CN114433228A - Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid - Google Patents

Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid Download PDF

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CN114433228A
CN114433228A CN202210124685.5A CN202210124685A CN114433228A CN 114433228 A CN114433228 A CN 114433228A CN 202210124685 A CN202210124685 A CN 202210124685A CN 114433228 A CN114433228 A CN 114433228A
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ionic liquid
independently selected
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catalyst
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成卫国
刘帅飞
苏倩
付梦倩
邓莉莉
董丽
刘一凡
杨子锋
张锁江
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Guangdong Provincial Laboratory Of Advanced Energy Science And Technology
Huizhou Green Energy And New Materials Research Institute
Institute of Process Engineering of CAS
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Guangdong Provincial Laboratory Of Advanced Energy Science And Technology
Huizhou Green Energy And New Materials Research Institute
Institute of Process Engineering of CAS
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    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
    • B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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    • 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
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract

The invention relates to a core-shell type polymerized ionic liquid catalyzed CO2The method for synthesizing the cyclic carbonate ester through mild conversion adopts imidazole ionic liquid monomers to polymerize on the surface of inorganic carrier silicon dioxide to form a core-shell type polymerization ionic liquid catalyst, the mass ratio of the ionic liquid monomers to the silicon dioxide is 1:0.5-1:10, and the size of the synthesized core-shell type polymerization ionic liquid catalyst is 1-1000 nm. In the mass ratio of the added amount of the catalyst to the epoxy compound1: 2-200, the reaction temperature is 30-180 ℃, the reaction pressure is 0.1-8MPa, the reaction time is 0.25-24h, and CO is catalyzed2And the cyclic carbonate is efficiently synthesized with the epoxy compound, and the yield can reach 97.2 percent. The invention has the characteristics that: the core-shell type polymerization ionic liquid catalyst has the advantages of multiple active sites, high catalytic efficiency, stability, difficult decomposition, simple preparation process, small addition amount, easy separation from a liquid phase and the like, and has higher industrial application value.

Description

Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid
Technical Field
The invention relates to the technical field of green and clean catalytic cyclic compounds, in particular to a method for catalytically synthesizing cyclic carbonate based on a core-shell type polyion liquid.
Background
Carbon dioxide is one of greenhouse gases, the efficient capture and conversion of the carbon dioxide are one of the research centers of numerous scholars at present, and carbon dioxide can be used for obtaining various high value-added compounds such as cyclic carbonate, dimethyl carbonate or isocyanate through various synthesis means. The cyclic carbonate serves as an aprotic polar solvent with a high boiling point, which has a wide application range, can serve as electrolyte in a lithium ion battery, and can also be used for synthesizing intermediates of medicines and fine chemicals, so that the cyclic carbonate is synthesized by taking carbon dioxide as a raw material through a green chemical means, and the cyclic carbonate belongs to the technical problem which needs to be solved urgently in the chemical industry at present.
Because of the poor reactivity of carbon dioxide gas, the preparation of cyclic carbonates using carbon dioxide gas as a raw material in the chemical industry is mainly carried out by reacting carbon dioxide gas and epoxy groups at high temperature and high pressure in the presence of a catalyst. The catalyst is very important for the reaction of synthesizing cyclic carbonate, and the catalysts for synthesizing cyclic carbonate reported at present can be divided into two types, namely homogeneous catalysts and heterogeneous catalysts, wherein the homogeneous catalysts mainly refer to a homogeneous catalytic system consisting of Lewis acid and halogen ions and comprise quaternary ammonium salts, quaternary phosphonium salts, imidazole ionic liquids, Lewis acid metal complexes and the like. For example, CN108299375A discloses a method for preparing cyclic carbonate by using a combined catalyst of succinimide and halide, which utilizes the synergistic effect of succinimide and halide, the reaction temperature is 25-90 ℃, the reaction pressure is 0.1-1 MPa, the reaction time is 1-10 h, and the yield of the obtained cyclic carbonate can reach more than 90%. However, the above homogeneous catalysts are usually used in large amounts, and have problems to be solved, such as difficult separation in a post-treatment process after completion of the reaction, use of a solvent harmful to the environment during the separation process, and difficulty in being applied to an industrial continuous reaction, and thus have a small application prospect.
