A heterogeneous catalyst for catalyzing the conversion of co2 and a method for preparing and using the same

Abstract

The present application relates to the technical field of catalysis and organic synthesis, and in particular to a heterogeneous catalyst for catalyzing CO2 conversion, and a preparation method and application thereof.The present application uses resin as a carrier, and immobilizes a sulfur-containing small molecule, a specific compound and an optional amino acid on the resin carrier through a chemical bond, thereby obtaining a heterogeneous catalyst for catalyzing CO2 conversion.The heterogeneous catalyst comprises a resin carrier and a catalytically active substance immobilized on the resin carrier through a chemical bond, and is a heterogeneous catalyst;the heterogeneous catalyst has the advantages of high efficiency of homogeneous catalysis and easy separation of heterogeneous catalysis, is easy to separate and recover from reaction products, solves the problems of difficult separation of products, high energy consumption of separation and poor recycling performance of homogeneous catalysts, and has the advantage of reusability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysis and organic synthesis, and further relates to a heterogeneous catalyst for catalyzing CO2 conversion and a preparation method and application thereof. BACKGROUND

[0002] CO2 is a non-toxic, non-flammable, renewable and inexpensive C1 resource. Developing and utilizing CO2 to convert it into fine chemicals can not only realize resource recycling, but also effectively reduce environmental pollution, and has significant economic value and environmental benefits. However, CO2 has high thermodynamic stability and kinetic inertness, and it is difficult to undergo chemical reactions under normal conditions. Therefore, a catalyst is needed to activate CO2 to promote the catalytic conversion of CO2.

[0003] At present, fine chemicals such as oxazolidinone, cyclic carbonate, nitrogen formylation product, nitrogen methylation product and benzimidazole compound synthesized by catalytic conversion of CO2 have been widely used in the fields of medicine, materials, chemical industry and the like. In the CO2 catalytic conversion technology, metal catalysts and organic catalysts constitute the main catalytic system. Among them, ionic liquids as an important part of organic catalysts are widely used in CO2 catalytic conversion reactions due to their outstanding advantages such as strong stability and controllable structure.

[0004] Ionic liquids are generally composed of organic cations and nucleophilic anions. The nucleophilic anion needs to have high affinity and easy leaving characteristics. There are obvious defects in using halogen elements as the nucleophilic anion of ionic liquids: in the reaction process, halogen will cause corrosion to the reactor, and at the same time, it will pollute the environment in the reaction and subsequent processing links. The interaction between nitrogen and oxygen as the nucleophilic anion of ionic liquids and CO2 is too strong, which is not conducive to the resolution and further conversion of CO2. The nucleophilicity of sulfur anion is higher than that of nitrogen and oxygen anions, which can react with CO2 to generate sulfide carbonates, and the C-S bond energy is smaller than the C-N and C-O bond energy in carbamate or carbonate, which is easy to release CO2, making it a potential CO2 activator. Therefore, ionic liquids with sulfur anion as the activation site appear. However, the sulfur-containing ionic liquid still faces problems such as time-consuming and energy-consuming in catalyst recovery, and difficulty in separation from reaction products in industrial applications. These problems lead to the fact that most related reactions can only be carried out in a tank reactor, which is difficult to realize continuous flow and other efficient production operations, greatly limiting the large-scale industrial production. SUMMARY

[0005] In order to solve the technical problem of difficult recovery of sulfur-containing ionic liquid as a catalyst in industrial applications, the present application provides a heterogeneous catalyst for catalyzing CO2 conversion and a preparation method and application thereof.

[0006] The present application uses resin as a carrier, and loads sulfur-containing small molecules, specific compounds and optional amino acids on the resin carrier through chemical bonds, thereby obtaining a heterogeneous catalyst for catalyzing CO2 conversion.

[0007] One of the purposes of the present application is to provide a heterogeneous catalyst for catalyzing CO2 conversion.

[0008] The heterogeneous catalyst is selected from at least one of the compounds shown in formula 1, formula 2, formula 3, formula 4;

[0009] Formula 1, Formula 2,

[0010] Formula 3, Formula 4;

[0011] In formulae 1-4, R is derived from a resin with a modified group connected to the surface; derived from an amino acid;

[0012] Sulfur source-S - derived from a sulfur-containing small molecule; E + derived from compound A; X + derived from compound B; n=0-10; the compound A is at least one of an organic salt or an organic base capable of providing a cation; the compound B is selected from at least one of a trialkyl phosphine, a triaryl phosphine, a trialkyl amine, and a triaryl amine.

[0013] The heterogeneous catalyst comprises a resin carrier and a catalytically active substance loaded on the resin carrier by chemical bonds, and is a heterogeneous catalyst. The catalytically active substance of the heterogeneous catalyst is formed by the reaction of a sulfur-containing small molecule, a compound A, a compound B and an optional amino acid. In the heterogeneous catalyst, the sulfur-containing small molecule (in the form of a sulfur anion) is connected to the compound A (in the form of a basic cation) through a covalent bond or an amino acid, and the sulfur anion and the compound B (in the form of a cation) are connected through an ionic bond.

