Pyridine amino bifunctional polyion liquid catalyst as well as preparation method and application thereof

Abstract

The invention discloses a pyridylamino bifunctional polyion liquid catalyst as well as a preparation method and application thereof. The preparation method comprises the following steps: taking brominated 1-(3-propylamine hydrobromide)-3-vinyl imidazole ionic liquid [PAVIm] Br. HBr and brominated 1-pyridyl-2-vinyl imidazole ionic liquid [PDVIM] Br as comonomers, adding a cross-linking agent and an initiator, and copolymerizing to synthesize a polyionic liquid catalyst I; the pyridylamino bifunctional polyion liquid catalyst provided by the invention has a developed porous structure and abundant ionic groups (carbonate ions and bicarbonate ions), shows relatively high CO2 adsorption performance, can catalyze one-pot synthesis of chain carbonate from CO2, an epoxy compound and methanol under the condition of no solvent and cocatalyst, and has the advantages of simple preparation process and low cost. And efficient utilization of CO2 is realized.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst preparation, and specifically relates to a pyridineamine bifunctional polyionic liquid catalyst and a preparation method and application thereof. Background Art

[0002] Excessive consumption of fossil energy causes CO in the atmosphere 2 , CH 4 The increasing content of greenhouse gases such as carbon dioxide and carbon monoxide has led to global warming, extreme weather changes, rising sea levels, and the deterioration of the human environment. my country's "dual carbon" strategy advocates a green, environmentally friendly, and low-carbon lifestyle to accelerate the pace of reducing carbon emissions. 2 As a non-toxic, cheap, and renewable carbon resource, it can convert waste products into valuable chemicals with low energy consumption, which has important research strategic value and application prospects and is the best choice for the sustainable development of human society. 2 There are more than 20 kinds of high value-added chemicals through multiple means, mainly by disconnecting CO 2 The carbon-oxygen double bonds in the carbon-oxygen double bonds are used to generate new chemical bonds (CC, CN, CO and CH) to form new compounds. 2 It can be converted into methanol, formic acid, urea, methane and dimethyl ether as the main raw material. It can also be used to synthesize various carbonates, carboxylic acids, carbamates and other important compounds with high added value.

[0003] Dimethyl carbonate is simply called DMC, with a molecular formula (CH 3 O) 2 CO, with a slight ester aroma, is a non-toxic, biodegradable and environmentally friendly organic compound. 3 ), methoxy (-OCH 3 ), and carboxyl (C=O) functional groups, and can undergo a variety of complex synthetic chemical reactions. DMC has a wide range of uses. It can be used as an intermediate for the synthesis of engineering plastics, pesticides and medicines, and can also be used as a green solvent, additive, and lithium-ion battery solvent. It can also be added to gasoline to increase the octane number of gasoline, enhance shock resistance, and significantly reduce PM2.5 and NO x emissions, thus achieving the effect of protecting the environment.

[0004] At present, the synthesis of dimethyl carbonate mainly has the following methods:

[0005] First, CO 2 Direct synthesis

[0006]

[0007] The disadvantages of this method are: 1. The DMC synthesis reaction is limited by thermodynamics and CO 2 Activation is limited by kinetic inertness; 2. Water, a side reaction product in the DMC synthesis reaction, causes reverse hydrolysis of the chain carbonate.

[0008] Second, traditional indirect synthesis method

[0009]

[0010] The shortcomings of this method are: 1. Based on the traditional indirect synthesis method including cycloaddition reaction and ester exchange reaction, different active sites are required for different reactions, so different catalysts are needed; 2. Based on the traditional indirect synthesis method including cycloaddition reaction and ester exchange reaction, different reaction conditions are required for different reactions, so different devices are needed.

[0011] Third, CO 2 One-step coupling reaction method

[0012] Methanol, epoxide and CH 3 OH are put into the same reaction device together to complete the coupling reaction together, which is called CO 2 One-step coupling reaction method. This method can be carried out simultaneously using the same catalyst, but the heterogeneous catalysts currently used cannot meet the multifunctional active sites required for one-pot coupling preparation of DMC.

[0013] Polyionic liquids (PILs) are heterogeneous materials composed of monomeric ILs or copolymers of ILs and crosslinkers, with repeated arrangement of anionic and cationic units, which have the functional properties of both ionic liquids and polymeric materials. 2 Due to the thermodynamic stability and kinetic inertness of PILs, the design of basic sites of PILs is of great significance. Through the functionalization design of ILs monomers, the diversification of copolymerization units and the surface modification of PILs skeleton, functionalized PILs catalysts can effectively overcome the limitations of traditional catalysts such as halogenated metal salts, organic amine liquid bases and metal oxides in CO 2 The problems of active components being easily soluble, difficulty in constructing functional sites, and large amounts of co-catalysts in the directional synthesis of chain carbonates are as follows. Among them, alkaline functionalized PILs catalysts can be further constructed in CO 2 Targeted activation of CO in coupling reactions 2 and dissociation of CH 3 OH, it is of great research value.

