1 of the present invention;

[0036] Figure 4 The scanning electron microscope image and thermogravimetric analysis comparison image of the two-component supported catalyst prepared in Example 1 of the present invention and the carrier (Merrifield resin) used;

[0037] Figure 5 This is the reaction scheme for preparing cyclic carbonates in Examples 2 to 22. DETAILED DESCRIPTION

[0038] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0039] In view of the problem of low reaction activity of catalysts for preparing cyclic carbonates in the prior art, the present application provides a two-component supported catalyst, which is a heterogeneous catalyst with adjustable ratio and supported by two components of Lewis acid and Lewis base. The catalyst is easy to synthesize and can achieve high activity preparation of cyclic carbonates under a wide range of reaction conditions such as temperature, pressure, and time. Experimental results show that under extremely low catalyst concentration (9*10 -5 mol%), the highest activity has reached TOF = 300000h -1 , which is the highest activity reported so far, and is a major breakthrough in this field. At the same time, after the reaction is completed, the two-component supported catalyst is easy to separate and can be effectively recycled many times to obtain colorless cyclic carbonate, which meets the needs of green and sustainable development.

[0040] Specifically, the present application first provides a two-component supported catalyst as shown in formula (I),

[0041]

[0042] Wherein, Carrier is an inorganic carrier, a polymer carrier or a composite carrier of an inorganic carrier and a polymer carrier;

[0043] The LA is a Lewis acid, and the LB is a Lewis base;

[0044] The x and y are load rates, 0<x<50%, y=1-x.

[0045] In the dual-component supported catalyst described in the present application, the inorganic carrier in the Carrier is selected from SiO 2 、Al 2 O 3 , MgO, ZnO, TiO 2 , functionalized SiO 2 , functionalized Al 2 O 3 , functionalized MgO, functionalized ZnO and functionalized TiO 2 One or more of the functionalization methods are bromination, chloromethyl functionalization, amino functionalization, hydroxyl functionalization or thiol functionalization. The polymer carrier is selected from one or more of cross-linked polystyrene, polyamide, polyethylene-glycol resin, functionalized cross-linked polystyrene, functionalized polyamide and functionalized polyethylene-glycol resin, and the functionalization methods are bromination, chloromethyl functionalization, amino functionalization, hydroxyl functionalization or thiol functionalization.

[0046] The LA is a metal porphyrin compound having a structure shown in formula a;

[0047]

[0048] Among them, R 1 ~R 19 Each is independently selected from hydrogen, halogen, amino, nitro, cyano, C1-C10 aliphatic group, C1-C10 substituted alkoxy group, C3-C10 substituted cycloalkyl group, C1-C10 heterocyclic group, C6-C12 substituted aryl or substituted C1-C12 heteroaryl;

[0049] The L 1 a functional group selected from amino, nitro, cyano or hydroxyl;

[0050] M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium;

[0051] X is selected from halogen, -NO 3 , CH 3 COO-、CCl 3 COO-, CF 3 COO-、ClO 4- , BF 4- BPh 4- 、-CN、-N 3, p-toluenesulfonate, p-toluenesulfonate, o-nitrophenolate anion, p-nitrophenolate anion, m-nitrophenolate anion, 2,4-dinitrophenolate anion, 3,5-dinitrophenolate anion, 2,4,6-trinitrophenolate anion, 3,5-dichlorophenolate anion, 3,5-difluorophenolate anion, 3,5-di-trifluoromethylphenolate anion or pentafluorophenolate anion.

[0052] The LB is one of the Lewis bases having structures of formula b to formula d;

[0053]

[0054] Among them, o, p, q are the number of methylene groups, ranging from 1 to 7;

[0055] Y is selected from halogen, NO 3 - , CH 3 COO - , CCl 3 COO - CF 3 COO - , ClO 4- , BF 4- BPh 4- , CN - 、-N 3 , p-toluenesulfonate, p-toluenesulfonate, o-nitrophenolate anion, p-nitrophenolate anion, m-nitrophenolate anion, 2,4-dinitrophenolate anion, 3,5-dinitrophenolate anion, 2,4,6-trinitrophenolate anion, 3,5-dichlorophenolate anion, 3,5-difluorophenolate anion, 3,5-di-trifluoromethylphenolate anion or pentafluorophenolate anion.

