Catalyst for synthesis of glycerol carbonate from carbon dioxide and glycerol, preparation method and application thereof

Abstract

The application discloses a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, a preparation method and application thereof, wherein the catalyst is a DBU onium polyion liquid, is applied to a one-pot method for synthesizing glycerol carbonate from carbon dioxide, glycerol and an epoxide compound, and is easier to separate and reuse while keeping higher catalytic activity, so that the operation cost is lower.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalysis technology, in particular, to a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, a preparation method and applications thereof. BACKGROUND

[0002] The massive use of fossil fuels leads to excessive carbon dioxide emissions, which exacerbates the greenhouse effect and extreme climate change. At the same time, carbon dioxide is widely available, abundant, low-cost and non-toxic, making it an attractive C1 raw material. Converting carbon dioxide into high-value-added products not only can alleviate the greenhouse effect, but also can improve the efficiency of waste resource utilization.

[0003] Glycerol can be derived from the production of renewable energy biodiesel, with a yield of about 10wt% of the biodiesel production. With the rapid development of the biodiesel industry, there is a large surplus of glycerol, and the oversupply leads to a rapid decline in the price of glycerol. At the same time, the treatment of excess crude glycerol also puts a certain pressure on the environment. Therefore, converting glycerol into high-value-added chemical products not only can reduce the pressure brought by the overcapacity of glycerol, but also can help improve the economic efficiency of the development of the biodiesel industry. Through different chemical reactions, a variety of chemical products can be synthesized from glycerol, such as glycerol carbonate, 1,3-propanediol and acrolein, etc.

[0004] Glycerol carbonate has many excellent properties, such as high boiling point, high flash point, low freezing point, low volatility, low toxicity, no odor and no pollution, strong polarity, good water solubility and biodegradability, etc. Due to these excellent properties, glycerol carbonate is considered as a green solvent and is widely used in the fields of glue, cosmetics, pharmaceuticals, dyes, varnish, detergents, adhesives, biological lubricants and electrolytes, etc. Glycerol carbonate molecules contain two active groups of hydroxyl and carbonyl, which can react with alcohol, amine, carboxylic acid, isocyanate, etc. to produce a variety of derivatives, including intermediates of polyesters, polycarbonates, polyamine esters, polyamides and other polymers.

[0005] The preparation of glycerol carbonate from carbon dioxide and glycerol has attracted extensive interest. This route can realize the co-conversion of large amounts of emitted carbon dioxide and industrial excess product glycerol, which not only effectively utilizes carbon dioxide, but also promotes the development of the biodiesel industry. However, the direct conversion of carbon dioxide and glycerol is limited by thermodynamics, and the yield of glycerol carbonate is still low under extremely harsh conditions. For example, Indiana University reported that in a eutectic solvent, using a Schiff base as a catalyst and a molecular sieve as a dehydrating agent, the yield of glycerol carbonate was only 8% after 24h of reaction at 0.7MPa and 90℃. By adding high-energy epoxide compounds, the reaction can be realized in one pot, which can be divided into two steps that are easy to occur: (1) carbon dioxide and epoxide compounds undergo cycloaddition to form cyclic carbonates; (2) cyclic carbonates exchange with glycerol to form glycerol carbonate and diols. Sichuan University reported in CN113816852A that using an organic amine halide homogeneous catalyst, due to its high catalytic and mass transfer capacity, it realized the efficient synthesis of glycerol carbonate from carbon dioxide, glycerol and epoxide compounds by "one-pot" reaction under mild conditions, and obtained a glycerol carbonate yield of 92%. However, the homogeneous catalyst reported in the patent is difficult to separate from the reaction system, resulting in increased cost and difficulty in large-scale utilization. Non-heterogeneous catalysts such as MgO (Fuel, 2023, 335: 126972.) are reported in the literature to catalyze the synthesis of glycerol carbonate from carbon dioxide, glycerol and epoxide compounds by "one-pot" reaction. However, the above non-heterogeneous catalysts can only obtain a maximum glycerol carbonate yield of 81%, and the catalytic effect is not ideal. Therefore, it is very important to develop a high-efficiency, easy-to-separate and stable non-heterogeneous catalyst for the synthesis of glycerol carbonate from carbon dioxide, glycerol and epoxide compounds by "one-pot" reaction.