[0014] The heterogeneous catalyst comprises a sulfur active site, an optional amino acid active site, and a basic active site. The sulfur active site utilizes the electron-donating ability of the sulfur atom lone pair to coordinate with the electron-deficient carbon center of CO2, effectively activating the CO2 molecule and weakening the stability of the C=O bond, thereby realizing the catalytic conversion of CO2. In the catalytic process of CO2, the sulfur active site can not only act as an electron donor to directly participate in the activation of CO2, but also can coordinate with its adjacent basic site (E + , X + ) to promote the ring-opening reaction of epoxide and other substrates.

[0015] The sulfur anion in the multi-phase catalyst has high nucleophilicity, and the S-C bond formed during the catalytic conversion of CO2 by the sulfur anion is more easily broken and removed, having a good catalytic regeneration effect on the catalyst. High catalytic efficiency is achieved, and the catalytic conversion reaction is more easily carried out.

[0016] The resin can be selected from any one or more than one resin that can be used as a catalyst carrier. As a preferred solution, the resin is selected from a resin containing an amino group, a hydroxyl group or a halogen and resistant to acid and alkali, more preferably at least one of polystyrene, polyacrylamide or polydimethylacrylamide, and further preferably at least one of polystyrene-divinylbenzene crosslinking.

[0017] The modification group is selected from , wherein represents the position of the fragment connected to the resin.

[0018] The resin to which the modification group is connected on the surface is preferably at least one of Rink Amide resin and 2-chlorotrityl chloride resin.

[0019] The structure of the Rink Amide resin is as follows: , The polystyrene-divinylbenzene crosslinking resin is as follows.

[0020] The structure of the 2-chlorotrityl chloride resin is as follows: , The polystyrene-divinylbenzene crosslinking resin is as follows.

[0021] The sulfur-containing small molecule is selected from at least one of benzene thiol with a molecular weight less than 500 or its dimer, substituted benzene thiol or its dimer, heterocyclic compound containing a mercapto group or its dimer, substituted heterocyclic compound containing a mercapto group or its dimer, thioctic acid, and inorganic sulfide; wherein the substituents in the substituted benzene thiol or its dimer, the substituted heterocyclic compound containing a mercapto group or its dimer are independently selected from halogen, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 carboxyl, nitro, aromatic ring or aromatic heterocyclic ring, preferably from sodium sulfide, hydrogen sulfide, potassium hydrosulfide, methyl mercaptan, ethyl mercaptan, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercaptonic acid, 6,6 ， -dithionicotinic acid, 5-mercaptonic acid, 4-mercaptonic acid, 3-mercaptoisonicotinic acid, 2-mercaptonic acid, 6-mercaptopicolinic acid, thioctic acid, 2-mercaptopyridine, 4-thiol pyridine, 2-thiol pyrimidine, 4-methyl benzene thiol, 4-bromobenzene thiol, 4-nitrobenzene thiol, 4-methoxybenzene thiol and sodium hydrosulfide, more preferably from 2-mercaptobenzoic acid ( ), 3-mercaptobenzoic acid ( ), 6-mercaptonic acid ( ), 6,6 ， - dithiodinic acid (DTN) ), lipoic acid (LA) ), 2-mercaptopyridine (2-MP) ) and sodium hydrosulfide (NaHS).

[0022] The compound A is used to abstract the hydrogen proton from the sulfydryl group in the sulfur source in a basic environment. The compound A can be selected from any one or more of the compounds having the above-mentioned function. As a preferred solution, the compound A is selected from at least one of a quaternary phosphonium salt, a quaternary phosphine base, a quaternary amine salt, a quaternary amine base, and an organic base selected from at least one of 1,8-diazabicyclo-undec-7-ene (DBU), tetramethylguanidine (TMG), 1,5,7-triazabicyclodec-5-ene (TBD), and choline hydroxide (ChOH).

[0023] Among them, the strong organic base DBU or TBD is used as a cation, which can efficiently abstract the hydrogen proton from the sulfydryl group (-SH) during the construction of the heterogeneous catalyst, and promote the formation of the salt reaction. The constructed heterogeneous catalyst not only facilitates the activation of CO2 molecules, but also cooperates with the nucleophilic property of the sulfur-containing anion to promote the efficient generation of the product, and can realize high product yield and selectivity under mild reaction conditions. Therefore, as a more preferred solution, the compound A is preferably selected from at least one of 1,8-diazabicyclo-undec-7-ene (DBU), 1,5,7-triazabicyclodec-5-ene (TBD), tetrabutylphosphonium hydroxide, and tetrabutylammonium hydroxide.

[0024] As a specific solution, the E + is selected from , , , .

[0025] The compound B is selected from at least one of tri-n-butylphosphine, triphenylphosphine, and trimethylamine.

[0026] As a specific solution, the X + is selected from , , ; wherein represents a connection position.