[0014] However, in the preparation and application of alkaline functionalized PILs catalysts, the screening of functional groups and the determination of modification methods still need further study. Summary of the invention

[0015] Purpose of the invention: The purpose of the present invention is to provide a pyridylamine bifunctional polyionic liquid catalyst and its preparation method and application in view of the deficiencies of the prior art. The pyridylamine bifunctional polyionic liquid catalyst provided by the present invention is used to catalyze CO 2 When DMC is prepared by one-pot coupling of epoxide and methanol, the problem that the existing heterogeneous catalysts cannot meet the multifunctional active sites required for one-pot coupling preparation of DMC can be overcome. The present invention obtains a high-yield product by copolymerizing primary amine ionic liquids (ILs), pyridyl ILs and DVB free radicals, and then introducing carbonate anions or acetate anions through continuous ion exchange to adjust the active sites of the polyionic liquid.

[0016] Technical solution: The purpose of the present invention is achieved through the following technical solution:

[0017] The invention provides a pyridylamine bifunctional polyionic liquid catalyst. The polyionic liquid catalyst I is prepared by copolymerizing 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid [PAVIm]Br·HBr and 1-pyridyl-2-vinylimidazolium bromide ionic liquid [PDVIM]Br as copolymer monomers, adding a crosslinking agent and an initiator.

[0018] The present invention also provides a method for preparing the above-mentioned pyridine amine bifunctional polyionic liquid catalyst, comprising the following steps:

[0019] (1) Preparation of 1-(3-propylamine hydrobromide)-3-vinylimidazolium ionic liquid [PAVIm]Br·HBr: N-vinylimidazole and 3-bromopropylamine hydrobromide were dissolved in acetonitrile and heated to 40 ℃ for 2 h. 2 The reaction was carried out under the conditions of 1:100 μm, the solvent was evaporated, the mixture was washed, and the mixture was dried to obtain [PAVIm]Br·HBr ionic liquid;

[0020] (2) Preparation of 1-pyridyl-2-vinylimidazole bromide [PDVIm]Br ionic liquid: N-vinylimidazole and 2-bromopyridine were dissolved in ethanol and heated to 40 °C. 2 The reaction was carried out under the conditions of 1:100 μm, the solvent was evaporated, the mixture was washed, and the mixture was dried to obtain [PDVIm]Br ionic liquid;

[0021] (3) Preparation of pyridineamine-based polyionic liquid PD-ILsBr·HBr catalyst: [PAVIm]Br·HBr ionic liquid, [PDVIm]Br ionic liquid, crosslinker divinylbenzene DVB and initiator azobisisobutyronitrile AIBN were added into a water / ethanol mixed solvent. 2 The mixture was reacted under reduced pressure, filtered, washed and dried to obtain the PD-ILsBr·HBr catalyst, i.e., the polyionic liquid catalyst I.

[0022] Preferably, in step (1), the molar ratio of N-vinylimidazole to 3-bromopropylamine hydrobromide is 1:1-2.5; the molar concentration of N-vinylimidazole in acetonitrile is 1-2 mmol / ml; the reaction temperature is 70-90°C, and the reaction time is 18-24h; the washing is performed by ethyl acetate washing; the drying is performed by vacuum drying, the drying temperature is 55-75°C, and the drying time is 18-24h.

[0023] Preferably, in step (2), the molar ratio of N-vinylimidazole to 2-bromopyridine is 1:1-2, the molar concentration of N-vinylimidazole in ethanol is 1-2 mmol / ml; the reaction temperature is 70-90°C, and the reaction time is 18-24h; the washing is performed by ethyl acetate washing; the drying is performed by vacuum drying, the drying temperature is 55-75°C, and the drying time is 18-24h.

[0024] Preferably, in step (3), the molar ratio of the [PAVIm]Br·HBr ionic liquid, [PDVIm]Br and the crosslinking agent DVB is 1:0.5-2:0.5-2; the amount of the initiator AIBN is 2.3-5.6wt% of the sum of the masses of [PAVIm]Br·HBr, [PDVIm]Br and the crosslinking agent DVB; the molar concentration of the [PAVIm]Br·HBr ionic liquid in the mixed solvent is 0.1-0.2mmol / ml; the volume ratio of water to ethanol is 1:4-9; the reaction temperature is 75-95°C, and the reaction time is 18-24h; the washing is ethanol washing; the drying is vacuum drying, the drying temperature is 55-75°C, and the drying time is 18-24h.

[0025] The present invention also provides a pyridineamine bifunctional polyionic liquid catalyst, wherein the polyionic liquid catalyst I is subjected to anion exchange reaction with a sodium carbonate aqueous solution to obtain a polyionic liquid catalyst II; and the polyionic liquid catalyst I is subjected to anion exchange reaction with a sodium acetate aqueous solution to obtain a polyionic liquid catalyst III.

[0026] The present invention also provides a preparation method of polyionic liquid catalyst II and polyionic liquid catalyst III. The concentration of the sodium carbonate aqueous solution or the sodium acetate aqueous solution is 0.7-1.7 mol / L. The anion exchange reaction is carried out under stirring at room temperature. After the reaction is completed, the reaction is filtered, washed with hot water, and vacuum dried to obtain the polyionic liquid catalyst. The stirring time is 48-72 hours. The drying temperature is 55-75° C., and the drying time is 18-24 hours.

