CN111393402A - Br nsted acid/quaternary ammonium salt composite catalytic CO2Method for preparing cyclic carbonate by cycloaddition with epoxide - Google Patents

Br nsted acid/quaternary ammonium salt composite catalytic CO2Method for preparing cyclic carbonate by cycloaddition with epoxide Download PDF

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CN111393402A
CN111393402A CN202010217715.8A CN202010217715A CN111393402A CN 111393402 A CN111393402 A CN 111393402A CN 202010217715 A CN202010217715 A CN 202010217715A CN 111393402 A CN111393402 A CN 111393402A
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acid
epoxide
quaternary ammonium
ammonium salt
cyclic carbonate
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CN111393402B (en
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王正
申烨华
谢倩杰
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Northwestern University
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    • 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
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • 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
    • 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
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C07D317/38—Ethylene carbonate
    • 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
    • C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations

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Abstract

The invention discloses a
Figure DDA0002424953660000011
Acid/quaternary ammonium salt composite catalysis CO2Method for preparing cyclic carbonate by cycloaddition with epoxide, and is suitable for various types of epoxide and CO2At the reaction temperature<100℃、CO2Pressure of<The method for catalytically synthesizing the cyclic carbonate under the operating condition of 1MPa has the characteristics of high catalytic efficiency, mild condition, high yield, high selectivity, no need of adding any solvent, easy separation of products after reaction and the like. The catalyst system is cheap and easy to obtain, and can efficiently utilize CO2The gas is a mixture of a gas and a water,has important significance for reducing carbon emission and relieving ecological environment crisis and is expected to become CO2The catalyst is used for preparing the next generation catalyst for the industrial production of the cyclic carbonate by cycloaddition with epoxide.

Description

Acid/quaternary ammonium salt composite catalysis CO2Method for preparing cyclic carbonate by cycloaddition with epoxide
Technical Field
The invention belongs to the technical field of preparation of cyclic carbonate, and particularly relates to a metal-free polycarbonate
Figure BDA0002424953650000012
Cheap acid/quaternary ammonium salt composite catalyst for catalyzing CO under mild condition2Preparation of cyclic carbonates by cycloaddition with epoxidesA method.
Background
The cyclic carbonate is an important chemical raw material and has wide application in the fields of textile printing and dyeing, plastic synthesis, electrochemistry, desorption of carbon dioxide and hydrogen sulfide, synthesis of medicine and fine chemical intermediates and the like; meanwhile, as an intermediate product, a wide variety of downstream products can be developed, such as dimethyl carbonate prepared by the transesterification of methanol from ethylene carbonate, which is already produced industrially in high tonnage. In addition, CO2The cycloaddition reaction with epoxide has important significance for reducing carbon emission and relieving the crisis of the ecological environment. In recent decades, the study of this reaction and in particular the development of new catalysts has attracted the attention of more and more researchers.
Many catalytic systems including organic bases, ionic liquids, ionic salts, transition metal organic complexes, metal organic framework materials, etc. (Energy environ.sci.,2014,7, 130; catal.sci.technol.,2014,4, 1513; coord.chem.rev.,1999,181, 27; mater.horiz.,2017,4,345) have been reported so far, for example: japanese patent JP 31-981 discloses that a yield of 90% cyclic carbonate is obtained using a combination of a Lewis acid and an organic base at 100 to 400 ℃ and 2 to 29 MPa; chinese patent CN 1432557A discloses a method for synthesizing ethylene carbonate by using tetraethylammonium bromide as a catalyst>130 ℃ and>a yield of 95% was obtained under 3 MPa; chinese patent CN 100410247C discloses a method for synthesizing cyclic carbonate by using chitosan-loaded zinc chloride and ionic liquid through composite catalysis, wherein the cyclic carbonate is synthesized at 100 ℃ and constant CO2Yields of over 99% were obtained under pressure; chinese patent CN101037431A discloses a method for catalytically synthesizing cyclic carbonate by using ionic liquid, metal salt and quaternary ammonium salt composite catalyst, wherein CO is constant at 1.5MPa and at 100 DEG C2Yields of over 99% were obtained under pressure conditions. However, these catalysts have the problems of low catalytic efficiency, high preparation cost, harsh reaction conditions, complex post-reaction treatment process, and the like. Therefore, the green preparation method for the cyclic carbonate with low price, high catalytic efficiency, mild catalytic conditions, high speed, high efficiency and high selectivity, which is easy to separate from the product, is developedEnvironmentally friendly catalysts are very important.