[0027] The amino acid is used as a molecular bridge between the resin carrier and the sulfur active site. The carboxyl group (-COOH) of the amino acid can be stably connected to the carrier through condensation reaction, while the amino (-NH2) functional group provides a reaction site for anchoring the sulfur source. More importantly, the amino acid exhibits a unique synergistic effect in the catalytic conversion of CO2: its zwitterionic nature can efficiently capture and activate CO2 molecules. The amino acid can be selected from any one or more of the existing amino acids. As a preferred solution, the amino acid is selected from at least one of glycine, D-alanine, L-alanine, D-valine, L-valine, D-leucine, L-leucine, D-isoleucine, L-isoleucine, D-methionine (methionine), L-methionine (methionine), D-proline, L-proline, D-tryptophan, L-tryptophan, D-serine, L-serine, D-tyrosine, L-tyrosine, D-cysteine, L-cysteine, D-phenylalanine, L-phenylalanine, D-asparagine, L-asparagine, D-glutamine, L-glutamine, D-threonine, L-threonine, D-aspartic acid, L-aspartic acid, D-glutamic acid, L-glutamic acid, D-arginine, L-arginine, D-histidine, L-histidine, selenocysteine, and at least one of D-lysine and L-lysine. As a more preferred solution, the amino acid is selected from L-lysine, L-cysteine, and L-glycine. Among them, L-lysine and L-cysteine have specific side chain groups, such as the amino group of L-lysine and the thiol group of L-cysteine, which can significantly improve the nucleophilicity of the sulfur active center; glycine has the simplest structure and small steric hindrance; L-lysine has multiple amino groups, which can enhance CO2 adsorption; and the thiol group of L-cysteine directly participates in the construction of the sulfur active center.

[0028] As a specific solution, the heterogeneous catalyst is selected from at least one of the compounds represented by formula 5, formula 6, formula 7, and formula 8.

[0029] Formula 5 Formula 6

[0030] Formula 7 Formula 8

[0031] wherein, is a polystyrene-divinylbenzene cross-linked resin, and n = 0-10.

[0032] The heterogeneous catalyst can be prepared from raw materials including a resin, a sulfur-containing small molecule, compound A, and optionally an amino acid; or can be prepared from raw materials including a resin, a sulfur-containing small molecule, compound B, a halogenated aliphatic acid, and optionally an amino acid.

[0033] The second object of the present application is to provide a preparation method of the multi-phase catalyst of one of the objects of the present application.

[0034] The preparation method comprises:

[0035] Method I: performing the reaction of resin connecting n amino acids, the reaction with a sulfur-containing small molecule, the reaction of breaking disulfide bond, and the reaction with compound A; or,

[0036] Method II: performing the reaction of resin connecting n amino acids, the reaction with a halogenated aliphatic acid, the reaction with compound B, and the reaction with a sulfur-containing small molecule.

[0037] In the method I and the method II, the reaction with compound B is performed at normal pressure and at 100-120°C, and the other reactions are all performed at normal temperature and normal pressure; each reaction is performed in a solvent.

[0038] In the method I and the method II, when Rink Amide resin is selected, the Fmoc (9-fluorenylmethoxycarbonyl) protecting group needs to be removed. That is, in the method I and the method II, optionally, the resin is subjected to the reaction of removing the Fmoc protecting group before participating in the reaction.

[0039] When n=0, the method I comprises:

[0040] The sulfur-containing small molecule, the alkaline auxiliary agent, and optionally the condensing agent A are dissolved in solvent A and then added to the resin to perform the condensation reaction, the blocking agent is added to perform the blocking reaction, the disulfide bond breaking reagent is added to perform the disulfide bond breaking reaction, and compound A is added to perform the salt formation reaction.

[0041] When n=1-10, the method I comprises:

[0042] The amino acid, the alkaline auxiliary agent, and optionally the condensing agent A are dissolved in solvent A and then added to the resin to perform the condensation reaction, the blocking agent is added to perform the blocking reaction, the Fmoc removing agent is added to perform the Fmoc removing reaction, the operation of “adding the amino acid, the condensing agent A, and the alkaline auxiliary agent to perform the condensation reaction, and adding the Fmoc removing agent to perform the Fmoc removing reaction” is performed for 0-9 times, the sulfur-containing small molecule, the condensing agent A, and the alkaline auxiliary agent are added to perform the condensation reaction, the disulfide bond breaking reagent is added to perform the disulfide bond breaking reaction, and compound A is added to perform the salt formation reaction.

[0043] When n=0, the method II comprises:

[0044] The halogenated aliphatic acid, the alkaline auxiliary agent, and optionally the condensing agent B are dissolved in solvent B and then added to the swelled resin to perform the condensation reaction, the blocking agent is added to perform the blocking reaction, compound B is added to perform the substitution reaction, and the sulfur-containing small molecule is added to perform the substitution reaction.

[0045] When n=1-10, the method II comprises:

[0046] After dissolving the amino acid, the basic auxiliary agent, and optionally the condensing agent A with the solvent B, the condensation reaction is performed by adding to the resin, the blocking reaction is performed by adding the blocking agent, the Fmoc removal reaction is performed by adding the Fmoc removal agent, the operation of "the condensation reaction by adding the amino acid, the condensing agent A, and the basic auxiliary agent, and the Fmoc removal reaction by adding the Fmoc removal agent" is performed 0-9 times, the condensation reaction is performed by adding the haloaliphatic acid and the condensing agent B, the substitution reaction is performed by adding the compound B, and the substitution reaction is performed by adding the sulfur-containing small molecule.

