CN110721727B - Oxford catalyst, preparation method thereof and application thereof in synthesis of multi-functionality five-membered cyclic carbonate - Google Patents

Oxford catalyst, preparation method thereof and application thereof in synthesis of multi-functionality five-membered cyclic carbonate Download PDF

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CN110721727B
CN110721727B CN201911068852.3A CN201911068852A CN110721727B CN 110721727 B CN110721727 B CN 110721727B CN 201911068852 A CN201911068852 A CN 201911068852A CN 110721727 B CN110721727 B CN 110721727B
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catalyst
pyrolysis
cyclic carbonate
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deionized water
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CN110721727A (en
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王军威
梁宏光
亢茂青
冯月兰
梁辰
李其峰
赵雨花
殷宁
张清运
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Shanxi Institute of Coal Chemistry of CAS
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract

The invention relates to a scarlet catalyst, a preparation method thereof and application thereof in synthesis of multi-functionality five-membered cyclic carbonate, belongs to the technical field of catalysts, solves the technical problem of poor use stability of the scarlet catalyst in synthesis of the multi-functionality five-membered cyclic carbonate, and adopts the following solution: the graphite-phase carbon nitride material is prepared by taking nitrogen-containing organic matters as raw materials through high-temperature pyrolysis, and the fenzine-type catalyst is obtained through further water treatment. The catalyst consists of melem hydrate and melem derivative, contains rich amine basic centers and hydroxyl acid centers, and can be used for synergistically catalyzing cycloaddition reaction of an epoxy compound and carbon dioxide to obtain five-membered cyclic carbonate. The heterogeneous catalyst has the characteristics of simple preparation, no additive, high catalytic activity, high repeated use stability, easy separation from products and the like.

Description

Oxford catalyst, preparation method thereof and application thereof in synthesis of multi-functionality five-membered cyclic carbonate
Technical Field
The invention belongs to the technical field of catalysts, relates to a fenzine catalyst in the synthesis of multi-functionality five-membered cyclic carbonate, and particularly relates to a fenzine catalyst, a preparation method thereof and application thereof in the synthesis of the multi-functionality five-membered cyclic carbonate.
Background
One of the main uses of the cyclic carbonates with multiple functionalities is as an important synthetic raw material for Polyhydroxyurethanes (PHU), as well as a plasticizer for epoxy resins. PHU is a special polyurethane material, because the whole preparation process does not use high-toxicity isocyanate raw materials, and the molecular structure contains free hydroxyl, intramolecular hydrogen bonds can be formed, the permeation resistance, the insulating property, the chemical resistance, the water resistance, the bonding property and the like of the material are obviously improved, the PHU becomes a novel environment-friendly high-performance non-isocyanate polyurethane material, and is an important development direction of the polyurethane material. Epoxy resins are a class of polymer materials with a wide range of applications, and are commonly used in the fields of engineering plastics, composites, coatings, adhesives, and the like. The polymerization of epoxy resin monomers and organic polyamine curing agents is an important way to prepare epoxy resin polymers, but the obtained polymers have high mechanical strength but high brittleness, and an aliphatic epoxy compound or other plasticizers are often required to improve the toughness and the impact resistance of polymer materials. The multifunctional cyclic carbonate can also react with organic polyamine, and when the multifunctional cyclic carbonate is used as a plasticizer of epoxy resin, the multifunctional cyclic carbonate can not only form a molecular interpenetrating network structure with the epoxy resin, but also can be connected with an epoxy monomer through the organic polyamine to enter the molecular structure of the epoxy resin to form a hybrid polymer, so that the permeation and loss of an additional plasticizer in the service period are avoided, and the service life of the material is prolonged. Therefore, the novel cyclic carbonate with multiple functionality has good application prospect.