Disclosure of Invention
The invention aims to provide a method for preparing a catalyst by using a cheap metal-free composite catalyst
Figure BDA0002424953650000021
Acid and quaternary ammonium salt, under relatively mild conditions, efficiently and environmentally friendly to realize CO2Cycloaddition with epoxide to produce cyclic carbonate.
Aiming at the purposes, the technical scheme adopted by the invention is as follows: an epoxide, a,
Figure BDA0002424953650000022
The acid and the quaternary ammonium salt are put into a high-pressure reaction kettle, and CO is introduced into the high-pressure reaction kettle2And (3) heating the gas to the pressure of 0.3-1 MPa, heating the high-pressure reaction kettle to 60-80 ℃, and stirring and reacting at constant temperature for 1-5 hours.
The epoxide is any one of ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, styrene oxide, allyl glycidyl ether and cyclohexene oxide.
The above
Figure BDA0002424953650000023
The acid is any one of formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, isobutyric acid, methacrylic acid, valeric acid, pivalic acid, caproic acid, benzoic acid, oleic acid, succinic acid, trimesic acid, phosphoric acid and hydrobromic acid, and preferably any one of acetic acid, propionic acid, formic acid, acrylic acid, butyric acid, isobutyric acid, valeric acid, succinic acid and trimesic acid.
The quaternary ammonium salt is any one of tetrabutylammonium chloride, tetrabutylammonium bromide, tetraethylammonium chloride and tetraethylammonium bromide.
In the above process, the epoxide is reacted with
Figure BDA0002424953650000026
The molar ratio of the acid to the quaternary ammonium salt is 1: 0.01-0.2, and preferably the molar ratio of the epoxide to the quaternary ammonium salt is
Figure BDA0002424953650000025
The molar ratio of the acid to the quaternary ammonium salt is 1: 0.05-0.15.
In the above method, it is further preferable that CO is introduced into the high-pressure reactor2And (3) heating the high-pressure reaction kettle to 80 ℃ until the pressure of the gas is 0.4-0.6 MPa, and stirring and reacting for 3 hours at constant temperature.
The invention has the following beneficial effects:
the reaction system is simple, and no solvent or metal salt compound is required to be added; the reaction condition is mild and can be in<100 ℃ (60-80 ℃) and<triggering reaction under the condition of 1 MPa; use of
Figure BDA0002424953650000024
The acid/quaternary ammonium salt catalyst is low in price, efficient, environment-friendly, easy to operate, high in catalytic efficiency, high in product yield and selectivity, and capable of achieving 100% selectivity and 99% yield of partial products within 0.5-3 hours; the product after reaction is easy to separate when used
Figure BDA0002424953650000027
When the acid is an organic carboxylic acid, the reaction is completed and then cooled to room temperature, white quaternary ammonium carboxylate is precipitated, and HBr or HCl remained in the product can be removed by using an alkali substance insoluble in the cyclic carbonate, when used
Figure BDA0002424953650000028
When the acid is inorganic acid, the acid can be separated and purified by direct reduced pressure distillation; can efficiently utilize CO2The gas has important significance for reducing carbon emission and relieving the crisis of the ecological environment, and is expected to realize CO2And the cyclic carbonate is prepared by cycloaddition with epoxide.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
In the following examples, the product yields and selectivities were determined by Nuclear Magnetic Resonance (NMR)When the used epoxide is ethylene oxide, propylene oxide or butylene oxide with low boiling point, the reaction is cooled to below 0 ℃ after the reaction is finished, and sampling analysis is carried out; simultaneously separating and purifying the product and the catalyst; when used, the
Figure BDA0002424953650000032
When the acid is an organic carboxylic acid, white quaternary ammonium carboxylate precipitates on cooling to room temperature after the reaction is completed, and HBr or HCl remaining in the product is removed with an alkali substance such as sodium carbonate and sodium hydrogencarbonate, etc., which are insoluble in the cyclic carbonate; when used, the
Figure BDA0002424953650000033
When the acid is inorganic acid, the acid is directly separated and purified by reduced pressure distillation.