[0047] The feeding ratio of the resin to the sulfur-containing small molecule is 500 mg: (1-1.5) mmol.

[0048] The feeding ratio of the resin to the amino acid is 500 mg: (1-1.5) mmol. The "feeding ratio of the resin to the amino acid" refers to the amount of amino acid required to link one amino acid.

[0049] The feeding ratio of the resin to the haloaliphatic acid is 500 mg: (1-1.5) mmol.

[0050] The feeding ratio of the resin to the compound A is 500 mg: (1-10) mmol.

[0051] The feeding ratio of the resin to the compound B is 500 mg: (1-10) mmol.

[0052] The basic auxiliary agent is selected from at least one of N,N-diisopropylethylamine, triethylamine.

[0053] The condensing agent A is selected from 2-(7-azabenzotriazol)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU), O-benzotriazol-tetramethyluronium hexafluorophosphate (HBTU), 6-chlorobenzotriazol-1,1,3,3-tetramethyluronium hexafluorophosphate (HCTU), 2-succinimidyl-1,1,3,3-tetramethyluronium tetrafluoroborate (TSTU), O-benzotriazol-N,N,N',N'-tetramethyluronium tetrafluoroborate (TBTU).

[0054] The solvent A is selected from N,N-dimethylformamide, dichloromethane.

[0055] The blocking agent consists of dichloromethane, alcohol, basic auxiliary agent, preferably, consists of dichloromethane, alcohol, basic auxiliary agent in a volume ratio of 17:2:1.

[0056] The disulfide bond cleavage reagent is selected from at least one of sodium sulfhydrate, DL-dithiothreitol.

[0057] The Fmoc removing agent consists of diethylamine and N,N-dimethylformamide or consists of piperidine and N,N-dimethylformamide, preferably consists of diethylamine and N,N-dimethylformamide in a volume ratio of 3:7 or consists of piperidine and N,N-dimethylformamide in a volume ratio of 2:8.

[0058] The halogenated fatty acid is selected from at least one of halogenated fatty acids with carbon atoms of 2-6, preferably selected from at least one of bromoacetic acid, chloroacetic acid, iodoacetic acid, bromopropionic acid, chloropropionic acid.

[0059] The condensing agent B is selected from N,N'-diisopropylcarbodiimide (DIC).

[0060] The solvent B is selected from N,N-dimethylformamide, dichloromethane.

[0061] In the above preparation method, the amount of the basic auxiliary agent, the solvent A, the solvent B, the condensing agent A, the condensing agent B, the blocking agent, the disulfide bond breaking reagent, and the Fmoc removing agent are all conventional amounts.

[0062] The amount of the solvent A is 15-20 mL, the amount of the solvent B is 15-20 mL, the amount of the condensing agent A is 1-1.5 mmol, the amount of the condensing agent B is 1-1.5 mmol, the amount of the blocking agent is 15-20 mL, the amount of the disulfide bond breaking reagent is 1-1.5 mmol, and the amount of the Fmoc removing agent is 15-20 mL, based on 500 mg of the resin mass.

[0063] As one solution, the method one (n=0) comprises the following steps:

[0064] Step 1: swelling the resin 2-chlorotrityl chloride resin in dichloromethane;

[0065] Step 2: dissolving the sulfur-containing small molecule and the basic auxiliary agent (DIEA) in the solvent A and then adding to the swollen resin for condensation reaction;

[0066] Step 3: adding the blocking agent to the product obtained in step 2 for blocking reaction;

[0067] Step 4: adding the disulfide bond breaking reagent (DTT) to the product obtained in step 3 for disulfide bond breaking reaction;

[0068] Step 5: adding the compound A to the product obtained in step 4 for salt formation reaction;

[0069] The reaction process is as follows:

[0070]

[0071] E is the compound A.

[0072] As one solution, Method One (n=l-10) comprises the following steps:

[0073] Step 1: Swell the resin 2-chlorotrityl chloride resin in dichloromethane;

[0074] Step 2: Dissolve the amino acid and basic auxiliary (DIEA) in solvent A, then add to the swollen resin for condensation reaction;

[0075] Step 3: Add blocking agent to the product of Step 2 for blocking reaction;

[0076] Step 4: Step 4.1, add Fmoc removing agent to the product of Step 3 for Fmoc removal reaction; Step 4.2, add amino acid, basic auxiliary (DIEA) and condensing agent A (HBTU) for condensation reaction, and add Fmoc removing agent for Fmoc removal reaction; Step 4.2 is repeated 0-9 times; 0 times means no Step 4.2 is performed;

[0077] Step 5: Add sulfur-containing small molecule, basic auxiliary (DIEA) and condensing agent A (HBTU) to the product of Step 4 for condensation reaction;

[0078] Step 6: Add disulfide bond breaking reagent (DTT) to the product of Step 5 for disulfide bond breaking reaction;

[0079] Step 7: Add Compound A to the product of Step 6 for salt formation reaction;

[0080] The reaction process is as follows:

[0081]

[0082] Wherein, E is Compound A.