For the synthesis of multifunctional cyclic carbonates, the simplest method is by reacting multifunctional epoxides with CO2By cycloaddition reaction of (a) and (b), this reaction route is also CO2One of the important routes for chemical immobilization. In this reaction, the catalyst used includes an alkali metal halide or an ionic liquid catalyst, and usually an organic solvent and a co-catalyst are required to work together. For example, Endo et al (Ochiai B, Inoue S, Endo T. Journal of Polymer Science Part A: Polymer Chemistry, 2005, 43(24): 6613-6618.) investigated bisphenol A epoxy resins with CO2The reaction of (1). However, homogeneous catalysts have problems in catalyst recovery and product separation and purification. Ke et al (Ke J, Li X, Jiang S, Wang J, et al. Journal of CO2Catalysis, 26 (2018): 302-2The conversion rate of epoxide can reach 99%, but the active component of the catalyst is easy to lose, and the recycling use is stableThe property is not good enough. In recent years, a great deal of research is focused on the application of carbon nitride in catalysis, the carbon nitride is composed of a fenzine structural unit, the material property is stable, the material contains a basic group, the structure is adjustable, and fenzine structures with different polymerization degrees can be easily prepared, and the carbon nitride is applied to epoxide and CO2Has potential application value in the reaction. The carbon nitride catalyst is modified by doping atoms, such as Zn-doped carbon nitride, and is loaded on gamma-Al2O3On the carrier, the conversion rate of butanediol diglycidyl ether can be promoted to 91.4%, and the selectivity can reach 98.9%, but repeated experiments prove that the catalyst has poor stability and the active component is easy to lose (Liang H, Wang J, et al, New Journal of Chemistry, 2018, 42, 16127-16137.). Zhu et al (Zhu J, Diao T, Wang W, et al, Applied Catalysis B: Environmental, 2017, 219: 92-100.) adopt B (OH)3The activity of the supported catalyst B0.1CN/SBA-15 obtained by modifying the catalyst is the best, and the conversion rate of Styrene Oxide (SO) can reach 97.8 percent, but the problem of reduced cycling stability also exists. Therefore, how to improve the use stability of the catalyst is of great significance to further application of the catalyst.
Disclosure of Invention
In order to overcome the defects in the prior art and solve the technical problem of poor stability of the use of a fenazine catalyst in the synthesis of the multi-functionality five-membered cyclic carbonate, the invention provides a method for preparing the multifunctional epoxide and CO, which has the advantages of low preparation cost, simple process, no additive, mild reaction condition, high conversion rate, good stability and easy separation2A reactive fenzine catalyst and a preparation method thereof.
The invention is realized by the following technical scheme.
A fenzine-type catalyst for the synthesis of multifunctional five-membered cyclic carbonates, wherein: the main active ingredients of the fenazine-based catalyst comprise melem hydrate and melem oligomer derivatives.
The application of a fenazine catalyst is characterized in that: the fenazine catalyst is applied to synthesis of five-membered cyclic carbonate through reaction of carbon dioxide and an epoxy compound.
The application of a fenazine catalyst comprises the following steps: firstly, taking epoxide with multiple functionality as a reactant, and weighing a fenfluramine catalyst, wherein the total amount of the fenfluramine catalyst accounts for 3% -10% of the weight of the epoxide; secondly, adding the reactants of epoxide and the fenzine catalyst into a high-pressure reaction kettle, and filling CO into the high-pressure reaction kettle2Until the pressure in the high-pressure reaction kettle is 0.5-3.0 MPa, the temperature of the high-pressure reaction kettle is raised to 100 ℃ and 150 ℃, and the catalyst is catalyzed and reacted for 10-30 h; thirdly, separating the product from the catalyst by adopting a filtering and centrifuging method after the reaction is finished to prepare the multi-functionality five-membered cyclic carbonate; finally, the composition of the product is analyzed by nuclear magnetism, and the catalyst is recovered for multiple recycling.
Further, the polyfunctional epoxide may be, but is not limited to, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether, bisphenol a diglycidyl ether, epoxidized soybean oil.