Example 1
Figure BDA0002424953650000031
68.9 μ L (1.26mmol) of acetic acid, 0.405g (1.26mmol) of tetrabutylammonium bromide and 1.1m L (15.7mmol) of propylene oxide are added into a 90m L high-pressure reaction kettle in sequence, the reaction kettle is quickly sealed, and then the reaction kettle is filled with CO2The pressure of the gas in the reaction kettle is 0.4 MPa; then placing the reaction kettle in an oil bath at the temperature of 80 ℃ to stir for reaction for 3 hours, after the reaction is finished, placing the reaction kettle in ice water to cool to room temperature, and slowly releasing CO2Then, the precipitated tetrabutylammonium acetate is filtered, sodium bicarbonate is added into the filtrate, the mixture is stirred and filtered evenly, and the filtrate is the pure product of the target product propylene carbonate, wherein the yield is 97.3 percent, and the selectivity is 100 percent.
Example 2
In this example, CO was charged2The pressure of the gas in the reaction kettle is 0.5MPa, other steps are the same as the example 1, the target product propylene carbonate is obtained, and the yield is high>99% and selectivity 100%.
Example 3
In this example, acetic acid in example 1 was replaced with an equimolar amount of propionic acid, and CO was charged2Gas to reaction kettle pressure of 0.5MPa, other steps and implementationThe same as in example 1, the target product propylene carbonate is obtained in yield>99% and selectivity 100%.
Example 4
In this example, the acetic acid in example 1 was replaced with an equal mole of formic acid, and the other steps were the same as in example 1, to obtain propylene carbonate as a target product with a yield of 98% and a selectivity of 100%.
Example 5
In this example, the acetic acid in example 1 was replaced with an equimolar amount of propionic acid, and the other steps were the same as in example 1, whereby propylene carbonate as an object was obtained in a yield of 95% and a selectivity of 100%.
Example 6
In this example, the target propylene carbonate was obtained in a yield of 96.9% and a selectivity of 100% by the same procedure as in example 1 except that acetic acid in example 1 was replaced with an equal mole of acrylic acid.
Example 7
In this example, the acetic acid in example 1 was replaced with an equimolar amount of butyric acid, and the other steps were the same as in example 1, to obtain propylene carbonate as a target product with a yield of 99% and a selectivity of 100%.
Example 8
In this example, the acetic acid in example 1 was replaced by equimolar isobutyric acid and the other steps were the same as in example 1 to obtain propylene carbonate as the target product in a yield of > 99% with a selectivity of 100%.
Example 9
In this example, the target propylene carbonate was obtained in a yield of 84.7% and a selectivity of 100% by the same procedure as in example 1 except that acetic acid in example 1 was replaced with an equal mole of methacrylic acid.
Example 10
In this example, the acetic acid in example 1 was replaced with an equal mole of valeric acid, and the other steps were the same as in example 1, to obtain the target product propylene carbonate with a yield of 97.1% and a selectivity of 100%.
Example 11
In this example, the acetic acid in example 1 was replaced with an equal mole of pivalic acid, and the other steps were the same as in example 1, to obtain propylene carbonate as a target product with a yield of 84.7% and a selectivity of 100%.
Example 12
In this example, acetic acid in example 1 was replaced with an equimolar amount of caproic acid, and the other steps were the same as in example 1, to obtain propylene carbonate as a target product with a yield of 93.5% and a selectivity of 100%.
Example 13
In this example, the acetic acid in example 1 was replaced with equimolar benzoic acid, and the other steps were the same as in example 1, to obtain propylene carbonate as a target product in a yield of 88.5% and a selectivity of 100%.
Example 14
In this example, the acetic acid in example 1 was replaced with an equimolar amount of oleic acid, and the other steps were the same as in example 1, whereby propylene carbonate was obtained as a target product in a yield of 82.6% and a selectivity of 100%.
Example 15
In this example, acetic acid in example 1 was replaced with equimolar succinic acid, and the other steps were the same as in example 1, to obtain propylene carbonate as a target product with a yield of 95.2% and a selectivity of 100%.
Example 16
In this example, the target propylene carbonate was obtained in a yield of 95% and a selectivity of 100% by the same procedure as in example 1 except that the acetic acid in example 1 was replaced with an equimolar amount of trimesic acid.