[0027] A specific preferred embodiment of the present invention is that the preparation method of the pyridine amine bifunctional polyionic liquid catalyst comprises the following steps:

[0028] (1) Disperse N-vinylimidazole in acetonitrile, add 3-bromopropylamine hydrobromide and mix well. 2 Under protection, react at 70-90°C for 18-24h, remove the solvent by rotary evaporation, wash with ethyl acetate, and dry under vacuum at 55-75°C for 18-24h to obtain 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid ([PAVIm]Br·HBr);

[0029] (2) Disperse N-vinylimidazole in ethanol, add 2-bromopyridine and mix well. 2 Under protection, react at 70-90°C for 18-24h, remove the solvent by rotary evaporation, wash with ethyl acetate, and dry under vacuum at 55-75°C for 18-24h to obtain 1-pyridyl-2-vinyl imidazolium bromide ionic liquid ([PDVIm]Br);

[0030] (3) The ionic liquid, DVB and AIBN obtained above were added into a water / ethanol mixed solvent, stirred at room temperature for 2 h, and then heated in N 2 Under protection, react at 75-95°C for 18-24h, filter, wash with ethanol, and dry in vacuum at 55-75°C for 18-24h to obtain catalyst PD-ILsBr·HBr;

[0031] (4) The catalyst PD-ILsBr·HBr obtained above is dispersed in a sodium carbonate aqueous solution or a sodium acetate aqueous solution, stirred at room temperature for 48 to 72 hours to perform anion exchange, the solid is filtered, washed with hot water, and vacuum dried at 55 to 75° C. for 18 to 24 hours to obtain PD-ILsCO 3 and PD-ILsAC catalyst.

[0032] The present invention also provides the above-mentioned pyridine amine bifunctional polyionic liquid catalyst in catalyzing CO 2 , and its application in the one-pot coupling preparation of DMC by epoxide and methanol.

[0033] A preferred embodiment of the present invention is to add the above-mentioned polyionic liquid catalyst, raw material epoxide and methanol into a reaction kettle, and use CO 2 After replacing the air in the kettle, the kettle is pressed and heated to the reaction temperature to start the reaction. After the reaction is completed, the catalyst and the reaction product are separated by centrifugation.

[0034] Further preferably, the raw material epoxide is any one of epichlorohydrin, styrene oxide or glycidol; the mass ratio of the raw material epoxide to the polyionic liquid catalyst is 1:0.036-0.09; the CO 2 The pressure is 5 to 12.5 bar; the molar ratio of methanol to epoxide is 10 to 25:1; the reaction temperature is 100 to 160° C., and the reaction time is 1 to 4 hours.

[0035] Beneficial effects:

[0036] (1) The pyridineamine bifunctional polyionic liquid ionic material prepared by the present invention has abundant basic sites and a developed pore structure, and can be used as a CO 2 It is a good catalyst for the one-pot coupling of epoxides and methanol to prepare linear carbonates, and it has a good synergistic effect on the coupling reaction.

[0037] (2) The present invention uses primary amine ILs, pyridyl ILs and DVB free radical copolymerization and continuous anion exchange to prepare a pyridylamino bifunctional polyionic liquid catalyst. By taking advantage of the material synthesis characteristics of PILs, an alkaline bifunctional PILs catalyst can be constructed.

[0038] (3) CO used in the present invention 2 , epoxy substrate and CH 3 OH is coupled to CO in the same reactor 2 Cycloaddition and CH 3 A new method for generating DMC by OH transesterification reaction can retain CO 2 The indirect synthesis method has a high yield and can omit the separation operation of the intermediate cyclic carbonate, thereby reducing energy consumption, investment and production costs. The material prepared by the present invention has an adjustable structure, stable properties and good adsorption catalytic repeat stability, while promoting the green transformation of low-value C1 resources to high-value-added chemicals, which meets the national "dual carbon" strategic needs and has good application prospects. DETAILED DESCRIPTION

[0039] The technical solution of the present invention is described in detail below through specific embodiments, but the protection scope of the present invention is not limited to the embodiments.

[0040] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased through regular channels.

[0041] The experimental methods in the following examples are conventional methods unless otherwise specified. The experimental materials used in the following examples are commercially available products unless otherwise specified.

[0042] Example 1

[0043] Step 1: Disperse 10 mmol N-vinylimidazole in 10 ml acetonitrile, add 10 mmol 3-bromopropylamine hydrobromide and mix well. 2Under protection, the reaction was carried out at 70°C for 18 hours, the solvent was removed by rotary evaporation, washed with ethyl acetate, and dried in vacuo at 55°C for 18 hours to obtain 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid ([PAVIm]Br·HBr).

[0044] Step 2: Disperse 10 mmol N-vinylimidazole in 10 ml ethanol, add 10 mmol 2-bromopyridine and mix well. 2 Under protection, the reaction was carried out at 70° C. for 18 h, the solvent was removed by rotary evaporation, the mixture was washed with ethyl acetate, and the mixture was dried under vacuum at 55° C. for 18 h to obtain 1-pyridyl-2-vinylimidazolium bromide ionic liquid ([PDVIm]Br).