[0056] The x and y are load rates, x is 0.1 to 48%, and in a specific embodiment, x is 0.5 to 45%.

[0057] In the bicomponent supported catalyst provided in the present application, in a specific embodiment, the LA is selected from the metal porphyrin shown in formula a, and R 1 ~R 19 is selected from hydrogen, said L 1 is selected from amino, M is selected from Al, and X is selected from Cl;

[0058] The LB is selected from the structure shown in formula bd, Y is selected from halogen, and o, p, and q are selected from 1.

[0059] In a specific embodiment, the two-component supported catalyst has the structure of formula (II) to (IV):

[0060]

[0061] In the two-component supported catalyst provided in the present application, the support surface has multiple functional groups, which can act as active sites to undergo nucleophilic substitution reactions with Lewis acids and Lewis bases, thereby achieving the loading of multiple Lewis acids and Lewis bases on the support surface.

[0062] The present application also provides a method for preparing a two-component supported catalyst, comprising:

[0063] The Lewis acid complex is reacted with a carrier compound, and then reacted with a Lewis base complex to obtain a two-component supported catalyst;

[0064] The carrier compound is selected from an inorganic carrier, a polymer carrier or a composite carrier of an inorganic carrier and a polymer carrier.

[0065] Taking the above-mentioned two-component catalyst having the structure of formula (II) to (IV) as an example, the specific preparation method thereof is: firstly reacting the monoaminoaluminum porphyrin ligand with a chloromethyl-functionalized styrene resin as a polymer carrier, and then adding an excess of a tertiary amine and quaternizing it to obtain a two-component supported catalyst having the structure of formula (II) to (IV) respectively.

[0066] In the process of preparing the two-component supported catalyst, a specific carrier, Lewis acid and Lewis base can be selected, and the loading ratio of Lewis acid and Lewis base can be adjusted, thereby obtaining different two-component supported catalysts.

[0067] The present invention also provides a method for preparing a cyclic carbonate, comprising the following steps:

[0068] Carbon dioxide and an epoxide are reacted under the action of a two-component supported catalyst to obtain a cyclic carbonate, wherein the two-component supported catalyst is the two-component supported catalyst described in the above scheme.

[0069] In the preparation process of cyclic carbonate, the two-component supported catalyst is 10% of the epoxide -6 ~10 -1 mol%, specifically, the content of the two-component supported catalyst is 5*10 -6 ~10 -2 mol%, more specifically, the content of the two-component supported catalyst is 9*10 -5 ~5*10 -2mol%; the reaction pressure is 1-10MPa, specifically, the pressure is 2-8MPa; the reaction temperature is 25-200°C, specifically, the reaction temperature is 50-180°C; the reaction time is 0.5-24h, specifically, the reaction time is 0.5-15h.

[0070] In the present application, the epoxy compound is selected from one or more of ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-hexylene oxide, 1,2-octane oxide, styrene oxide, cyclohexene oxide, cyclopentane oxide, epichlorohydrin methacrylate glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide.

[0071] In the present invention, the two-component supported catalyst can carry out the coupling reaction of carbon dioxide and epoxy compounds under a wide range of reaction conditions such as temperature, pressure, time, etc., at extremely low catalyst concentration and in the absence of solvent, and prepare colorless cyclic carbonates with high selectivity and ultra-high activity, and has broad application prospects. At the same time, after the reaction is completed, it is easy to separate and can be effectively recycled for multiple times, which meets the needs of green and sustainable development.