[0083] As one solution, Method One (n=0) comprises the following steps:

[0084] Step 1: Swell the resin Rink Amide resin in dichloromethane, then add Fmoc removing agent for Fmoc removal reaction;

[0085] Step 2: Dissolve sulfur-containing small molecule, condensing agent A (HBTU) and basic auxiliary (DIEA) in solvent A, then add to the Fmoc-removed resin for condensation reaction;

[0086] Step 3: Add blocking agent to the product of Step 2 for blocking reaction;

[0087] Step 4: Add disulfide bond breaking reagent (DTT) to the product of Step 3 for disulfide bond breaking reaction;

[0088] Step 5: To the product from Step 4, add Compound A to form a salt;

[0089] The reaction process is as follows:

[0090]

[0091] wherein E is Compound A.

[0092] As one solution, Method One (n=l-10) includes the following steps:

[0093] Step 1: Swell the resin Rink Amide resin in dichloromethane, then add Fmoc-removing agent to remove Fmoc;

[0094] Step 2: Dissolve the amino acid, basic auxiliary agent (DIEA), and condensing agent A (HBTU) in solvent A, then add to the Fmoc-removed resin to condense;

[0095] Step 3: To the product from Step 2, add blocking agent to block;

[0096] Step 4: Step 4.1, to the product from Step 3, add Fmoc-removing agent to remove Fmoc; Step 4.2, add amino acid, basic auxiliary agent (DIEA), and condensing agent A (HBTU) to condense, and add Fmoc-removing agent to remove Fmoc; Step 4.2 is repeated 0-9 times; 0 times means that Step 4.2 is not performed;

[0097] Step 5: To the product from Step 4, add sulfur-containing small molecule and condensing agent A (HBTU) to condense;

[0098] Step 6: To the product from Step 5, add disulfide bond-breaking reagent (DTT) to break the disulfide bond;

[0099] Step 7: To the product from Step 6, add Compound A to form a salt;

[0100] The reaction process is as follows:

[0101]

[0102] wherein E is Compound A.

[0103] As one solution, Method Two (n=0) includes the following steps:

[0104] Step 1: Swell the resin 2-chlorotrityl chloride resin in dichloromethane;

[0105] Step 2: After dissolving bromoacetic acid and basic auxiliary (DIEA) in solvent B, add to the swollen resin for condensation reaction;

[0106] Step 3: Add blocking agent to the product of step 2 for blocking reaction;

[0107] Step 4: Add compound B to the product of step 3 for substitution reaction;

[0108] Step 5: Add sulfur-containing small molecule to the product of step 4 for substitution reaction;

[0109] The reaction process is as follows:

[0110]

[0111] Wherein, X is compound B.

[0112] As a solution, method two (n = 1-10) includes the following steps:

[0113] Step 1: Swell the resin 2-chlorotrityl chloride resin in dichloromethane;

[0114] Step 2: After dissolving amino acid and basic auxiliary (DIEA) in solvent B, add to the swollen resin for condensation reaction;

[0115] Step 3: Add blocking agent to the product of step 2 for blocking reaction;

[0116] Step 4: Step 4.1, add Fmoc removing agent to the product of step 3 for Fmoc removal reaction; Step 4.2, add amino acid, basic auxiliary DIEA and condensing agent A (HBTU) for condensation reaction, and add Fmoc removing agent for Fmoc removal reaction; Step 4.2 is repeated 0-9 times; 0 times means no step 4.2 is performed;

[0117] Step 5: Add bromoacetic acid and condensing agent B to the product of step 4 for condensation reaction;

[0118] Step 6: Add compound B to the product of step 5 for substitution reaction;

[0119] Step 7: Add sulfur-containing small molecule to the product of step 6 for substitution reaction;

[0120] The reaction process is as follows:

[0121]

[0122]

[0123] Wherein, X is compound B.

[0124] As one solution, Method Two (n=0) includes the following steps:

[0125] Step 1: Swell the resin Rink Amide resin in dichloromethane, then add Fmoc removing agent to remove Fmoc;

[0126] Step 2: Dissolve bromoacetic acid and condensing agent B (DIC) in solvent B, then add to the Fmoc-removed resin to condense;

[0127] Step 3: Add blocking agent to the product of Step 2 to block;

[0128] Step 4: Add compound B to the product of Step 3 to substitute;

[0129] Step 5: Add sulfur-containing small molecule to the product of Step 4 to substitute;

[0130] The reaction process is as follows:

[0131]

[0132] Wherein, X is compound B.

[0133] As one solution, Method Two (n=1-10) includes the following steps:

[0134] Step 1: Swell the resin Rink Amide resin in dichloromethane, then add Fmoc removing agent to remove Fmoc;

[0135] Step 2: Dissolve amino acid, basic auxiliary (DIEA) and condensing agent A (HBTU) in solvent B, then add to the Fmoc-removed resin to condense for 2h;

[0136] Step 3: Add blocking agent to the product of Step 2 to block;

[0137] Step 4: Step 4.1, add Fmoc removing agent to the product of Step 3 to remove Fmoc; Step 4.2, add amino acid, basic auxiliary (DIEA) and condensing agent A (HBTU) to condense, and add Fmoc removing agent to remove Fmoc; Step 4.2 is repeated 0-9 times; 0 times means that Step 4.2 is not performed;

[0138] Step 5: Add bromoacetic acid and condensing agent B to the product of Step 4 to condense;

[0139] Step 6: Add compound B to the product of Step 5 to substitute;

[0140] Step 7: adding a sulfur-containing small molecule to the product obtained in step 6 to perform a substitution reaction;

[0141] The reaction process is as follows:

[0142]

[0143] wherein X is compound B.