Furthermore, the high-pressure reaction kettle is made of stainless steel, the volume of the high-pressure reaction kettle is 100 mL, and an air inlet, an air outlet and a mechanical stirrer are arranged on the high-pressure reaction kettle.
A preparation method of a fenzine catalyst for synthesizing multifunctional five-membered cyclic carbonate comprises the following steps:
s1, placing 1-20 g of nitrogenous organic compounds in a crucible with a cover, then placing the crucible in roasting equipment for heating and roasting, wherein the pyrolysis program of the nitrogenous organic compounds is as follows: the heating rate is 2-15 ℃/min, the pyrolysis final temperature is 500 ℃ and the roasting time is 1-20 h; after the high-temperature pyrolysis is finished, naturally cooling the crucible and roasting equipment to obtain a pyrolysis product, and reserving the pyrolysis product for later use;
s2, adding deionized water into the pyrolysis product obtained in the step S1, wherein the mass ratio of deionized water to the pyrolysis product is 5-50: 1, preparing a catalyst solid suspension, centrifuging the catalyst solid suspension, pouring out supernatant, and drying the obtained solid substrate at room temperature or in an oven at the temperature of 100 ℃ and 150 ℃ for 10-20 hours to obtain the prazine catalyst for synthesizing the multi-functionality five-membered cyclic carbonate.
Further, in the step S1, the nitrogen-containing organic substance is melamine, cyanamide, dicyandiamide, guanidine salt, urea, biuret, piperazine, imidazole, etc., and preferably one or more of melamine, cyanamide, and dicyandiamide.
Further, in the step S1, the baking device is a muffle furnace or a tube-type heating furnace, and the baking atmosphere in the baking device is air or inert atmosphere of nitrogen or argon.
Further, in the step S1, the roasting temperature of the roasting equipment is 300-500 ℃, the temperature rising rate is 1-50 ℃/min, and the roasting time is 1-20 h.
Preferably, the roasting temperature of the roasting equipment is 400-450 ℃, the heating rate is 5-20 ℃/min, and the roasting time is 2-10 h.
Further, in the step S2, adding deionized water into the pyrolysis product, and stirring in a container at room temperature to 100 ℃ for 0.5 to 10 hours; or adding deionized water into the pyrolysis product and then mixing in an ultrasonic vibrator, wherein the mixing time of the ultrasonic vibrator at room temperature is 0.5-2.0 h; or adding deionized water into the pyrolysis product and then mixing in a hydrothermal kettle, wherein the temperature of the hydrothermal kettle is room temperature-200 ℃, and the mixing time is 5-30 h.
Preferably, deionized water is added into the pyrolysis product and then stirred in a container, wherein the stirring temperature is 50-90 ℃, and the stirring time is 2-8 hours; or adding deionized water into the pyrolysis product and then mixing in an ultrasonic vibrator, wherein the mixing time of the ultrasonic vibrator at room temperature is 0.5-2.0 h; or adding deionized water into the pyrolysis product and mixing in a hydrothermal kettle, wherein the temperature of the hydrothermal kettle is 50-150 ℃, and the mixing time is 10-20 h.
Compared with the prior art, the invention has the beneficial effects that:
1. the raw materials for preparing the fenzine catalyst are cheap and easy to obtain, no metal component is contained, the preparation method is simple and rapid, and no additive is needed;
2. for the reaction of polyfunctional epoxides with CO2Synthesis of the corresponding polyfunctional cyclic carbonatesThe catalyst has high reaction activity and excellent recycling stability, and is easy to separate from the product.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
10 g of melamine is placed in a crucible with a cover, placed in a muffle furnace, heated and roasted under the condition of inert atmosphere, and the pyrolysis program is set as follows: the heating rate is 15 ℃/min, the pyrolysis final temperature is 450 ℃, and the roasting time is 3 h. And after the high-temperature pyrolysis is finished, naturally cooling to obtain an initial pyrolysis product. Adding deionized water into the initial product, wherein the mass ratio of the deionized water to the pyrolysis product is 25: 1, carrying out ultrasonic treatment in an ultrasonic oscillator, and carrying out ultrasonic treatment for 0.5 h at room temperature to obtain a solid suspension. And after the ultrasonic treatment is finished, centrifuging the solid suspension, and drying the final solid precipitate in an oven at 100 ℃ for 15 h to obtain the required fenzine catalyst.