[0045] Step 3: 10 mmol [PAVIm]Br·HBr ionic liquid, 5 mmol [PDVIm]Br ionic liquid and 5 mmol DVB were added to a mixed solvent consisting of 10 ml water and 90 ml ethanol, followed by 116 mg AIBN. The mixture was stirred at room temperature for 2 h and heated to 40 °C under N 2 Under protection, the reaction was carried out at 75°C for 18 h, filtered, washed with ethanol (3×20 mL), and dried in vacuo at 55°C for 18 h to obtain the catalyst PD-ILsBr·HBr.

[0046] Step 4: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 0.7 mol / L sodium carbonate aqueous solution and stirred at room temperature for 48 h, filtered, washed with hot water (3×20 mL), and dried under vacuum at 55°C for 18 h to obtain PD-ILsCO 3 catalyst.

[0047] Step 5: The PD-ILsBr·HBr catalyst prepared above was dispersed in 0.7 mol / L sodium acetate aqueous solution and stirred at room temperature for 48 h, filtered, washed with hot water (3×20 mL), and vacuum dried at 55° C. for 18 h to obtain the PD-ILsAC catalyst.

[0048] Example 2

[0049] Step 1: Disperse 10 mmol N-vinylimidazole in 5 ml acetonitrile, add 25 mmol 3-bromopropylamine hydrobromide and mix well. 2 Under protection, the reaction was carried out at 90°C for 24 hours, the solvent was removed by rotary evaporation, the mixture was washed with ethyl acetate, and the mixture was dried under vacuum at 75°C for 24 hours to obtain 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid ([PAVIm]Br·HBr).

[0050] Step 2: Disperse 10 mmol N-vinylimidazole in 5 ml ethanol, add 20 mmol 2-bromopyridine and mix well. 2Under protection, the reaction was carried out at 90° C. for 24 h, the solvent was removed by rotary evaporation, washed with ethyl acetate, and dried in vacuo at 75° C. for 24 h to obtain 1-pyridyl-2-vinylimidazolium bromide ionic liquid ([PDVIm]Br).

[0051] Step 3: 10 mmol [PAVIm]Br·HBr ionic liquid, 20 mmol [PDVIm]Br ionic liquid and 20 mmol DVB were added to a mixed solvent consisting of 10 ml water and 40 ml ethanol, followed by 560 mg AIBN. The mixture was stirred at room temperature for 2 h and heated to 40 °C under N 2 Under protection, the reaction was carried out at 95°C for 24 h, filtered, washed with ethanol (3×20 mL), and dried in vacuo at 75°C for 24 h to obtain the catalyst PD-ILsBr·HBr.

[0052] Step 4: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 1.7 mol / L sodium carbonate aqueous solution and stirred at room temperature for 72 h, filtered, washed with hot water (3×20 mL), and dried under vacuum at 75°C for 24 h to obtain PD-ILsCO 3 catalyst.

[0053] Step 5: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 1.7 mol / L sodium acetate aqueous solution and stirred at room temperature for 72 h, filtered, washed with hot water (3×20 mL), and vacuum dried at 75° C. for 24 h to obtain the PD-ILsAC catalyst.

[0054] Example 3

[0055] Step 1: Disperse 10 mmol N-vinylimidazole in 6 ml acetonitrile, add 15 mmol 3-bromopropylamine hydrobromide and mix well. 2 Under protection, the reaction was carried out at 80°C for 24 hours, the solvent was removed by rotary evaporation, washed with ethyl acetate, and dried in vacuo at 60°C for 22 hours to obtain 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid ([PAVIm]Br·HBr).

[0056] Step 2: Disperse 10 mmol N-vinylimidazole in 8 ml ethanol, add 15 mmol 2-bromopyridine and mix well. 2 Under protection, the reaction was carried out at 80° C. for 24 h, the solvent was removed by rotary evaporation, the mixture was washed with ethyl acetate, and the mixture was dried under vacuum at 60° C. for 22 h to obtain 1-pyridyl-2-vinylimidazolium bromide ionic liquid ([PDVIm]Br).

[0057] Step 3: 10 mmol [PAVIm] Br·HBr ionic liquid, 5 mmol [PDVIm] Br ionic liquid and 10 mmol DVB were added to a mixed solvent consisting of 10 ml water and 50 ml ethanol, followed by 170 mg AIBN. The mixture was stirred at room temperature for 2 h and heated to 40 °C under N 2 Under protection, the reaction was carried out at 85°C for 24 h, filtered, washed with ethanol (3×20 mL), and dried in vacuo at 55°C for 24 h to obtain the catalyst PD-ILsBr·HBr.

[0058] Step 4: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 0.7 mol / L sodium carbonate aqueous solution and stirred at room temperature for 48 h, filtered, washed with hot water (3×20 mL), and dried under vacuum at 55°C for 24 h to obtain PD-ILsCO 3 catalyst.

[0059] Step 5: The PD-ILsBr·HBr catalyst prepared above was dispersed in 0.7 mol / L sodium acetate aqueous solution and stirred at room temperature for 48 h, filtered, washed with hot water (3×20 mL), and vacuum dried at 55° C. for 24 h to obtain the PD-ILsAC catalyst.

[0060] Example 4

[0061] Step 1: Disperse 10 mmol N-vinylimidazole in 5 ml acetonitrile, add 10 mmol 3-bromopropylamine hydrobromide and mix well. 2 Under protection, the reaction was carried out at 75°C for 24 hours, the solvent was removed by rotary evaporation, washed with ethyl acetate, and dried in vacuo at 60°C for 24 hours to obtain 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid ([PAVIm]Br·HBr).