[0144] A third object of the present application is to provide an application of the heterogeneous catalyst of one of the objects of the present application or the heterogeneous catalyst prepared by the preparation method of the second object of the present application in the field of catalytic conversion of CO2. Specifically, to provide a method for catalytic conversion of CO2.

[0145] The method for catalytic conversion of CO2 comprises: reacting a raw material with CO2 under the catalysis of a catalyst;

[0146] The raw material is selected from at least one of o-phenylenediamine compounds, oxirane compounds, nitrogen aryl epoxy amine compounds and N-methylaniline compounds;

[0147] The catalyst is selected from the heterogeneous catalyst of one of the objects of the present application or the heterogeneous catalyst prepared by the preparation method of the second object of the present application.

[0148] In the method for catalytic conversion of CO2, the reaction conditions such as temperature, pressure and time can be conventional conditions, and the amount of catalyst used can be a conventional amount.

[0149] As a scheme, the reaction temperature in the method for catalytic conversion of CO2 is 70.0-140.0℃, for example, 80.0℃, 90.0℃, 100.0℃, 110.0℃, 120.0℃, 130.0℃.

[0150] As a scheme, the reaction pressure in the method for catalytic conversion of CO2 is 0.5-3.0MPa, for example, 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa.

[0151] As a scheme, the reaction time in the method for catalytic conversion of CO2 is 0.5-36.0h, for example, 1.0h, 2.0h, 5.0h, 8.0h, 10.0h, 15.0h, 24.0h.

[0152] As an option, the molar ratio of active sites of the heterogeneous catalyst to the raw material in the CO2 catalytic conversion method is (0.01-0.5):1, for example, 0.01:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1. The active sites of the heterogeneous catalyst refer to the remaining part of the heterogeneous catalyst after removing the resin carrier.

[0153] As an option, the reaction in the CO2 catalytic conversion method is carried out in a solvent; the solvent is at least one selected from N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), acetonitrile (MeCN), dimethyl sulfoxide (DMSO), 1,4-dioxane, ethanol (EtOH), methanol (MeOH), dichloromethane (DCM), water, tetrahydrofuran (THF).

[0154] The amount of the solvent can be a conventional amount, preferably 0.5-4.0 mL, for example, 1.0 mL, 1.5 mL, 2.0 mL.

[0155] The CO2 catalytic conversion method can specifically include:

[0156] A method for catalyzing the reaction of an oxirane compound and carbon dioxide to generate a cyclic carbonate; or,

[0157] A method for catalyzing the reaction of a nitrogen aryl epoxy amine compound and carbon dioxide to generate an oxazolidinone or a cyclic carbonate; or,

[0158] A method for catalyzing the reaction of an N-methylaniline compound and carbon dioxide to generate an N-formylated or N-methylated compound; or,

[0159] A method for catalyzing the reaction of an o-phenylenediamine compound and carbon dioxide to generate a benzimidazole.

[0160] Compared with the prior art, the present application has the following advantages:

[0161] The heterogeneous catalyst provided by the present application has the advantages of high efficiency of homogeneous catalysis and easy separation of heterogeneous catalysis, is easy to separate and recover from the reaction product, solves the problems of difficult separation of products, high energy consumption of separation, and poor recycling performance of homogeneous catalysts, and has the advantages of reusability.

[0162] The heterogeneous catalyst provided by the application is completely free of metal, avoids product pollution and post-processing problems that may be caused by traditional metal catalysts, and eliminates the damage of corrosive ions to reaction equipment due to the halogen-free characteristics. The low-cost advantage of the resin carrier greatly reduces the preparation cost of the catalyst, and the mechanical strength and flexible skeleton make it suitable for long-term stable operation of the fixed bed, and the recovery process only needs simple filtration to be reused multiple times. The heterogeneous catalyst has wide potential in the field of green synthesis, meets the demand for sustainable development, and improves industrial economy by simplifying the process and reducing compliance costs.

[0163] Compared with existing immobilized ionic liquid catalysts, the heterogeneous catalyst provided by the application has excellent ability to activate and convert CO2 (high yield, high selectivity, and improved reaction rate). When the heterogeneous catalyst provided by the application is used to activate and convert CO2 to generate cyclic carbonate, oxazolidinone, nitrogen formylation, and benzimidazole, it exhibits excellent catalytic performance and stable recovery and reuse performance. BRIEF DESCRIPTION OF DRAWINGS

[0164] Figure 1 SEM characterization diagram of the heterogeneous catalyst 1 prepared for Example 1;

[0165] Figure 2 EDS characterization diagram of the heterogeneous catalyst 1 prepared for Example 1;

[0166] Figure 3 Actual picture of the heterogeneous catalyst 1 prepared for Example 1. DETAILED DESCRIPTION

[0167] The following specific description of the application is combined with specific drawings and examples. It is necessary to point out that the following examples are only used to further illustrate the application and cannot be understood as limiting the protection scope of the application. Some non-essential improvements and adjustments of the application made by those skilled in the art based on the content of the application still fall within the protection scope of the application.