[0072] In order to further understand the present invention, the dual-component supported catalyst, its preparation method and application provided by the present invention are described in detail below in conjunction with the examples. The protection scope of the present invention is not limited by the following examples.

[0073] Example 1

[0074] 1) 50 g (470 mmol) of benzaldehyde and 31 g (470 mmol) of pyrrole were added to 500 mL of propionic acid, refluxed at 130° C. for 1.5 h, cooled to room temperature, added with 500 mL of methanol, and then filtered and purified by silica gel column chromatography to obtain an intermediate compound with a yield of about 20%;

[0075] 2) Under nitrogen protection, 1 g (1.63 mmol) of the intermediate compound was dissolved in 10 mL (1.63 mmol) of trifluoroacetic acid, 0.2 g (2.93 mmol) of sodium nitrite was added, and the reaction was carried out at room temperature for 3 min. Then, 50-100 mL of ice deionized water was added to quench the reaction, and the acidic system was neutralized to neutrality with a saturated sodium bicarbonate solution. The organic phase was collected, dried after rotary evaporation, and dissolved in 20 mL of concentrated hydrochloric acid. At the same time, a concentrated hydrochloric acid solution containing 1.44 g (7.58 mmol) of stannous chloride was added, and the reaction was carried out at 65° C. for 8 h. After the reaction was completed, concentrated ammonia was slowly added to quench the reaction system to neutrality, and the mixture was filtered, and the filter cake was dried and purified by silica gel column chromatography to obtain the product aminoporphyrin ligand EL1 with a yield of 40%;

[0076] 3) Under nitrogen protection, 0.4 g EL1 (0.64 mmol) of the above ligand was dissolved in dichloromethane, and 0.4 mL AlEt 2 Cl (diethylaluminum chloride) (2 mol / L, 0.77 mmol), stirred at room temperature for 2 h; the obtained product was purified by column chromatography and dried to obtain the desired complex EL2; the schematic diagram of the above reaction route is shown in Figure 1 ; The corresponding H NMR spectra of complexes EL1 and EL2 are as follows Figure 2 As shown;

[0077] 4) Under nitrogen protection, 2.0 g of cross-linked polystyrene resin (Merrifield resin) (DVB: 1%, Cl: 2-3 mmol / g) was fully swollen in 20 mL of anhydrous DMF at 70°C for 24 h; 1 g (1.4 mmol) of EL2, K 2 CO 3 120mg (0.84mmol) KI 23mg (0.14mmol) was added to the fully swollen resin, and 10mL anhydrous DMF was added. The temperature was raised to 90℃ and reacted for 24h before filtering. The filter cake was repeatedly washed with anhydrous DMF, anhydrous chloroform, and anhydrous dichloromethane and centrifuged until the supernatant was colorless. After the solid was dried, it was swollen again in 20mL anhydrous DMF, and excess triethylamine (505mg5mmol) was added thereto. After reacting at 90℃ for 24h, the above filtration and centrifugation operations were repeated. The solid product obtained was the two-component supported catalyst; the corresponding x and y values ​​were obtained by ICP analysis. The synthetic route of the corresponding two-component supported catalyst is as follows: Figure 3 As shown in the figure, it can be seen that EL2 is a Lewis acid complex, and its amino group as a functional group can undergo nucleophilic substitution reaction with the benzyl chloride group on the Merrifield resin support, firstly obtaining a catalyst loaded with only Lewis acid, and then adding excess triethylamine (Lewis base) to react with the remaining benzyl chloride groups on the Merrifield resin support, thereby obtaining a two-component supported catalyst. Figure 4 The scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) shown were used to characterize the dual-component supported catalyst.

[0078] The structure of the two-component supported catalyst prepared in this embodiment is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=45%, y=55%;

[0079] This embodiment uses the above compound as an example to prepare a two-component supported catalyst. The two-component catalysts in other embodiments of the present invention all adopt the preparation method of this embodiment, and the preparation is achieved by controlling the amount of raw materials and the reaction time.