The heterogeneous catalyst is difficult to dissolve in a reaction system, does not need to separate the catalyst from a product and the like, and belongs to a research hotspot in the field of cyclic carbonate synthesis. Heterogeneous catalysts developed so far include quaternary phosphonium salt supported system catalysts, alkali metal salt supported catalysts, alkali modified ion exchange resin catalysts and the like, and heterogeneous catalysts such as supported metal catalysts, supported quaternary ammonium salt catalysts and the like can solve the problems of difficult catalyst recovery and the like to a certain extent. For example, CN101318949A discloses a method for catalytically synthesizing cyclic carbonate by using an immobilized ionic liquid catalyst, in which a mesoporous molecular sieve is used as a carrier, and imidazolium salt ionic liquid is loaded on the surface of the carrier, and the obtained catalyst can catalytically synthesize cyclic carbonate at a lower temperature and a higher pressure, but has a lower catalytic efficiency and a shorter service life. CN103030623A discloses a composite catalyst composed of a silica carrier loaded with metal silicate and a silica carrier grafted with alkyl silicate, which has high catalytic efficiency and less addition amount when used for catalyzing the reaction of ethylene oxide and carbon dioxide to prepare cyclic carbonate, but the used carrier has limited loading capacity, is expensive, and the service life of the obtained catalyst is still short.
In recent years, core-shell type polymerized ionic liquid polymers have attracted extensive attention of researchers because of their advantages of stable carrier, long service life, many active sites, and the like, and the structure of the polymers can be modified or modified by different groups, and thus have great potential for being used as cyclic carbonate synthesis catalysts. Therefore, based on the prior art, those skilled in the art need to further try to utilize the core-shell ionic liquid polymer, especially to utilize the cheap and stable inorganic carrier, to polymerize the ionic liquid on the surface thereof and then use it as a heterogeneous cyclic carbonate synthesis catalyst, so that it can efficiently catalyze and synthesize cyclic carbonate under the conditions of no solvent, high temperature and high pressure, and increase the service life thereof, thus proving the potential of the heterogeneous catalyst in the industrial production of cyclic carbonate.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for efficiently and catalytically synthesizing cyclic carbonate under the conditions of no solvent, high temperature and high pressure, and proves the potential of a heterogeneous catalyst in the industrial production of cyclic carbonate.
To achieve the above object, one of the objects of the present invention is to provide a method for preparing a cyclic carbonate, the method comprising the steps of:
carbon dioxide and a compound containing epoxy groups are subjected to addition reaction under the catalysis of a core-shell catalyst to obtain cyclic carbonate.
The preparation process of the core-shell ionic liquid polymer is as follows:
Figure RE-GDA0003530618560000031
wherein m and n are each independently selected from any natural number, and m + n.gtoreq.4, such as 5, 8, 12, 20, 40, 60, 100, 120, 150, 180, 200, 250, 300, or the like.
R1Independently selected from a hydrogen atom or any one of an alkane group, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, etc.
R2Independently selected from any one of the functional groups, such as carbon-carbon double bond, carbon-carbon triple bond, hydroxyl, carboxyl, ether bond, aldehyde group, carbonyl, benzyl, phenyl, ester group, etc.
R3～R4Each independently selected from any one of the alkane groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or the like.
A is independently selected from any one of halogen anions, such as fluorine, bromine, chlorine, iodine, and the like.
R5Each independently selected from any one of an alkane group, a hydroxyl-terminated alkane group, a carboxyl-terminated alkane group or a sulfonate-terminated alkane group.
Preferably, in the structure shown in the formula I, 4 is less than or equal to m + n is less than or equal to 136, and the catalytic efficiency is easily reduced due to the high polymerization degree.
Preferably, R1Hydrogen atom, methyl or ethyl;
preferably, R2Independently selected from aldehyde groups, carbonyl groups, benzyl groups, phenyl groups, ester groups, and the like.
Preferably, R3～R4Any of the alkane groups having 4 or less carbon atoms is preferred.
Preferably, A is independently selected from bromide ions,
preferably, R5Each group is independently selected from any one of methyl, ethyl, butyl or hydroxyethyl,in the catalytic reaction, the carrier containing hydroxyl can interact with epoxide through forming hydrogen bonds, so that the activation energy of the reaction is greatly reduced, and the reactants are promoted to be efficiently converted into products.
Preferably, the particle size of the catalyst is 10-100 nm, for example, 12nm, 15nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 95nm, and the like, and the suitable particle size of the catalyst is favorable for promoting the adsorption of carbon dioxide, thereby improving the conversion rate of carbon dioxide.
Preferably, the mass ratio of the carrier to the ionic liquid in the catalyst synthesis process is 1: 0.5-10, such as 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:5 or 1: 10.