[0168] Unless otherwise specified, the reagents used in the examples are commercially available. Among them, part of the reagents are as follows.

[0169]

[0170] The nuclear magnetic resonance spectrometer used in the examples is Agilent 500MHz DD2.

[0171] Example 1

[0172] Step 1: Swell 500 mg of 2-chlorotrityl chloride resin in dichloromethane for 10 min, and then remove the dichloromethane.

[0173] Step 2: Add 308 mg of 6,6， - dithiodinic acid, 330 microliters of DIEA in DMF was added to the product of step 1 and reacted for 2 h; after the reaction was completed, it was washed with DMF for 3 times, and 20 mL of a blocking agent (DCM:MeOH:DIEA=17:2:1 (volume ratio)) was added to block for 30 min; after the reaction was completed, it was washed with DCM and DMF for 3 times, respectively.

[0174] Step 3: 1 mmol of DL-dithiothreitol was added to the product obtained in step 2, and DMF was used as the reaction solvent for 4 h. After the reaction was completed, it was washed with DMF for 3 times, and the solvent was removed by suction.

[0175] Step 4: 760 mg of DBU (1,8-diazabicyclo-[5.4.0]-undec-7-ene) was added to the product obtained in step 3, and DMF was used as the solvent for 12 h. After the reaction was completed, it was washed with DMF and DCM for 3 times, respectively, and the dichloromethane solvent was removed by suction to constant weight to obtain the heterogeneous catalyst 1; the weight was 644 mg. The active site content of the heterogeneous catalyst 1 was 0.78 mmol / mg.

[0176] The formula for calculating the active site content is: m is the mass, M is the molar mass, is the mass of the product obtained in step 3; and M is the molar mass, is the molar mass of DBU.

[0177] The SEM characterization graph of the 2-chlorotrityl chloride resin and the heterogeneous catalyst 1 is shown in Figure 1 . Figure 1 On the left is the SEM characterization graph of the heterogeneous catalyst 1, and on the right is the SEM characterization graph of the 2-chlorotrityl chloride resin. As can be seen from the electron microscope characterization graph, the surface of the 2-chlorotrityl chloride resin is smooth, and the surface of the heterogeneous catalyst 1 is uneven with obvious protrusions; among them, the protruding part is the part loaded from 6,6 ， dithiodinic acid and DBU.

[0178] The EDS characterization graph of the heterogeneous catalyst 1 is shown in Figure 2 . Figure 2 The EDS characterization graph of the heterogeneous catalyst 1 is shown in

[0179] The actual graph of the heterogeneous catalyst 1 is shown in Figure 3 .

[0180] The organic element analysis of the heterogeneous catalyst 1 showed that the content of each element in the heterogeneous catalyst 1 was: N 3.83 wt%, C 73.99 wt%, H 5.73 wt%, and S 2.78 wt%.

[0181] Example 2

[0182] Step 1: 500 mg of 2-chlorotrityl chloride resin was swelled in dichloromethane for 10 min, and then dichloromethane was removed.

[0183] Step 2: Then Fmoc-Gly 297.3 mg, 330 microliters of DIEA were dissolved in DMF and added to the product of step 1 to react for 2 h; after the reaction was completed, it was washed with DMF for 3 times; 20 mL of blocking agent (DCM:MeOH:DIEA=17:2:1 (volume ratio)) was added to block for 30 min. After the reaction was completed, it was washed with DCM, DMF for 3 times respectively.

[0184] Step 3: 20 mL of Fmoc removal agent (diethylamine:DMF=3:7 (volume ratio)) was added to the product of step 2 to react for 30 min, and after the reaction was completed, it was washed with DMF for 3 times.

[0185] Step 4: 308 mg of 6,6 ， - dithiodinic acid, 379.2 mg of HBTU, 330 microliters of DIEA were dissolved in DMF and added to the product of step 3 to react for 2 h. After the reaction was completed, it was washed with DMF for 3 times.

[0186] Step 5: 154 mg of DL-dithiothreitol was added to the product of step 4 to react for 4 h with DMF as the reaction solvent. After the reaction was completed, it was washed with DMF, DCM for 3 times respectively, and the dichloromethane solvent was extracted to constant weight of the sample.

[0187] Step 6: 760 mg of DBU was added to the product of step 5 to react with DMF as the solvent. After the reaction was completed, it was washed with DMF, DCM for 3 times respectively, and the dichloromethane solvent was extracted to constant weight of the sample to obtain the heterogeneous catalyst 2; the weight was 688.6 mg. The active site content of the heterogeneous catalyst 2 was 0.73 mmol / mg.

[0188] Active site content calculation formula: Wherein, m is the mass, and M is the molar mass.

[0189] Example 3

[0190] Step 1: 500 mg of 2-chlorotrityl chloride resin was swelled in dichloromethane for 10 min, and then dichloromethane was removed.

[0191] Step 2: Then 139 mg of bromoacetic acid was dissolved in DMF and added to the product of step 1 to react for 2 h. After the reaction was completed, it was washed with DMF for 3 times.