[0080] Example 2

[0081] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=45%, y=55%.

[0082] In the glove box, 1.7*10 -2 mol% (33 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and after reacting for 4 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 650h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0083] Example 3

[0084] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=15%, y=85%.

[0085] In the glove box, 5*10 -3 mol% (20 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and after the reaction for 1 hour, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 7380h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0086] Example 4

[0087] The two-component supported catalyst is shown in Formula II, wherein the carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=4%, and y=96%.

[0088] In the glove box, 1.3*10 -3mol% (22 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and the reaction was placed in cold water to cool to room temperature after 0.5 h, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 83000h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0089] Example 5

[0090] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=1.2%, y=98.8%.

[0091] In the glove box, 4*10 -4 mol% (35 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and after reacting for 2 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 84700h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0092] Example 6

[0093] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=0.5%, y=99.5%.

[0094] In the glove box, 2*10 -4 mol% (17 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and the reaction was placed in cold water to cool to room temperature after 4 hours, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 69400h -1The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0095] Example 7

[0096] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=0.3%, y=99.7%.

[0097] In the glove box, 2*10 -4 mol% (23 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and after reacting for 4 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 95300h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0098] Example 8

[0099] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=0.2%, y=99.8%.

[0100] In the glove box, 6.7*10 -5 mol% (11 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and after reacting for 6 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 23500h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0101] Example 9

[0102] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=0.3%, y=99.7%.

[0103] In the glove box, 4*10 -4 mol% (46 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and the reaction was placed in cold water to cool to room temperature after 0.5 h, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 300000h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0104] Example 10

[0105] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=0.3%, y=99.7%.

[0106] In the glove box, 9*10 -5 mol% (11 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and the reaction was placed in cold water to cool to room temperature after 0.5 h, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 200000h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0107] Embodiment 11

[0108] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=1.2%, y=98.8%.

[0109] In the glove box, 4*10 -4mol% (35 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 70 ° C, and the reaction was placed in cold water to cool to room temperature after 24 hours, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 5260h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0110] Example 12

[0111] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=1.2%, y=98.8%.

[0112] In the glove box, 4*10 -4 mol% (35 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 110 ° C, and after reacting for 10 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 17400h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0113] Embodiment 13

[0114] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=1.2%, y=98.8%.

[0115] In the glove box, 4*10 -4 mol% (35 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 160 ° C, and after reacting for 2 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 90000h -1The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0116] Embodiment 14

[0117] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=1.2%, y=98.8%.

[0118] In the glove box, 4*10 -4 mol% (28 mg) of catalyst and 47 mmol (4 mL) of dry butylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 160 ° C, and the reaction was placed in cold water to cool to room temperature after 4 hours. The carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 43400h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0119] Embodiment 15

[0120] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=1.2%, y=98.8%.

[0121] In the glove box, 4*10 -4 mol% (31 mg) of catalyst and 51 mmol (4 mL) of dry epichlorohydrin, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 160°C, and after reacting for 2 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 73500h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0122] Example 16

[0123] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=1.2%, y=98.8%.

[0124] In the glove box, 4*10 -4 mol% (20 mg) of catalyst and 35 mmol (4 mL) of dry 1,2-epoxyhexane, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 160 ° C, and after reacting for 0.5 h, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 42400h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0125] Embodiment 17

[0126] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=1.2%, y=98.8%.

[0127] In the glove box, 4*10 -4 mol% (16 mg) of catalyst and 26 mmol (4 mL) of dry 1,2-epoxyoctane, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 160 ° C, and after reacting for 2 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 14900h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0128] Embodiment 18

[0129] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=1.2%, y=98.8%.

[0130] In the glove box, 4*10 -4mol% (18 mg) of catalyst and 35 mmol (4 mL) of dry styrene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 160°C, and after reacting for 4 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 11200h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0131] Embodiment 19

[0132] The two-component supported catalyst is shown in Formula II, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=1.2%, y=98.8%.