The invention utilizes the core-shell ionic liquid polymer as the catalyst to catalyze and synthesize the cyclic carbonate, utilizes the characteristic that the ionic liquid is rich in ions, is beneficial to stabilizing reaction intermediates and reducing the activation energy of the reaction, and simultaneously, the characteristics of the polymer ensure that the ionic liquid can be used as a heterogeneous catalyst, is beneficial to the separation of the catalyst and the reduction of side reactions, and further improves the conversion rate of the cyclic carbonate synthesis reaction.
Preferably, the reaction temperature of the addition reaction is 80 to 150 ℃, for example, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃ or 140 ℃, etc.
Preferably, the reaction pressure of the addition reaction is 1 to 5MPa, for example, 1.5MPa, 1.8MPa, 2.0MPa, 2.5MPa, 3.2MPa, 3.5MPa, 4.0MPa or 4.5 MPa.
Preferably, the reaction time of the addition reaction is 1 to 8 hours, such as 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours and the like.
Preferably, the mass ratio of the catalyst to the epoxy group in the epoxy group-containing compound is 1:2 to 10, for example, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or 1: 10.
Preferably, the compound containing an epoxy group is any one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide, cyclohexene oxide or cyclopentane oxide.
Preferably, the preparation method comprises the following steps:
and (2) placing the compound containing the epoxy group and catalyst powder with the particle size of 10-100 nm in a closed reaction kettle, uniformly mixing, maintaining the temperature of the reaction kettle within the range of 80-150 ℃, continuously introducing carbon dioxide gas into the reaction kettle, maintaining the pressure of a reaction system in the kettle within the range of 1-5 MPa, and performing addition reaction for 1-8 hours to obtain the cyclic carbonate.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a novel core-shell type polymerization ionic liquid heterogeneous catalyst, which is used for catalyzing carbon dioxide to perform addition reaction with a compound containing an epoxy group to obtain cyclic carbonate, the cyclic carbonate prepared by the method has high selectivity and conversion rate, and the purity of the obtained cyclic carbonate product can reach 99.9%.
(2) Compared with the traditional method for preparing cyclic carbonate, the core-shell ionic liquid polymer catalyst used in the invention has the advantages of more active sites, high catalytic efficiency, stability, difficulty in decomposition, simple preparation process, small addition amount, easiness in separation from a liquid phase and the like, and has higher industrial application value.
Drawings
FIG. 1 shows the synthesis process and structure of example 1 of the present invention. The first formula is the synthesis process of the core-shell ionic liquid polymer obtained in example 1.
The second formula is the core-shell ionic liquid polymer structure obtained in the example 1 of the invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
The ionic liquid polymers used in the following examples and comparative examples were obtained by self-synthesis.
Illustratively, the core-shell type polymerized ionic liquid compound can be synthesized by the following steps:
step (1), adding a certain amount of ethyl orthosilicate into a 100mL flask, stirring for 12 hours at 25 ℃ to react, repeatedly washing a reaction product for 3 times by using ethyl acetate after the reaction is finished, and then drying the reaction product in vacuum at 70 ℃ overnight to obtain a white powdery substance, namely spherical silicon dioxide;
and (2) adding 1g of spherical silica synthesized in the step (1) and 50mL of ethanol into a 100mL flask, then adding a silane coupling agent with the mass being 10 wt% of the mass of the carrier, reacting the mixed solution at 25 ℃ in a nitrogen atmosphere, centrifuging for 24h by using a desktop high-speed centrifuge to remove the residual solvent, repeatedly washing the residual product with ethanol and acetone for 3 times, and finally drying in vacuum at 70 ℃ overnight to obtain the modified silica carrier.
And (3) adding 0.15g of spherical silicon dioxide synthesized in the step (2) and 100mL of ethanol into a 100mL three-neck flask, then adding 0.1g of ionic liquid monomer, then adding 0.3 wt% of oil-soluble initiator Azobisisobutyronitrile (AIBN) in mass of the monomer, then carrying out free radical polymerization reaction on the mixed solution at 70 ℃ under nitrogen atmosphere, after 24h of reaction, removing residual solvent by using a rotary evaporator, repeatedly washing the residual product for 3 times by using diethyl ether and acetone, finally carrying out vacuum drying at 70 ℃ overnight to obtain the core-shell polyion liquid polymer 1, and determining the stability.
By increasing and changing the mass of the polymerized monomer or changing the adding amount of the initiator, the core-shell type polyionic liquid with any structure and polymerization degree can be obtained by the person skilled in the art.
In each example of the present invention, the yield of the product was quantitatively determined by gas chromatography of model 8890GC-TCD, manufactured by Agilent.