Butanediol diglycidyl ether as a reactant, with a catalyst mass fraction of 7% relative to the epoxide, was introduced into a 100 mL stainless steel autoclave equipped with a gas inlet, a gas outlet and a mechanical stirrer, with CO2The pressure is 2.0 MPa, the temperature is 140 ℃, and the reaction time is 20 h. Separating the product and the catalyst by filtering and centrifuging after reaction by adopting1The product composition was analyzed by H NMR and the yield of butanediol diglycidyl ether based pentacyclic carbonate was 92.4%. The yield of the butanediol diglycidyl ether five-membered cyclic carbonate after 5 times of recycling of the recovered catalyst is 91.8 percent.
Example 2:
10 g of dicyandiamide was put in a crucible with a lid, and placed in a muffle furnace, and temperature-raised and baked in air. The heating rate is 12 ℃/min, and the temperature is kept for 4 h after being heated to 480 ℃. And then stopping heating, and naturally cooling to room temperature to obtain a pyrolysis product. Adding deionized water into the pyrolysis product, wherein the mass ratio of water to the pyrolysis product is 20: 1, and carrying out ultrasonic treatment in an ultrasonic oscillator for 1.0 h to obtain a solid suspension. And after the ultrasonic treatment is finished, centrifuging the solid suspension, and drying the final solid precipitate in an oven at 120 ℃ for 10 hours to obtain the fentrazine catalyst.
Butanediol diglycidyl ether as a reactant, 10% by weight of catalyst relative to the epoxide, was introduced into a 100 mL stainless steel autoclave equipped with a gas inlet, a gas outlet and a mechanical stirrer, with CO2The pressure is 1.0 MPa, the temperature is 140 ℃, and the reaction time is 25 h. After the reaction, the catalyst and the product are separated through the processes of filtration and centrifugation, and then the composition of the product is analyzed by nuclear magnetism, and the yield of the butanediol diglycidyl ether five-membered cyclic carbonate is 96.1 percent. The yield of the butanediol diglycidyl ether five-membered cyclic carbonate after 5 times of recycling of the recovered catalyst is 96.0 percent.
Example 3:
15 g of melamine was placed in a crucible with a lid, placed in a muffle furnace, and baked at an elevated temperature under ambient conditions, with the pyrolysis procedure set to: the heating rate is 8 ℃/min, the pyrolysis final temperature is 500 ℃, and the roasting time is 3 h. And after the high-temperature pyrolysis is finished, naturally cooling to obtain an initial roasted product. Adding deionized water into the initial product, wherein the mass ratio of water to the pyrolysis product is 30: 1, and carrying out ultrasonic treatment in an ultrasonic oscillator for 0.5 h at room temperature to obtain a solid suspension. And after the ultrasonic treatment is finished, centrifuging the solid suspension, and drying the final solid precipitate in an oven at 110 ℃ for 10 hours to obtain the fentrazine catalyst.
Using butanediol diglycidyl ether as a reactant and a catalyst in a mass fraction of 15% relative to the epoxide, the mixture is introduced into a 100 mL stainless steel autoclave equipped with a gas inlet, a gas outlet and a mechanical stirrer, and CO is introduced into the autoclave2The pressure is 3.0 MPa, the temperature is 150 ℃, and the reaction time is 30 h. After the reaction, the catalyst and the product are filtered and centrifugally separated, and then the composition of the product is analyzed by nuclear magnetism, and the yield of the butanediol diglycidyl ether five-membered cyclic carbonate is 77.2 percent. The yield of the butanediol diglycidyl ether five-membered cyclic carbonate after 5 times of recycling of the recovered catalyst is 76.9 percent.