[0062] Step 2: Disperse 10 mmol N-vinyl imidazole in 5 ml ethanol, add 10 mmol 2-bromopyridine and mix well. 2 Under protection, the reaction was carried out at 75° C. for 24 h, the solvent was removed by rotary evaporation, the mixture was washed with ethyl acetate, and the mixture was dried under vacuum at 60° C. for 24 h to obtain 1-pyridyl-2-vinylimidazolium bromide ionic liquid ([PDVIm]Br).

[0063] Step 3: 10 mmol [PAVIm] Br·HBr ionic liquid, 5 mmol [PDVIm] Br ionic liquid and 10 mmol DVB were added to a mixed solvent consisting of 10 ml water and 60 ml ethanol, followed by 233 mg AIBN. The mixture was stirred at room temperature for 2 h and heated to 40 °C under N 2 Under protection, the reaction was carried out at 85°C for 24 h, filtered, washed with ethanol (3×20 mL), and dried in vacuo at 55°C for 24 h to obtain the catalyst PD-ILsBr·HBr.

[0064] Step 4: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 0.7 mol / L sodium carbonate aqueous solution and stirred at room temperature for 48 h, filtered, washed with hot water (3×20 mL), and dried under vacuum at 55°C for 24 h to obtain PD-ILsCO 3 catalyst.

[0065] Step 5: The PD-ILsBr·HBr catalyst prepared above was dispersed in 0.7 mol / L sodium acetate aqueous solution and stirred at room temperature for 48 h, filtered, washed with hot water (3×20 mL), and vacuum dried at 55° C. for 24 h to obtain the PD-ILsAC catalyst.

[0066] Example 5

[0067] Step 1: Disperse 10 mmol N-vinylimidazole in 5 ml acetonitrile, add 20 mmol 3-bromopropylamine hydrobromide and mix well. 2 The mixture was reacted at 90° C. for 18 h under protection, and the solvent was removed by rotary evaporation. The mixture was washed with ethyl acetate and dried under vacuum at 70° C. for 20 h to obtain 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid ([PAVIm]Br·HBr).

[0068] Step 2: Disperse 10 mmol N-vinylimidazole in 5 ml ethanol, add 16 mmol 2-bromopyridine and mix well. 2 Under protection, the reaction was carried out at 90° C. for 18 h, the solvent was removed by rotary evaporation, the mixture was washed with ethyl acetate, and the mixture was dried under vacuum at 70° C. for 20 h to obtain 1-pyridyl-2-vinylimidazolium bromide ionic liquid ([PDVIm]Br).

[0069] Step 3: 10 mmol [PAVIm] Br·HBr ionic liquid, 10 mmol [PDVIm] Br ionic liquid and 10 mmol DVB were added to a mixed solvent consisting of 10 ml water and 70 ml ethanol, followed by 260 mg AIBN. The mixture was stirred at room temperature for 2 h and heated to 40 °C under N 2 Under protection, the reaction was carried out at 85°C for 20 h, filtered, washed with ethanol (3×20 mL), and dried in vacuo at 55°C for 24 h to obtain the catalyst PD-ILsBr·HBr.

[0070] Step 4: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 1.4 mol / L sodium carbonate aqueous solution and stirred at room temperature for 48 h, filtered, washed with hot water (3×20 mL), and dried under vacuum at 60°C for 22 h to obtain PD-ILsCO 3 catalyst.

[0071] Step 5: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 1.4 mol / L sodium acetate aqueous solution and stirred at room temperature for 72 h, filtered, washed with hot water (3×20 mL), and dried in vacuo at 70° C. for 24 h to obtain the PD-ILsAC catalyst.

[0072] Example 6

[0073] Step 1: Disperse 10 mmol N-vinylimidazole in 8 ml acetonitrile, add 23 mmol 3-bromopropylamine hydrobromide and mix well. 2 Under protection, the reaction was carried out at 75°C for 18 hours, the solvent was removed by rotary evaporation, washed with ethyl acetate, and dried in vacuo at 75°C for 18 hours to obtain 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid ([PAVIm]Br·HBr).

[0074] Step 2: Disperse 10 mmol N-vinylimidazole in 7 ml ethanol, add 15 mmol 2-bromopyridine and mix well. 2 Under protection, the reaction was carried out at 80° C. for 24 h, the solvent was removed by rotary evaporation, washed with ethyl acetate, and dried in vacuo at 65° C. for 22 h to obtain 1-pyridyl-2-vinylimidazolium bromide ionic liquid ([PDVIm]Br).

[0075] Step 3: 10 mmol [PAVIm] Br·HBr ionic liquid, 17 mmol [PDVIm] Br ionic liquid and 16 mmol DVB were added to a mixed solvent consisting of 10 ml water and 70 ml ethanol, followed by 432 mg AIBN. The mixture was stirred at room temperature for 2 h and heated to 40 °C under N 2 Under protection, the reaction was carried out at 75°C for 22 h, filtered, washed with ethanol (3×20 mL), and dried in vacuo at 70°C for 24 h to obtain the catalyst PD-ILsBr·HBr.