[0006] In view of this, the present application is proposed. SUMMARY

[0007] The present application aims to provide a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, a preparation method and applications thereof, and to overcome the shortcomings of the existing catalysts for synthesizing glycerol carbonate from carbon dioxide, glycerol and alkylene oxide, which are difficult to recycle.

[0008] The present application is implemented as follows:

[0009] In a first aspect, the present application provides a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, comprising a polymer containing a unit of formula 1:

[0010]

[0011] wherein R is an alkyl group with 1-10 carbon atoms, and X is I - , Br - or Cl - .

[0012] It should be noted that since the nucleophilicity of halide anion is the key to the ring opening of alkylene oxide, and the protonated organic amine cation is also conducive to the ring opening of alkylene oxide, the unit comprising formula 1 can play a catalytic role in the "one-pot" synthesis of glycerol carbonate from carbon dioxide, glycerol and epoxide. Wherein R can be a straight-chain alkyl group containing 1-10 carbon atoms or an alkyl group containing a branched chain.

[0013] Compared with the reported homogeneous catalysts for the "one-pot" synthesis of glycerol carbonate from carbon dioxide, glycerol and epoxide, the 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) onium polyionic liquid catalyst obtained in the present application has higher catalytic activity while being more easily separated and reused due to polymerization, thereby reducing the operation cost; and compared with the reported homogeneous catalysts for the "one-pot" synthesis of glycerol carbonate from carbon dioxide, glycerol and epoxide, the DBU onium polyionic liquid catalyst in the present application is easy to recycle while having high catalytic activity, and has more industrial application prospects.

[0014] In some optional embodiments, a polymer comprising units of formula 1 is included.

[0015] In some optional embodiments, a polymer comprising units of formula 2 is included,

[0016]

[0017] Wherein, CR is a group containing a phenyl group, an alcohol ester group or an amide group.

[0018] In a second aspect, the present application provides a preparation method of the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to any one of the preceding embodiments, comprising polymerizing monomers formed by 1,8-diazabicyclo[5.4.0]undec-7-ene and a vinyl halogenated alkylbenzene to obtain the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol.

[0019] Wherein, when R is methylene, the monomers formed by 1,8-diazabicyclo[5.4.0]undec-7-ene and a vinyl benzyl halide are as shown in formula 3, and the monomers of formula 3 can be homopolymerized or copolymerized under the action of a crosslinking agent to obtain the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol.

[0020]

[0021] In some optional embodiments, the preparation of the monomers is also included: taking 1,8-diazabicyclo[5.4.0]undec-7-ene and a vinyl halogenated alkylbenzene as reactants, and performing a quaternary ammonium reaction in a first solvent to generate the monomers.

[0022] Preferably, the molar ratio of 1,8-diazabicyclo[5.4.0]undec-7-ene and vinyl halogenated alkylbenzene is 0.25-4:1;

[0023] Preferably, the initial concentration of vinyl halogenated alkylbenzene in the first solvent is 0.1-2 mol / L;

[0024] Preferably, the vinyl halogenated alkylbenzene is one of 4-vinylbenzyl iodide, 4-vinylbenzyl bromide and 4-vinylbenzyl chloride;

[0025] Preferably, the first solvent is acetonitrile;

[0026] Preferably, the temperature of the quaternization reaction is 0-70°C, and the time is 4-24 h;

[0027] Preferably, the product is washed and subjected to the first vacuum drying after the quaternization reaction is completed to obtain the monomer;

[0028] More preferably, the crude product is washed with diethyl ether after the quaternization reaction is completed;

[0029] More preferably, the temperature of the first vacuum drying is 40-80°C, and the time is 4-12 h.

[0030] In some optional embodiments, the polymerization step comprises placing the reactants in a second solvent to perform a polymerization reaction to obtain the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol; the reactants comprise a monomer and an initiator;

[0031] Preferably, the initiator is azobisisobutyronitrile, and the initiator accounts for 2.5-20 wt% of the total mass of the reactants;

[0032] Preferably, the second solvent is methanol, and the second solvent accounts for 50-200 wt% of the total mass of the reactants;

[0033] Preferably, the reactants further comprise a crosslinking agent, and the molar ratio of the crosslinking agent to the monomer is 0-4:1;

[0034] Preferably, the temperature of the polymerization reaction is 60-100°C, and the time is 4-24 h;

[0035] Preferably, the product is washed and subjected to the second vacuum drying after the polymerization reaction is completed to obtain the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol;

[0036] More preferably, the crude product is washed with methanol and ethanol respectively after the polymerization reaction is completed;

[0037] More preferably, the second vacuum drying is performed at a temperature of 40-80℃ for 4-12h.