Example 17
In this example, equimolar phosphoric acid was used instead of acetic acid in example 1, and after the reaction, the mixture was separated and purified by distillation under reduced pressure, and the other steps were the same as in example 1, to obtain propylene carbonate as a target product with a yield of 80.6% and a selectivity of 100%.
Example 18
In this example, acetic acid in example 1 was replaced with equimolar hydrobromic acid, and after completion of the reaction, the mixture was separated and purified by distillation under reduced pressure, and the other steps were the same as in example 1 to obtain propylene carbonate as an object in a yield of 81.3% and a selectivity of 100%.
Example 19 in this example, the procedure was the same as in example 1 except that tetrabutylammonium bromide in example 1 was replaced with an equimolar amount of tetrabutylammonium chloride, and the target product propylene carbonate was obtained in a yield of 98% and a selectivity of 100%.
Example 20
In this example, the tetrabutylammonium bromide in example 1 was replaced with an equal mole of tetraethylammonium chloride, and the other steps were the same as in example 1, to obtain the target product propylene carbonate with a yield of 95% and a selectivity of 100%.
Example 21
In this example, the tetrabutylammonium bromide in example 1 was replaced with equimolar tetraethylammonium bromide, and the other steps were the same as in example 1, to obtain the target product propylene carbonate with a yield of 96% and a selectivity of 100%.
Example 22
Figure BDA0002424953650000051
In this example, propylene oxide from example 1 was replaced with an equimolar amount of ethylene oxide, and CO was charged2The pressure of the gas to the reaction kettle is 0.5MPa, other steps are the same as the example 1, the target product ethylene carbonate is obtained, and the yield is high>99% and selectivity 100%.
Example 23
In this example, the acetic acid in example 22 was replaced by an equimolar amount of propionic acid and the other procedure was the same as in example 22 to obtain the desired product, ethylene carbonate, in a yield of > 99% with a selectivity of 100%.
Example 24
Figure BDA0002424953650000061
In this example, the ethylene oxide in example 22 was replaced with an equimolar amount of epichlorohydrin, and the other steps were the same as in example 22 to obtain the desired 4-chloromethyl- [1,3] dioxolan-2-one in a yield of 98% and a selectivity of 100%.
Example 25
In this example, the acetic acid in example 24 was replaced with an equimolar amount of propionic acid and the other procedures were the same as in example 24 to obtain the desired product, 4-chloromethyl- [1,3] dioxolan-2-one, in a yield of 97.1% with a selectivity of 100%.
Example 26
Figure BDA0002424953650000062
In this example, the ethylene oxide in example 22 was replaced with an equimolar amount of chlorobutylene oxide, and the other steps were the same as in example 22, to obtain a target product, butenylcarbonate, in a yield of 99% and a selectivity of 100%.
Example 27
In this example, acetic acid in example 26 was replaced with an equimolar amount of propionic acid, and the other steps were the same as in example 26, to obtain a target product, butenylcarbonate, in a yield of 99% and a selectivity of 100%.
Example 28
Figure BDA0002424953650000071
In this example, the ethylene oxide in example 22 was replaced with an equimolar amount of allyl glycidyl ether, and the other steps were carried out in the same manner as in example 22 to obtain 4- [ (2-propenyloxy) methyl ] -1, 3-dioxolan-2-one as a target product in a yield of 94.3% and a selectivity of 100%.
Example 29
In this example, the desired 4- [ (2-propenyloxy) methyl ] -1, 3-dioxolan-2-one was obtained in the same manner as in example 28 except that acetic acid in example 28 was replaced with an equimolar amount of propionic acid in a yield of 88.5% and a selectivity of 100%.
Example 30
Figure BDA0002424953650000072
In this example, the ethylene oxide in example 22 was replaced with styrene oxide in equimolar amount, and the other steps were the same as in example 22 to obtain 4-benzo- [1,3] dioxolan-2-one as a target product in a yield of 83.3% with a selectivity of 100%.
Example 31
In this example, acetic acid in example 30 was replaced with an equimolar amount of propionic acid, and the other steps were the same as in example 30 to obtain 4-benzo- [1,3] dioxolan-2-one as a target product in a yield of 83.3% with a selectivity of 100%.
Example 32
Figure BDA0002424953650000073
In this example, the target product, cyclohexyl [1,3] dioxolan-2-one, was obtained in a yield of 72% and a selectivity of 100%, in the same manner as in example 22 except that ethylene oxide in example 22 was replaced with an equimolar amount of cyclohexene oxide.