Example 1
Putting 273mmol of propylene oxide and 100mg of core-shell ionic liquid polymer 1 powder with the particle size of 100nm into a 100mL closed reaction kettle, uniformly mixing, keeping the temperature of the reaction kettle at 120 ℃, continuously introducing carbon dioxide gas into the reaction kettle, keeping the pressure of a reaction system in the kettle at 2MPa, and carrying out addition reaction for 2h to obtain a product propylene carbonate, wherein the yield of the propylene carbonate is 95.5%.
The structure of the core-shell ionic liquid polymer is synthesized by the formula I
The formula II is as follows:
Figure RE-GDA0003530618560000071
example 2
The difference from example 1 is only that the mass ratio of silica to monomer in the core-shell type ionic liquid polymer 1 is changed from 1:1.5 to 1:0.5, and the core-shell type ionic liquid polymer 2 is obtained.
Example 2 the product propylene carbonate was obtained in 89.7% yield.
Example 3
The difference from example 1 is only that the mass ratio of silica to monomer in the core-shell type ionic liquid polymer 1 is changed from 1:1.5 to 1:1, and the core-shell type ionic liquid polymer 3 is obtained.
Example 3 the product propylene carbonate was obtained in a yield of 91.8%.
Example 4
The difference from example 1 is only that the mass ratio of silica to monomer in the core-shell ionic liquid polymer 1 is changed from 1:1.5 to 1:2, and the core-shell ionic liquid polymer 4 is obtained.
Example 4 gave the product propylene carbonate in a yield of 81.6%.
Example 5
The difference from example 1 is only that the mass ratio of silica to monomer in the core-shell ionic liquid polymer 1 was changed from 1:0.5 to 1:2.5 to obtain a core-shell ionic liquid polymer 5.
Example 5 gave the product propylene carbonate in 83.2% yield.
Example 6
The difference from example 1 is only that the mass ratio of silica to monomer in the core-shell ionic liquid polymer 1 is changed from 1:0.5 to 1:3 to obtain a core-shell ionic liquid polymer 6.
Example 6 gave the product propylene carbonate in a yield of 76.1%.
Example 7
The only difference from example 1 is that the temperature of the reaction kettle is controlled at 100 ℃, the pressure of the reaction system in the kettle is controlled at 2MPa, and the time of the addition reaction is 2 h.
Example 7 gave the product propylene carbonate in a yield of 55.9%.
Example 8
The only difference from example 1 is that the temperature of the reaction kettle is controlled at 110 ℃, the pressure of the reaction system in the kettle is controlled at 3MPa, and the time of the addition reaction is 2 h.
Example 8 gave the product propylene carbonate in a yield of 76%.
Example 9
The only difference from example 1 is that the temperature of the reaction kettle is controlled at 130 ℃, the pressure of the reaction system in the kettle is controlled at 3MPa, and the time of the addition reaction is 2 h. .
Example 9 gave the product propylene carbonate in a yield of 96.2%.
Example 10
The only difference from example 1 is that the temperature of the reaction kettle is controlled at 140 ℃, the pressure of the reaction system in the kettle is controlled at 3MPa, and the time of the addition reaction is 2 h.
Example 10 gave the product propylene carbonate in 97.2% yield.
Example 11
The only difference from example 1 is that the temperature of the reaction kettle is controlled at 120 ℃, the pressure of the reaction system in the kettle is controlled at 1.5MPa, and the time of the addition reaction is 2 h.
Example 11 gave the product propylene carbonate in a yield of 96.4%.
Example 12
The only difference from example 1 is that the propylene oxide therein was replaced by the same molar amount of styrene oxide.
Example 12 gave styrene carbonate as a product in a yield of 90.1%.
Comparative example 1
The only difference from example 1 is the unmodified silica of the catalyst used, the other conditions being unchanged.
Comparative example 1 gave a product of propylene carbonate having a yield of 7.6%.
Comparative example 2
The only difference from example 1 is that the catalyst used was silica modified with a silane coupling agent, and the other conditions were unchanged.
Comparative example 2 gave a product of propylene carbonate with a yield of 4.9%.
Comparative example 3
The only difference from example 1 is that the catalyst used is brominated 1-butyl-3-vinylimidazole, the other conditions remaining unchanged.
Comparative example 3 gave the product propylene carbonate in a yield of 93.8%.
Comparative example 4
The only difference from example 1 is that the catalyst used is polymerized brominated 1-butyl-3-vinylimidazole, the other conditions remaining unchanged.
Comparative example 4 gave the product propylene carbonate in a yield of 92.9%.