[0038] In some alternative embodiments, the reaction mixture further comprises a crosslinking agent, and the molar ratio of the crosslinking agent to the monomer is 0-4:1.

[0039] Preferably, the crosslinking agent is at least one of p-vinylbenzene, ethylene glycol dimethacrylate, N,N-methylene bisacrylamide and polyethylene glycol diacrylate, and the specific structures are shown as follows.

[0040]

[0041] In a third aspect, the present application provides a method for synthesizing glycerol carbonate from carbon dioxide and glycerol, which comprises using the catalyst according to any one of the preceding embodiments to catalyze the reaction of carbon dioxide, glycerol and an epoxide compound to synthesize glycerol carbonate.

[0042] The method directly uses carbon dioxide and glycerol as raw materials to prepare glycerol carbonate with high added value, which is economic and environmentally friendly and in line with the main theme of green chemistry.

[0043] In some alternative embodiments, the epoxide compound is at least one of ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, butylene oxide, hexene oxide, glycidol, styrene oxide, glycidyl ether and allyl glyceryl ether.

[0044] And / or, the molar ratio of the epoxide compound to glycerol is 1-10:1, the catalyst is used in an amount of 0.1-20wt% of glycerol, and the carbon dioxide partial pressure is 0.1-5MPa.

[0045] And / or, the synthesis reaction is performed at a temperature of 70-130℃ for 0.5-24h.

[0046] The method synthesizes glycerol carbonate, and the conversion rate of the epoxide compound can reach 98%, the conversion rate of glycerol can reach 91%, the yield of glycerol carbonate can reach 91%, and even under a carbon dioxide pressure of 0.1MPa, the yield of glycerol carbonate can reach 91%.

[0047] The present application has the following beneficial effects:

[0048] Compared with the reported homogeneous catalysts for the one-pot synthesis of glycerol carbonate from carbon dioxide, glycerol and epoxide, the DBU onium polyionic liquid catalyst in the application has higher catalytic activity, is easier to separate and reuse, and has lower operation cost; compared with the reported homogeneous catalysts for the one-pot synthesis of glycerol carbonate from carbon dioxide, glycerol and epoxide, the DBU onium polyionic liquid catalyst in the application is convenient to recycle, has higher catalytic activity, and has more industrial application prospects. BRIEF DESCRIPTION OF DRAWINGS

[0049] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some of the embodiments of the present application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0050] Figure 1 For the infrared spectrum of the polyionic liquid synthesized in the application, (a) DBU VBI, and the infrared spectrum of the polyionic liquid synthesized with different DVB / DBU VBI molar ratios, (b) the infrared spectrum of the polyionic liquid synthesized with different cross-linking agents and DBU VBI. DETAILED DESCRIPTION

[0051] In order to make the purpose, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be described clearly and completely below. The specific conditions not mentioned in the embodiments are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments not mentioned by the manufacturer are all conventional products that can be purchased on the market.

[0052] The following embodiments of the present application provide a method for the one-pot synthesis of glycerol carbonate from carbon dioxide, glycerol and epoxide, comprising the following steps:

[0053] The 0.1-2 mol / L vinylbenzyl halide acetonitrile solution is stirred at 0-50℃ under N2 atmosphere; 0.1-2 mol / L DBU acetonitrile solution is added to the vinylbenzyl halide acetonitrile solution according to the molar ratio of DBU to vinylbenzyl halide of 0.25-4:1, and the stirring is continued at 0-70℃ for 4-24h; after the reaction is completed, the crude product is washed with ether for several times, and the washed crude product is dried under vacuum at a temperature of 40-80℃ and a pressure of 0.01-0.1 MPa for 4-12h, and the obtained product is a DBU onium ionic liquid monomer.

[0054] The crosslinking agent and the DBU onium ionic liquid monomer are mixed in a molar ratio of 0-4:1, 2.5-20wt% of azobisisobutyronitrile initiator based on the total mass of the reactants and 50-200wt% of methanol as a solvent are added under N2 atmosphere, and the reaction is stirred at 60-100℃ for 4-24h. After the reaction is completed, the crude product is washed several times with methanol and ethanol respectively, and centrifuged to obtain the crude product. The washed crude product is dried under vacuum at a temperature of 40-80℃ and a pressure of 0.01-0.1MPa for 4-12h, and the obtained product is the DBU onium polyionic liquid.