[0133] In the glove box, 4*10 -4 mol% (21 mg) of catalyst and 30 mmol (4 mL) of dry phenyl glycidyl ether, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 160 ° C, and the reaction was placed in cold water to cool to room temperature after 4 hours, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 24100h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0134] Embodiment 20

[0135] The two-component supported catalyst is shown in Formula II, wherein the carrier is selected from Al with a surface methyl functionalization 2 O 3 Inorganic support, x=0.3%, y=99.7%.

[0136] In the glove box, 4*10 -4mol% (46 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and after reacting for 6 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 220000h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0137] Embodiment 21

[0138] The two-component supported catalyst is shown in Formula III, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=0.3%, y=99.7%.

[0139] In the glove box, 4*10 -4 mol% (45 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and after reacting for 6 hours, it was placed in cold water to cool to room temperature, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 285600h -1 The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0140] Embodiment 22

[0141] The two-component supported catalyst is shown in Formula IV, wherein Carrier is selected from a chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x=0.3%, y=99.7%.

[0142] In the glove box, 4*10 -4 mol% (42 mg) of catalyst and 57 mmol (4 mL) of dry propylene oxide, the autoclave was sealed and taken out from the glove box, carbon dioxide was introduced to make the initial pressure in the autoclave 4 MPa, the reaction temperature was 140 ° C, and the reaction was placed in cold water to cool to room temperature after 6 hours, and the carbon dioxide in the autoclave was slowly released. When the pressure reading dropped to 0, an appropriate amount of the stock solution was taken for nuclear magnetic hydrogen spectrum characterization. The selectivity of the obtained cyclic carbonate was 99%. The catalyst activity TOF in this embodiment was 264000h -1The reaction scheme for the preparation of cyclic carbonates is as follows: Figure 5 shown.

[0143] As can be seen from the above embodiments, the present invention provides an ultra-high activity two-component supported catalyst having a structure of formula (I), and the heterogeneous catalyst is applied to the preparation of cyclic carbonates. The two-component supported catalyst described in the present invention is mainly composed of a carrier and an active component (including Lewis acid and Lewis base), and the Lewis acid-base ratio in the catalyst can be controlled by the amount of raw materials and the reaction time. Under the action of the two-component supported catalyst or the two-component supported catalyst prepared by the above preparation method, the coupling reaction of carbon dioxide and epoxy compounds is carried out, and it can be carried out under a wide range of reaction conditions such as temperature, pressure, time, extremely low catalyst concentration and solvent-free conditions with high selectivity (>99%) and ultra-high activity (TOF=3*10 5 h -1 ) to prepare colorless cyclic carbonate, which has broad application prospects. After the reaction of the two-component supported catalyst of the present invention is completed, it is easy to separate and can be effectively recycled for many times, which meets the requirements of green and sustainable development.

[0144] The above embodiments are only used to help understand the method and core idea of ​​the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

[0145] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a cyclic carbonate, comprising the following steps: Carbon dioxide and an epoxide are reacted under the action of a two-component supported catalyst to obtain a cyclic carbonate, wherein the two-component supported catalyst has a structure of formula (II): （Ⅱ）； Carrier is selected from chloromethyl functionalized cross-linked polystyrene resin polymer carrier, x = 0.3%, y = 99.7%; Or, Carrier is selected from Al2O3 inorganic carrier functionalized with chloromethyl on the surface, x = 0.3%, y = 99.7%; The two-component supported catalyst is 9*10 of the epoxy compound -5 ~4*10 -4 mol%, the reaction pressure is 4 MPa, the reaction temperature is 140°C, and the reaction time is 0.5-6 h.

2. The preparation method according to claim 1, characterized in that: The epoxy compound is selected from one or more of ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-hexylene oxide, 1,2-octane oxide, styrene oxide, cyclohexene oxide, cyclopentane oxide, epichlorohydrin methacrylate glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide.

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