[0076] Step 4: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 1.6 mol / L sodium carbonate aqueous solution and stirred at room temperature for 70 h, filtered, washed with hot water (3×20 mL), and dried under vacuum at 55°C for 24 h to obtain PD-ILsCO 3 catalyst.

[0077] Step 5: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 1.6 mol / L sodium acetate aqueous solution and stirred at room temperature for 70 h, filtered, washed with hot water (3×20 mL), and vacuum dried at 55° C. for 24 h to obtain the PD-ILsAC catalyst.

[0078] Example 7

[0079] Step 1: Disperse 10 mmol N-vinylimidazole in 10 ml acetonitrile, add 20 mmol 3-bromopropylamine hydrobromide and mix well. 2 Under protection, the reaction was carried out at 85°C for 20 hours, the solvent was removed by rotary evaporation, the mixture was washed with ethyl acetate, and the mixture was dried under vacuum at 60°C for 24 hours to obtain 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid ([PAVIm]Br·HBr).

[0080] Step 2: Disperse 10 mmol N-vinylimidazole in 10 ml ethanol, add 20 mmol 2-bromopyridine and mix well. 2 Under protection, the reaction was carried out at 85° C. for 20 h, the solvent was removed by rotary evaporation, the mixture was washed with ethyl acetate, and the mixture was dried under vacuum at 60° C. for 22 h to obtain 1-pyridyl-2-vinylimidazolium bromide ionic liquid ([PDVIm]Br).

[0081] Step 3: 10 mmol [PAVIm] Br·HBr ionic liquid, 15 mmol [PDVIm] Br ionic liquid and 15 mmol DVB were added to a mixed solvent consisting of 10 ml water and 78 ml ethanol, followed by 500 mg AIBN. The mixture was stirred at room temperature for 2 h and heated under N 2 Under protection, the reaction was carried out at 85°C for 20 h, filtered, washed with ethanol (3×20 mL), and dried in vacuo at 60°C for 24 h to obtain the catalyst PD-ILsBr·HBr.

[0082] Step 4: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 1.0 mol / L sodium carbonate aqueous solution and stirred at room temperature for 65 h, filtered, washed with hot water (3×20 mL), and dried under vacuum at 75°C for 24 h to obtain PD-ILsCO 3 catalyst.

[0083] Step 5: The PD-ILsBr·HBr catalyst prepared above was dispersed in 1.0 mol / L sodium acetate aqueous solution and stirred at room temperature for 70 h, filtered, washed with hot water (3×20 mL), and vacuum dried at 70° C. for 22 h to obtain the PD-ILsAC catalyst.

[0084] Example 8

[0085] Step 1: Disperse 10 mmol N-vinylimidazole in 6 ml acetonitrile, add 20 mmol 3-bromopropylamine hydrobromide and mix well. 2 Under protection, the reaction was carried out at 80°C for 20 hours, the solvent was removed by rotary evaporation, washed with ethyl acetate, and dried in vacuo at 55°C for 24 hours to obtain 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid ([PAVIm]Br·HBr).

[0086] Step 2: Disperse 10 mmol N-vinylimidazole in 8 ml ethanol, add 18 mmol 2-bromopyridine and mix well. 2 Under protection, the reaction was carried out at 90° C. for 18 h, the solvent was removed by rotary evaporation, the mixture was washed with ethyl acetate, and the mixture was dried under vacuum at 60° C. for 20 h to obtain 1-pyridyl-2-vinylimidazolium bromide ionic liquid ([PDVIm]Br).

[0087] Step 3: 10 mmol [PAVIm] Br·HBr ionic liquid, 15 mmol [PDVIm] Br ionic liquid and 20 mmol DVB were added to a mixed solvent consisting of 10 ml water and 80 ml ethanol, followed by 489 mg AIBN. The mixture was stirred at room temperature for 2 h and heated to 40 °C under N 2 Under protection, the reaction was carried out at 80°C for 20 h, filtered, washed with ethanol (3×20 mL), and dried in vacuo at 70°C for 22 h to obtain the catalyst PD-ILsBr·HBr.

[0088] Step 4: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 1.6 mol / L sodium carbonate aqueous solution and stirred at room temperature for 58 h, filtered, washed with hot water (3×20 mL), and dried under vacuum at 70°C for 23 h to obtain PD-ILsCO 3 catalyst.

[0089] Step 5: The PD-ILsBr·HBr catalyst prepared above was dispersed in a 1.6 mol / L sodium acetate aqueous solution and stirred at room temperature for 56 h, filtered, washed with hot water (3×20 mL), and vacuum dried at 75° C. for 20 h to obtain a PD-ILsAC catalyst.

[0090] The P-DILsBr·HBr and P-DILsCO prepared in the above examples were 3 P-DILsAC catalyst was used for catalytic CO 2 , epoxide, and methanol are coupled in one pot to prepare DMC reaction, as follows:

[0091] Application Example 1

[0092] 1.10 g (15 mmol) of propylene oxide, 0.06 g of P-DILsBr·HBr and 5.2 g (165 mmol) of methanol were weighed in turn and added into a 50 mL high pressure microreactor. 2 After replacing the air in the reactor, the pressure was increased to 12.5 bar, and the temperature was raised to 100°C before the reaction began. The reaction time was 1.5 hours, and the catalyst and the reaction product were separated by centrifugation after the reaction. The liquid obtained by the reaction was analyzed by gas chromatography, and the conversion rate of propylene oxide was 98.4%, and the yield of DMC was 50.4%.