[0055] The epoxide compound and glycerol are added to a reaction kettle in a molar ratio of 1-10:1, the polyionic liquid catalyst is used in an amount of 0.1-20wt% of glycerol, 0.1-5MPa of carbon dioxide is filled in the reaction kettle, and the reaction is carried out at 70-130℃ for 0.5-24h.

[0056] The features and properties of the present application are further described in detail below in combination with examples.

[0057] Example 1:

[0058] The 1mol / L 4-vinylbenzyl iodine acetonitrile solution is stirred at 5℃ under N2 atmosphere, 1mol / L DBU acetonitrile solution is added to the 4-vinylbenzyl iodine acetonitrile solution in a molar ratio of 1:1 of DBU and vinylbenzyl iodine, and the stirring is continued at 25℃ for 24h. After the reaction is completed, the crude product is washed with diethyl ether for 3 times, and the washed crude product is dried under vacuum at a temperature of 70℃ and a pressure of 0.01MPa for 7h, and the obtained ionic liquid monomer is named as DBUVBI.

[0059] The DVB and DBUVBI are mixed in a molar ratio of 1:2, 10wt% of azobisisobutyronitrile initiator based on the total mass of the mixture and 100wt% of methanol are added under N2 atmosphere, and the reaction is stirred at 70℃ for 24h. After the reaction is completed, the crude product is obtained by washing with methanol and ethanol for 3 times respectively and centrifuging. The washed crude product is dried under vacuum at a temperature of 70℃ and a pressure of 0.01MPa for 7h, and the obtained polyionic liquid is named as P-DVB-DBUVBI-1.

[0060] The propylene oxide and glycerol are added to a reaction kettle in a molar ratio of 4:1, the polyionic liquid catalyst is used in an amount of 10wt% of glycerol, 2MPa of carbon dioxide is filled in the reaction kettle, and the reaction is carried out at 100℃ for 6h. The conversion rate of propylene oxide is 98%, the conversion rate of glycerol is 91%, and the yield of glycerol carbonate is 91%.

[0061] Example 2:

[0062] The catalyst preparation and reaction process were the same as Example 1, except that 4-vinylbenzyl chloride was used instead of 4-vinylbenzyl iodide in Example 1. The conversion of propylene oxide was 53%, the conversion of glycerol was 42%, and the yield of glycerol carbonate was 36%.

[0063] Example 3:

[0064] The catalyst preparation and reaction process were the same as Example 1, except that EDGMA was used instead of DVB in Example 1, and the resulting polyionic liquid was named P-EDGMA-DBUVBI. The conversion of propylene oxide was 95%, the conversion of glycerol was 90%, and the yield of glycerol carbonate was 82%.

[0065] Example 4:

[0066] The catalyst preparation and reaction process were the same as Example 1, except that MBAAm was used instead of DVB in Example 1, and the resulting polyionic liquid was named P-MBAAm-DBUVBI. The conversion of propylene oxide was 98%, the conversion of glycerol was 91%, and the yield of glycerol carbonate was 86%.

[0067] Example 5:

[0068] The catalyst preparation and reaction process were the same as Example 1, except that the molar ratio of DVB and DBUVBI in Example 1 was adjusted to 0:1, and the resulting polyionic liquid was named P-DBUVBI. The conversion of propylene oxide was 98%, the conversion of glycerol was 91%, and the yield of glycerol carbonate was 88%.

[0069] Example 6:

[0070] The catalyst preparation and reaction process were the same as Example 1, except that the molar ratio of DVB and DBUVBI in Example 1 was adjusted to 1:1, and the resulting polyionic liquid was named P-DVB-DBUVBI-2. The conversion of propylene oxide was 91%, the conversion of glycerol was 89%, and the yield of glycerol carbonate was 86%.

[0071] Example 7:

[0072] The catalyst preparation and reaction process were the same as Example 1, except that the molar ratio of DVB and DBUVBI in Example 1 was adjusted to 2:1, and the resulting polyionic liquid was named P-DVB-DBUVBI-3. The conversion of propylene oxide was 89%, the conversion of glycerol was 87%, and the yield of glycerol carbonate was 85%.