Example 4:
placing 5 g of melamine in a crucible with a cover, placing in a muffle furnace, heating and roasting under the environmental condition, and setting the pyrolysis program as follows: the heating rate is 5 ℃/min, the pyrolysis final temperature is 425 ℃, and the roasting time is 8 h. And after the high-temperature pyrolysis is finished, naturally cooling to obtain an initial roasted product. Deionized water is added into the initial compound, the mass ratio of water to pyrolysis products is 50: 1, the solid suspension is stirred for 3 hours at 100 ℃ to remove impurities, then hydrothermal reaction is carried out in a hydrothermal reaction kettle at 200 ℃, after the reaction is finished, the obtained suspension is subjected to centrifugal treatment, and the final solid precipitate is dried for 20 hours at room temperature to obtain the required oxaziclo-zine catalyst.
Butanediol diglycidyl ether as a reactant, 5% by weight of catalyst relative to the epoxide, was introduced into a 100 mL stainless steel autoclave equipped with a gas inlet, a gas outlet and a mechanical stirrer, and CO was introduced into the autoclave2The pressure is 1.5 MPa, the temperature is 130 ℃, and the reaction time is 15 h. After the reaction, the product composition is subjected to filtration and centrifugation treatment, and nuclear magnetic analysis is adopted, so that the yield of the butanediol diglycidyl ether five-membered cyclic carbonate is 80.1%. The yield of the butanediol diglycidyl ether five-membered cyclic carbonate after 5 times of recycling of the recovered catalyst is 78.9 percent.
Example 5:
10 g of dicyandiamide was placed in a crucible with a lid, placed in a muffle furnace, and baked at an elevated temperature under ambient conditions, with the pyrolysis procedure set as: the heating rate is 10 ℃/min, the pyrolysis final temperature is 450 ℃, and the roasting time is 4 h. And after the high-temperature pyrolysis is finished, naturally cooling to obtain an initial roasting product. Adding deionized water into the initial product, wherein the mass ratio of water to the pyrolysis product is 50: 1, and carrying out ultrasonic treatment in an ultrasonic oscillator for 1 h at room temperature. And after the ultrasonic treatment is finished, centrifuging the solid suspension, and drying the final solid precipitate in an oven at the temperature of 130 ℃ for 12 hours to obtain the required fenzine catalyst.
Butanediol diglycidyl ether as a reactant, 10% by weight of catalyst relative to the epoxide, was introduced into a 100 mL stainless steel autoclave equipped with a gas inlet, a gas outlet and a mechanical stirrer, with CO2The pressure is 1.0 MPa, the temperature is 140 ℃, and the reaction time is 25 h. After reaction, the catalyst is separated out by filtration and centrifugation, and then a nuclear magnetism method is adoptedThe product composition was analyzed and the yield of butanediol diglycidyl ether based five-membered cyclic carbonate was 82.2%. The recovery rate of butanediol diglycidyl ether five-membered cyclic carbonate after 5 times of recycling of the recovered catalyst is 82.2 percent.
Example 6:
10 g of melamine is placed in a crucible with a cover, placed in a muffle furnace, heated and roasted under the environmental condition, and the pyrolysis program is set as follows: the heating rate is 15 ℃/min, the pyrolysis final temperature is 450 ℃, and the roasting time is 4 h. And after the high-temperature pyrolysis is finished, naturally cooling to obtain an initial roasted product. And adding deionized water into the initial product, wherein the mass ratio of water to the pyrolysis product is 20: 1, and carrying out ultrasonic treatment in an ultrasonic oscillator for 40 min at room temperature to obtain a solid suspension. And after the ultrasonic treatment is finished, centrifuging the solid suspension, and drying the final solid substrate in an oven at 150 ℃ for 12 h to obtain the fentrazine catalyst.