[0093] Application Example 2

[0094] Weigh 1.10 g (12 mmol) of epichlorohydrin, 0.06 g of P-DILsCO 3 and 5.3 g (166 mmol) of methanol were added to a 50 mL high pressure microreactor and CO 2 After replacing the air in the reactor, the pressure was increased to 10 bar, and the temperature was raised to 120°C before the reaction began. The reaction time was 2 hours, and the catalyst and the reaction product were separated by centrifugation. The liquid obtained by the reaction was analyzed by gas chromatography, and the conversion rate of propylene oxide was 99.1%, and the yield of DMC was 53.1%.

[0095] Application Example 3

[0096] 1.10 g (9 mmol) of styrene oxide, 0.05 g of P-DILsAC, and 4.7 g (148 mmol) of methanol were weighed in turn and added into a 50 mL high pressure microreactor. 2 After replacing the air in the reactor, the pressure was increased to 12.5 bar, and the temperature was raised to 120°C before the reaction began. The reaction time was 1 hour, and the catalyst and the reaction product were separated by centrifugation. The liquid obtained by the reaction was analyzed by gas chromatography, and the conversion rate of propylene oxide was 98.8%, and the yield of DMC was 52.4%.

[0097] Application Example 4

[0098] 1.10 g (12 mmol) of epichlorohydrin, 0.04 g of P-DILsBr·HBr and 7.5 g (233 mmol) of methanol were weighed in turn and added into a 50 mL high pressure microreactor. 2 After replacing the air in the reactor, the pressure was increased to 10 bar, and the temperature was raised to 140°C before the reaction began. The reaction time was 1 hour, and the catalyst and the reaction product were separated by centrifugation after the reaction. The liquid obtained by the reaction was analyzed by gas chromatography, and the conversion rate of propylene oxide was 97.9%, and the yield of DMC was 51.4%.

[0099] Application Example 5

[0100] 1.10 g (12 mmol) of epichlorohydrin, 0.04 g of P-DILsAC and 8.4 g (264 mmol) of 22.00 g of methanol were weighed in turn and added into a 50 mL high pressure microreactor. 2 After replacing the air in the reactor, the pressure was increased to 10 bar, and the temperature was raised to 160°C before the reaction began. The reaction time was 1 hour, and the catalyst and the reaction product were separated by centrifugation after the reaction. The liquid obtained by the reaction was analyzed by gas chromatography, and the conversion rate of propylene oxide was 99.2%, and the yield of DMC was 54.6%.

[0101] Application Example 6

[0102] 1.10 g (12 mmol) of epichlorohydrin, 0.05 g of P-DILsBr·HBr and 6.4 g (200 mmol) of methanol were weighed in turn and added into a 50 mL high pressure microreactor. 2 After replacing the air in the reactor, the pressure was increased to 10 bar, and the temperature was raised to 120°C before the reaction began. The reaction time was 1 hour, and the catalyst and the reaction product were separated by centrifugation. The liquid obtained by the reaction was analyzed by gas chromatography, and the conversion rate of propylene oxide was 95.1%, and the yield of DMC was 51.4%.

[0103] Application Example 7

[0104] Weigh 1.10 g (12 mmol) of epichlorohydrin, 0.05 g of P-DILsCO 3 and 6.4 g (200 mmol) of methanol were added to a 50 mL high pressure microreactor and CO 2 After replacing the air in the reactor, the pressure was increased to 10 bar, and the temperature was raised to 120°C before the reaction began. The reaction time was 1 hour, and the catalyst and reaction product were separated by centrifugation after the reaction. The liquid obtained by the reaction was analyzed by gas chromatography, and the conversion rate of propylene oxide was 98.7%, and the yield of DMC was 54.1%.

[0105] Application Example 8

[0106] 1.10 g (15 mmol) of propylene oxide, 0.04 g of P-DILsBr·HBr and 4.8 g (150 mmol) of methanol were weighed in turn and added into a 50 mL high pressure microreactor. 2 After replacing the air in the reactor, the pressure was increased to 5 bar, and the temperature was raised to 100°C before the reaction began. The reaction time was 1 hour, and the catalyst and the reaction product were separated by centrifugation after the reaction. The liquid obtained by the reaction was analyzed by gas chromatography, and the conversion rate of propylene oxide was 96.2%, and the yield of DMC was 49.8%.

[0107] Application Example 9

[0108] 1.10 g (15 mmol) of propylene oxide, 0.1 g of P-DILsBr·HBr, and 7.2 g (225 mmol) of methanol were weighed in sequence and added into a 50 mL high pressure microreactor. 2 After replacing the air in the reactor, the pressure was increased to 12.5 bar, and the temperature was raised to 140°C before the reaction began. The reaction time was 4 hours, and the catalyst and the reaction product were separated by centrifugation. The liquid obtained by the reaction was analyzed by gas chromatography, and the conversion rate of propylene oxide was 99.1, and the yield of DMC was 54.2%.

[0109] The experimental results of the application example are shown in Table 1.