[0073] Example 8:

[0074] The catalyst preparation and reaction process were the same as Example 1, and the molar ratio of propylene oxide to glycerol in Example 1 was adjusted to 3:1. The conversion rate of propylene oxide obtained by the reaction was 95%, the conversion rate of glycerol was 88%, and the yield of glycerol carbonate was 86%.

[0075] Example 9:

[0076] The catalyst preparation and reaction process were the same as Example 1, and the amount of polyionic liquid catalyst added in Example 1 was adjusted to 8wt% of glycerol. The conversion rate of propylene oxide obtained by the reaction was 86%, the conversion rate of glycerol was 89%, and the yield of glycerol carbonate was 86%.

[0077] Example 10:

[0078] The catalyst preparation and reaction process were the same as Example 1, and the carbon dioxide pressure in Example 1 was adjusted to 1.5 MPa. The conversion rate of propylene oxide obtained by the reaction was 91%, the conversion rate of glycerol was 91%, and the yield of glycerol carbonate was 85%.

[0079] Example 11:

[0080] The catalyst preparation and reaction process were the same as Example 1, and the reaction temperature in Example 1 was adjusted to 90°C. The conversion rate of propylene oxide obtained by the reaction was 89%, the conversion rate of glycerol was 86%, and the yield of glycerol carbonate was 82%.

[0081] Example 12:

[0082] The catalyst preparation and reaction process were the same as Example 1, and the reaction time in Example 1 was adjusted to 4h. The conversion rate of propylene oxide obtained by the reaction was 87%, the conversion rate of glycerol was 87%, and the yield of glycerol carbonate was 81%.

[0083] Example 13:

[0084] The catalyst preparation and reaction process were the same as Example 1, and propylene oxide in Example 1 was replaced by epichlorohydrin. The conversion rate of epichlorohydrin obtained by the reaction was 90%, the conversion rate of glycerol was 52%, and the yield of glycerol carbonate was 51%.

[0085] Example 14:

[0086] The catalyst preparation and reaction process were the same as Example 1, and propylene oxide in Example 1 was replaced by styrene oxide, and the carbon dioxide pressure was adjusted to 0.1 MPa. The conversion rate of styrene oxide obtained by the reaction was 75%, the conversion rate of glycerol was 84%, and the yield of glycerol carbonate was 83%.

[0087] Example 15:

[0088] The catalyst was prepared and the reaction process was the same as that of Example 14, and the reaction time in Example 14 was adjusted to 12 h. The conversion rate of the obtained styrene oxide was 96%, the conversion rate of glycerol was 91%, and the yield of glycerol carbonate was 91%.

[0089] The catalyst obtained in some examples in the present application was characterized, wherein, Figure 1 The infrared spectra of DBUVBI, DBUVBI and different crosslinking agents polymerized in different proportions are given. As can be seen from the figure, for DBUVBI monomer, at 1610 cm -1 and 1190 cm -1 , respectively, C=N bond and C-N bond on DBU. In P-DBUVBI, P-DVB-DBUVBI-1, P-DVB-DBUVBI-2 and P-DVB-DBUVBI-3 polyionic liquid, there are respectively C=N bond and C-N bond stretching vibration peaks at 1610 cm -1 and 1190 cm -1 , respectively, which shows that DBUVBI is successfully introduced into the structure of P-DVB-DBUVBI-n polyionic liquid. The polymer synthesized by DBUVBI, EDGMA and MBAAm shows C=N and C-N bond stretching vibration peaks at 1610 cm -1 and 1190 cm -1 , respectively, which also shows the successful introduction of DBUVBI.

[0090] Example 16:

[0091] The catalyst in Example 1 was centrifuged and washed with ethanol three times, and then recovered by vacuum drying; the recovered catalyst was added to the high-pressure reaction kettle for the next catalytic cycle. The other steps are the same as described in Example 1, and the repeated use results are shown in Table 1.

[0092] Table 1. Repeated use performance of polyionic liquid P-DVB-DBUVBI-1

[0093]

[0094] As can be seen from Table 1, the catalytic activity of the DUB onium polyionic liquid catalyst P-DVB-DBUVBI-1 does not change significantly after five cycles, which shows that the DBU onium polyionic liquid has good stability and can be used repeatedly.

[0095] The above only describes the preferred embodiments of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, characterized by, A polymer comprising a unit represented by Formula 1; wherein R is a C1-C10 alkyl group, and X is I, Br, or Cl. Formula 1 A polymer comprising a unit represented by Formula 1; wherein R is a C1-C10 alkyl group, and X is I, Br, or Cl.