Ethylene glycol diglycidyl ether was used as a reactant, and the catalyst was added in a mass fraction of 7% relative to the epoxide in a 100 mL stainless steel autoclave equipped with a gas inlet, a gas outlet and a mechanical stirrer, and CO was added2The pressure is 2.0 MPa, the temperature is 140 ℃, and the reaction time is 20 h. After the reaction, the product composition is subjected to filtration and centrifugation treatment, and then nuclear magnetic analysis is carried out on the product composition, wherein the yield of the ethylene glycol diglycidyl ether five-membered cyclic carbonate is 96.5%. The yield of the butanediol diglycidyl ether five-membered cyclic carbonate after 5 times of recycling of the recovered catalyst is 95.5 percent.
Example 7:
12 g of melamine is placed in a crucible with a cover, placed in a tube furnace, heated and roasted in a nitrogen atmosphere, and the pyrolysis procedure is set as follows: the heating rate is 12 ℃/min, the pyrolysis final temperature is 450 ℃, and the roasting time is 3 h. And after the high-temperature pyrolysis is finished, naturally cooling to obtain an initial roasted product. And adding deionized water into the initial compound, wherein the mass ratio of water to pyrolysis products is 15: 1, and carrying out ultrasonic treatment in an ultrasonic oscillator for 20 min to obtain a solid suspension. And after the ultrasonic treatment is finished, centrifuging the solid suspension, and drying the final solid substrate at room temperature for 15 h to obtain the mepazine catalyst.
Polyethylene glycol diglycidyl ether as a reactant, 10% by weight of a catalyst relative to an epoxide, was charged into a 100 mL stainless steel autoclave equipped with a gas inlet, a gas outlet and a mechanical stirrer, and CO was added2The pressure is 2.0 MPa, the temperature is 140 ℃, and the reaction time is 30 h. After the reaction, the reaction product is filtered and centrifuged, and the nuclear magnetic analysis is adopted to analyze the composition of the product, wherein the yield of the polyethylene glycol diglycidyl ether five-membered cyclic carbonate is 70.3 percent. The yield of the five-membered cyclic carbonate of the polyethylene glycol diglycidyl ether group after 5 times of recycling of the recovered catalyst is 70.2 percent.
Example 8:
15 g of melamine was placed in a crucible with a lid, placed in a muffle furnace, and baked at an elevated temperature under ambient conditions, with the pyrolysis procedure set to: the heating rate is 10 ℃/min, the pyrolysis final temperature is 450 ℃, and the roasting time is 3 h. And after the high-temperature pyrolysis is finished, naturally cooling to obtain an initial roasted product. And adding deionized water into the initial compound, wherein the mass ratio of water to pyrolysis products is 25: 1, and carrying out ultrasonic treatment in an ultrasonic oscillator for 30 min at room temperature to obtain a solid suspension. And after the ultrasonic treatment is finished, centrifuging the solid suspension, and drying the final solid substrate in an oven at 100 ℃ for 10 hours to obtain the fentrazine catalyst.