Example 33
In this example, acetic acid in example 32 was replaced with an equimolar amount of propionic acid, and the other procedure was conducted in the same manner as in example 32 to obtain cyclohexyl [1,3] dioxolan-2-one as a target product in a yield of 65% and a selectivity of 100%.
Example 34
In this example, acetic acid was used in an amount of 8.6. mu. L (0.157mmol), tetrabutylammonium bromide was used in an amount of 0.051g (0.157mmol), and CO was charged2The pressure from the gas to the reaction kettle is 0.8MPa, the reaction time is 5 hours, other steps are the same as the example 1, the target product propylene carbonate is obtained, the yield is 91%, and the selectivity is 100%.
Example 35
In this example, acetic acid was used in an amount of 8.6. mu. L (0.157mmol), tetrabutylammonium bromide was used in an amount of 0.051g (0.157mmol), and CO was charged2The pressure of the gas to the reaction kettle is 0.5MPa, the reaction temperature is 60 ℃, the reaction time is 5 hours, other steps are the same as the example 1, the target product propylene carbonate is obtained, the yield is 96.4%, and the selectivity is 100%.

Claims (7)

1. A kind of
Figure FDA0002424953640000011
Acid/quaternary ammonium salt composite catalysis CO2A method for preparing cyclic carbonate by cycloaddition with epoxide is characterized in that: an epoxide, a,
Figure FDA0002424953640000012
The acid and the quaternary ammonium salt are put into a high-pressure reaction kettle, and CO is introduced into the high-pressure reaction kettle2Heating the gas to the pressure of 0.3-1 MPa, heating the high-pressure reaction kettle to 60-80 ℃, and stirring and reacting at constant temperature for 1-5 hours;
the above
Figure FDA0002424953640000013
The acid is any one of formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, isobutyric acid, methacrylic acid, valeric acid, pivalic acid, caproic acid, benzoic acid, oleic acid, succinic acid, trimesic acid, phosphoric acid and hydrobromic acid;
the quaternary ammonium salt is any one of tetrabutylammonium chloride, tetrabutylammonium bromide, tetraethylammonium chloride and tetraethylammonium bromide.
2. The method of claim 1
Figure FDA0002424953640000014
Acid/quaternary ammonium salt composite catalysis CO2A method for preparing cyclic carbonate by cycloaddition with epoxide is characterized in that: the epoxide is any one of ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, styrene oxide, allyl glycidyl ether and cyclohexene oxide.
3. The method of claim 1
Figure FDA0002424953640000015
Acid/quaternary ammonium salt composite catalysis CO2Cycloaddition preparation with epoxidesA process for the preparation of a cyclic carbonate, characterized in that: said
Figure FDA0002424953640000016
The acid is any one of acetic acid, propionic acid, formic acid, acrylic acid, butyric acid, isobutyric acid, valeric acid, succinic acid and trimesic acid.
4. The method according to any one of claims 1 to 3
Figure FDA0002424953640000017
Acid/quaternary ammonium salt composite catalysis CO2A method for preparing cyclic carbonate by cycloaddition with epoxide is characterized in that: said epoxide and
Figure FDA0002424953640000018
the molar ratio of the acid to the quaternary ammonium salt is 1: 0.01-0.2.
5. The method of claim 4
Figure FDA0002424953640000019
Acid/quaternary ammonium salt composite catalysis CO2A method for preparing cyclic carbonate by cycloaddition with epoxide is characterized in that: said epoxide and
Figure FDA00024249536400000110
the molar ratio of the acid to the quaternary ammonium salt is 1: 0.05-0.15.
6. The method of claim 1
Figure FDA00024249536400000111
Acid/quaternary ammonium salt composite catalysis CO2A method for preparing cyclic carbonate by cycloaddition with epoxide is characterized in that: introducing CO into the high-pressure reaction kettle2The gas is pressurized to 0.4 to 0.6 MPa.
7. The method of claim 1 or 6
Figure FDA00024249536400000112
Acid/quaternary ammonium salt composite catalysis CO2A method for preparing cyclic carbonate by cycloaddition with epoxide is characterized in that: heating the high-pressure reaction kettle to 80 ℃, and stirring and reacting for 3 hours at constant temperature.
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