[0110] Table 1 Application example experimental results

[0111]

[0112]

[0113] As described above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the present invention itself. Various changes in form and details may be made without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims

1. A pyridineamine bifunctional polyionic liquid catalyst, characterized in that: The polyionic liquid catalyst I was copolymerized by using 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid [PAVIm]Br·HBr and 1-pyridyl-2-vinylimidazolium bromide ionic liquid [PDVIM]Br as comonomers, adding a crosslinking agent and an initiator.

2. The method for preparing the pyridineamine bifunctional polyionic liquid catalyst according to claim 1, characterized in that: The following steps are involved: (1) Preparation of 1-(3-propylamine hydrobromide)-3-vinylimidazolium bromide ionic liquid [PAVIm]Br·HBr: N-vinylimidazole and 3-bromopropylamine hydrobromide were dissolved in acetonitrile, reacted under N2, the solvent was evaporated, washed, and dried to obtain [PAVIm]Br·HBr ionic liquid; (2) Preparation of 1-pyridyl-2-vinylimidazole bromide [PDVIM]Br ionic liquid: N-vinylimidazole and 2-bromopyridine were dissolved in ethanol, reacted under N2, the solvent was evaporated, washed, and dried to obtain [PDVIm]Br ionic liquid; (3) Preparation of pyridineamine-based polyionic liquid PD-ILsBr·HBr catalyst: [PAVIm]Br·HBr ionic liquid, [PDVIm]Br ionic liquid, crosslinker DVB and initiator AIBN were added together into a water / ethanol mixed solvent, reacted under N2, filtered, washed and dried to obtain PD-ILsBr·HBr catalyst, i.e., polyionic liquid catalyst I.

3. The preparation method according to claim 2, characterized in that: In step (1), the molar ratio of N-vinylimidazole to 3-bromopropylamine hydrobromide is 1:1-2.5; the molar concentration of N-vinylimidazole in acetonitrile is 1-2 mmol / ml; the reaction temperature is 70-90°C, and the reaction time is 18-24h; the washing is performed by ethyl acetate washing; the drying is performed by vacuum drying, the drying temperature is 55-75°C, and the drying time is 18-24h.

4. The preparation method according to claim 2, characterized in that: In step (2), the molar ratio of N-vinylimidazole to 2-bromopyridine is 1:1-2, the molar concentration of N-vinylimidazole in ethanol is 1-2 mmol / ml; the reaction temperature is 70-90°C, and the reaction time is 18-24h; the washing is performed by ethyl acetate washing; the drying is performed by vacuum drying, the drying temperature is 55-75°C, and the drying time is 18-24h.

5. The preparation method according to claim 2, characterized in that: In step (3), the molar ratio of the [PAVIm]Br·HBr ionic liquid, [PDVIm]Br and the crosslinking agent DVB is 1:0.5-2:0.5-2; the amount of the initiator AIBN is 2.3-5.6wt% of the sum of the masses of [PAVIm]Br·HBr, [PDVIm]Br and the crosslinking agent DVB; the molar concentration of the [PAVIm]Br·HBr ionic liquid in the mixed solvent is 0.1-0.2mmol / ml; the volume ratio of water to ethanol is 1:4-9; the reaction temperature is 75-95°C, and the reaction time is 18-24h; the washing is ethanol washing; the drying is vacuum drying, the drying temperature is 55-75°C, and the drying time is 18-24h.

6. A pyridineamine bifunctional polyionic liquid catalyst, characterized in that: The polyionic liquid catalyst I described in claim 1 is subjected to anion exchange reaction with a sodium carbonate aqueous solution to obtain a polyionic liquid catalyst II; the polyionic liquid catalyst I described in claim 1 is subjected to anion exchange reaction with a sodium acetate aqueous solution to obtain a polyionic liquid catalyst III.

7. The method for preparing the pyridineamine bifunctional polyionic liquid catalyst according to claim 6, characterized in that: The concentration of the sodium carbonate aqueous solution or the sodium acetate aqueous solution is 0.7-1.7 mol / L; the anion exchange reaction is carried out under stirring at room temperature, and after the reaction is completed, the reaction is filtered, washed with hot water, and vacuum dried to obtain a polyionic liquid catalyst; the stirring time is 48-72 hours; the drying temperature is 55-75° C., and the drying time is 18-24 hours.

8. Use of the pyridineamine bifunctional polyionic liquid catalyst according to any one of claims 1 or 6 in catalyzing the one-pot coupling of CO2, epoxide and methanol to prepare DMC.

9. The use according to claim 8, characterized in that: The polyionic liquid catalyst according to claim 1 or 6, raw material epoxide and methanol are added to the reaction kettle, the air in the kettle is replaced by CO2, and then the kettle is pressed and heated to the reaction temperature to start the reaction. After the reaction is completed, the catalyst and the reaction product are separated by centrifugation.

10. The use according to claim 9, characterized in that: The raw material epoxide is any one of epichlorohydrin, styrene oxide or glycidol; the mass ratio of the raw material epoxide to the polyionic liquid catalyst is 1:0.036-0.09; the CO2 pressure is 5-12.5 bar; the molar ratio of methanol to epoxide is 10-25:1; the reaction temperature is 100-160°C, and the reaction time is 1-4 hours.

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