2. The catalyst for synthesis of glycerol carbonate from carbon dioxide and glycerol according to claim 1, characterized by that, A polymer comprising a unit represented by Formula 2, 3. The catalyst for synthesizing carbonic acid glycerol ester from carbon dioxide and glycerol according to claim 1, characterized by, Formula 2 A polymer comprising a unit represented by Formula 2, Formula 2 4. A method for producing the catalyst for synthesizing carbonic acid glycerol ester from carbon dioxide and glycerol according to any one of claims 1 to 3, characterized by, CR is a group comprising a phenyl group, an alcohol ester group, or an amide group.

5. The method for producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 4, characterized by, A catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, wherein the catalyst is obtained by polymerizing a monomer formed from 1,8-diazabicyclo[5.4.0]undec-7-ene and a vinyl halogenated alkylbenzene.

6. The method for producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 5, characterized by, Also included is the preparation of the monomer, wherein the monomer is prepared by subjecting 1,8-diazabicyclo[5.4.0]undec-7-ene and a vinyl halogenated alkylbenzene to a quaternization reaction in a first solvent to form the monomer.

7. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 5, characterized by, The molar ratio of 1,8-diazabicyclo[5.4.0]undec-7-ene to the vinyl halogenated alkylbenzene is 0.25-4:

1.

8. The method for preparing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 5, characterized by, The initial concentration of the vinyl halogenated alkylbenzene in the first solvent is 0.1-2 mol / L.

9. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 5, characterized by, The vinyl halogenated alkylbenzene is one of 4-vinylbenzyl iodide, 4-vinylbenzyl bromide, and 4-vinylbenzyl chloride.

10. The method for preparing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 5, characterized by, The first solvent is acetonitrile.

11. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 5, characterized by, The temperature of the quaternization reaction is 0-70 °C, and the time is 4-24 h.

12. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 5, characterized by, The monomer is obtained after washing and first vacuum drying of the product after the quaternization reaction.

13. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 11, characterized by, The crude product is washed with diethyl ether after the quaternization reaction.

14. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 4, characterized by, The temperature of the first vacuum drying is 40-80 °C, and the time is 4-12 h.

15. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 14, characterized by, The polymerization step comprises subjecting reactants including the monomer and an initiator to a polymerization reaction in a second solvent to obtain the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol.

16. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 14, characterized by, The initiator is azobisisobutyronitrile, and the initiator accounts for 2.5-20 wt% of the total mass of the reactants.

17. The method for preparing the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to claim 14, characterized in that, The second solvent is methanol, and the second solvent accounts for 50-200 wt% of the total mass of the reactants.

18. The method for preparing the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to claim 14, characterized in that, The temperature of the polymerization reaction is 60-100 °C, and the time is 4-24 h.

19. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 14, characterized by, The catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol is obtained after washing and second vacuum drying of the product after the polymerization reaction.

20. The method for preparing the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to claim 18, characterized in that, The crude product is washed with methanol and ethanol, respectively, after the polymerization reaction.

21. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 14, characterized by, The temperature of the second vacuum drying is 40-80 °C, and the time is 4-12 h.

22. The method of producing a catalyst for synthesizing a glycerol carbonate from carbon dioxide and glycerol according to claim 21, characterized by, The reactants further include a crosslinking agent, and the molar ratio of the crosslinking agent to the monomer is 0-4:

1.

23. A method of synthesizing a glycerol carbonate from carbon dioxide and glycerol, characterized by, The crosslinking agent is at least one of p-vinylbenzene, ethylene glycol dimethacrylate, N,N-methylenebisacrylamide, and polyethylene glycol diacrylate.

24. The method for synthesizing glycerol carbonate from carbon dioxide and glycerol according to claim 23, characterized in that, The catalyst is used to catalyze a reaction of carbon dioxide, glycerol, and an epoxide compound to synthesize glycerol carbonate. The epoxide compound is at least one of oxirane, oxetane, epichlorohydrin, epibromohydrin, epoxy butane, epoxy hexane, glycidol, styrene oxide, and glycidyl ether. And / or, the molar ratio of the epoxy compound and glycerol is 1-10:1, the catalyst is used in an amount of 0.1-20 wt% of glycerol, and the carbon dioxide partial pressure is 0.1-5 MPa; And / or, the synthesis reaction temperature is 70-130 °C, and the time is 0.5-24 h.

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