In conclusion, the invention provides a novel core-shell type polymerization ionic liquid heterogeneous catalyst, which is used for catalyzing carbon dioxide and an epoxy group-containing compound to perform addition cycloaddition reaction to obtain cyclic carbonate. The cyclic carbonate prepared by the method has high selectivity and conversion rate, and the purity of the obtained cyclic carbonate product can reach 99.9%. Compared with the traditional method for preparing cyclic carbonate, the core-shell type polymerization ionic liquid catalyst used in the invention has the advantages of more active sites, high catalytic efficiency, stability, difficult decomposition, simple preparation process, less addition amount, easy separation from a liquid phase and the like, and has higher industrial application value.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for synthesizing cyclic carbonate ester based on core-shell type polymeric ionic liquid catalysis is characterized in that the core-shell type polymeric ionic liquid has the following preparation processes:
Figure FDA0003499977350000011
wherein m and n are independently selected from any natural number, and m + n is more than or equal to 4;
R1independently selected from a hydrogen atom or any one of an alkane group;
R2each independently selected from any one functional group;
R3～R4each independently selected from any alkane group;
a is independently selected from any one halide anion;
R5each independently selected from any one of an alkane group, a hydroxyl-terminated alkane group, a carboxyl-terminated alkane group or a sulfonate-terminated alkane group;
wherein a, b and c represent the mass of a carrier, an ionic liquid monomer and a cross-linking agent added in the synthesis process, a: b is 1: 0.1-200, and b: c is 1: 0.1-1.
The size of the synthesized core-shell type polymerization ionic liquid catalyst is 1-1000 nm,
2. according to claimThe process of claim 1, characterized in that CO is used2And preparing cyclic carbonate by using a cyclic compound as a raw material:
wherein the mass ratio of the addition amount of the catalyst to the epoxy compound is 1: 2-200;
the reaction temperature of the cycloaddition reaction is 30-180 ℃;
the reaction pressure of the cycloaddition reaction is 0.1-8 MPa;
the reaction time of the cycloaddition reaction is 0.25-24 h.
3. The production method according to claim 2;
preferably, the mass ratio of the addition amount of the catalyst to the epoxy compound is 1: 2-10;
preferably, the reaction temperature of the cycloaddition reaction is 80-150 ℃;
preferably, the reaction pressure of the cycloaddition reaction is 1-5 MPa;
preferably, the reaction time of the cycloaddition reaction is 1-8 h.
4. The method according to any one of claims 1 to 3, wherein the epoxy compound is any one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide, cyclohexene oxide, and cyclopentane oxide.
5. The method according to claim 1, wherein R in the structure represented by formula I1Independently selected from a hydrogen atom or any one of an alkane group; r2Independently selected from any one functional group; r3～R4Each independently selected from any one alkane group;
preferably, R1Hydrogen atom, methyl or ethyl;
preferably, R2Aldehyde group, carbonyl, benzyl, phenyl, ester group and the like.
Preferably, R3～R4Any alkane radical with the carbon atom number less than or equal to 4 is selected.
6. The method according to claim 1, wherein R in the structure represented by formula I5Independently selected from any one of an alkane group, a hydroxyl-terminated alkane group, a carboxyl-terminated alkane group or a sulfonate-terminated alkane group;
preferably, R5Any one group independently selected from methyl, ethyl, butyl or hydroxyethyl;
7. the preparation method according to claim 1, wherein in the structure shown in formula I, A is selected from any one of halogen anions, such as fluorine, bromine, chlorine, iodine and the like;
preferably, a is selected from bromide.
8. The preparation method according to claim 1, wherein a, b and c represent the mass of the carrier, ionic liquid monomer and cross-linking agent added during the synthesis, and a, b and c are each independently selected from any natural number;
preferably, in the synthesis process, a: b is 1:0.5-1:10, and b: c is 1: 0.25.
9. The method according to claim 1, wherein the catalyst has a particle size of 1 to 1000 nm; preferably, the particle size of the catalyst is 10-100 nm.
10. The production method according to any one of claims 1 to 9, wherein the evaluation method comprises the steps of:
and (2) placing the epoxy compound and catalyst powder with the particle size of 10-100 nm into a closed reaction kettle, uniformly mixing, maintaining the temperature of the reaction kettle within the range of 80-150 ℃, continuously introducing carbon dioxide gas into the reaction kettle, maintaining the pressure of a reaction system in the kettle within the range of 1-5 MPa, and performing addition reaction for 1-8 hours to obtain the cyclic carbonate.
CN202210124685.5A 2022-02-10 2022-02-10 Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid Pending CN114433228A (en)

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