Adding polybutylene glycol diglycidyl ether serving as a reactant and 10 mass percent of a catalyst relative to an epoxide into a 100 mL stainless steel autoclave provided with an air inlet, an air outlet and a mechanical stirrer, and adding CO2The pressure is 2.0 MPa, the temperature is 140 ℃, and the reaction time is 30 h. After the reaction, the catalyst and the product are filtered and centrifugally separated, and the product composition is analyzed by nuclear magnetism, and the yield of the polytetramethylene glycol diglycidyl ether five-membered cyclic carbonate is 56.3%. The recovery rate of the polytetramethylene glycol diglycidyl ether five-membered cyclic carbonate after 5 times of recycling of the recovered catalyst is 56.2 percent.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (6)

1. The application of the fenazine catalyst in synthesizing five-membered cyclic carbonate by reacting carbon dioxide with an epoxy compound is characterized by comprising the following steps:
firstly, taking epoxide with multiple functionality as a reactant, and weighing a fenfluramine catalyst, wherein the total amount of the fenfluramine catalyst accounts for 3% -10% of the weight of the epoxide; secondly, adding the reactants of epoxide and the fenzine catalyst into a high-pressure reaction kettle, and filling CO into the high-pressure reaction kettle2Until the pressure in the high-pressure reaction kettle is 0.5-3.0 MPa, the temperature of the high-pressure reaction kettle is raised to 100 ℃ and 150 ℃, and the catalyst is catalyzed and reacted for 10-30 h; thirdly, separating the product from the catalyst by adopting a filtering and centrifuging method after the reaction is finished to prepare the multi-functionality five-membered cyclic carbonate; finally, analyzing the composition of the product by nuclear magnetism, and recycling the catalyst for multiple times of recycling;
the multifunctional epoxide is one or more selected from ethylene glycol diglycidyl ether, butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, bisphenol A diglycidyl ether and epoxidized soybean oil;
the preparation method of the fenzine catalyst comprises the following steps:
s1, placing 1-20 g of nitrogenous organic compounds in a crucible with a cover, then placing the crucible in roasting equipment for heating and roasting, wherein the pyrolysis program of the nitrogenous organic compounds is as follows: the heating rate is 2-15 ℃/min, the pyrolysis final temperature is 500 ℃ and the roasting time is 1-20 h; after the high-temperature pyrolysis is finished, naturally cooling the crucible and roasting equipment to obtain a pyrolysis product, and reserving the pyrolysis product for later use;
s2, adding deionized water into the pyrolysis product obtained in the step S1, wherein the mass ratio of the deionized water to the pyrolysis product is 5-50: 1, preparing a catalyst solid suspension, centrifuging the catalyst solid suspension, pouring out supernatant, and drying the obtained solid substrate at room temperature or in an oven at the temperature of 100 ℃ and 150 ℃ for 10-20 hours to obtain the oxapizin catalyst for synthesizing the multi-functionality five-membered cyclic carbonate.
2. Use according to claim 1, characterized in that: the high-pressure reaction kettle is made of stainless steel, the volume of the high-pressure reaction kettle is 100 mL, and an air inlet, an air outlet and a mechanical stirrer are arranged on the high-pressure reaction kettle.
3. Use according to claim 1, characterized in that: in the step S1, the nitrogen-containing organic compound is melamine, cyanamide, dicyandiamide, a guanidine salt, urea, biuret, piperazine, or imidazole.
4. Use according to claim 1, characterized in that: the method is characterized in that: in the step S1, the baking device is a muffle furnace or a tube-type heating furnace, and the baking atmosphere in the baking device is air or inert atmosphere of nitrogen or argon.
5. Use according to claim 1, characterized in that: in the step S2, adding deionized water into the pyrolysis product, and stirring in a container at room temperature to 100 ℃ for 0.5-10 h; or adding deionized water into the pyrolysis product and then mixing in an ultrasonic vibrator, wherein the mixing time of the ultrasonic vibrator at room temperature is 0.5-2.0 h; or adding deionized water into the pyrolysis product and then mixing in a hydrothermal kettle, wherein the temperature of the hydrothermal kettle is room temperature-200 ℃, and the mixing time is 5-30 h.
6. Use according to claim 1, characterized in that: adding deionized water into the pyrolysis product, and stirring in a container at 50-90 deg.C for 2-8 h; or adding deionized water into the pyrolysis product and then mixing in an ultrasonic vibrator, wherein the mixing time of the ultrasonic vibrator at room temperature is 0.5-2.0 h; or adding deionized water into the pyrolysis product and mixing in a hydrothermal kettle, wherein the temperature of the hydrothermal kettle is 50-150 ℃, and the mixing time is 10-20 h.
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