[0192] Step 3: 20 mL of capping reagent (DCM:MeOH:DIEA=17:2:1 (volume ratio)) was added to the product from Step 2 and allowed to react for 30 min. After the reaction was completed, the product was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was removed by suction until the sample was constant in weight.

[0193] Step 4: 2 g of tri-n-butylphosphine was added to the product from Step 3 and allowed to react at 100°C for 12 h. After the reaction was completed, the product was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was removed by suction until the sample was constant in weight.

[0194] Step 5: 111 mg of dimercaptopyridine was dissolved in DMF and added to the product from Step 4 and allowed to react for 12 h. After the reaction was completed, the product was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was removed by suction until the sample was constant in weight to obtain the heterogeneous catalyst 3; 690 mg was weighed. The active site content of the heterogeneous catalyst 3 was 0.72 mmol / mg.

[0195] Active site content calculation formula: wherein m is mass and M is molar mass.

[0196] Example 4

[0197] Step 1: 500 mg of 2-chlorotrityl chloride resin was swelled in dichloromethane for 10 min, and then the dichloromethane was removed.

[0198] Step 2: 297.3 mg of Fmoc-Gly, 330 microliters of DIEA were dissolved in DMF, and then added to the product from Step 1 and allowed to react for 2 h. After the reaction was completed, the product was washed with DMF three times.

[0199] Step 3: 20 mL of capping reagent (DCM:MeOH:DIEA=17:2:1 (volume ratio)) was added to the product from Step 2 and allowed to react for 30 min. After the reaction was completed, the product was washed with DCM, DMF three times, respectively.

[0200] Step 4: 20 mL of Fmoc removal reagent (diethylamine:DMF=3:7 (volume ratio)) was added to the product from Step 3 and allowed to react for 30 min. After the reaction was completed, the product was washed with DMF three times. Subsequently, 387 mg of Fmoc-Phe, 379.2 mg of HBTU, 330 microliters of DIEA were dissolved in DMF, and then added to the reaction and allowed to react for 2 h. After the reaction was completed, the product was washed with DMF three times.

[0201] Step 5: 20 mL of Fmoc removal reagent (diethylamine:DMF=3:7 (volume ratio)) was added to the product from Step 4 and allowed to react for 30 min. After the reaction was completed, the product was washed with DMF three times.

[0202] Step 6: To the product obtained in Step 5, 139 mg of bromoacetic acid, 144 mg of DIC dissolved in DMF was added and reacted for 2 h. After the reaction was completed, it was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was evaporated to constant weight of the sample.

[0203] Step 7: To the product obtained in Step 6, 2 g of tri-n-butylphosphine was added and reacted at 100°C for 12 h. After the reaction was completed, it was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was evaporated to constant weight of the sample.

[0204] Step 8: 111 mg of dimercaptopyridine was dissolved in DMF and added to the product obtained in Step 7 and reacted for 12 h. After the reaction was completed, it was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was evaporated to constant weight of the sample to obtain a heterogeneous catalyst 4; weighed 710 mg. The active site content of the heterogeneous catalyst 4 was 0.70 mmol / mg.

[0205] Active site content calculation formula: Wherein, m is the mass, and M is the molar mass.

[0206] Example 5

[0207] Step 1: 500 mg of Rink Amide resin was swelled with dichloromethane for 10 min, then the dichloromethane was removed, and then 20 mL of Fmoc removal agent (diethylamine: DMF = 3:7 (volume ratio)) was added and reacted for 30 min. After the reaction was completed, it was washed with DMF three times.

[0208] Step 2: 154 mg of 6,6 ， - dithiodithionic acid, 379.2 mg of HBTU, 165 microliters of DIEA were dissolved in DMF and added to the product obtained in Step 1 and reacted for 2 h. After the reaction was completed, it was washed with DMF three times.

[0209] Step 3: To the product obtained in Step 2, 20 mL of blocking agent (DCM: MeOH: DIEA = 17:2:1 (volume ratio)) was added and blocked for 30 min. After the reaction was completed, it was washed with DCM, DMF three times, respectively.

[0210] Step 4: To the product obtained in Step 3, 154 mg of disulfide bond breaking agent (DL-dithiothreitol) was added and reacted for 4 h. After the reaction was completed, it was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was evaporated to constant weight of the sample.

[0211] Step 5: 760 mg DBU was added to the product from Step 4 in DMF and reacted for 12 h. After the reaction was completed, it was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was removed by drying to constant weight of the sample to obtain the heterogeneous catalyst 5; 471 mg. The active site content of the heterogeneous catalyst 5 was 0.3 mmol / mg.

[0212] The formula for calculating the active site content is: wherein m is the mass and M is the molar mass.

[0213] Example 6

[0214] Step 1: 500 mg of Rink Amide resin was swelled with dichloromethane for 10 min, then the dichloromethane was removed, and then 20 mL of Fmoc removal agent (diethylamine: DMF = 3:7 (volume ratio)) was added and reacted for 30 min. After the reaction was completed, it was washed with DMF three times.

[0215] Step 2: 297.3 mg of Fmoc-Gly, 379.2 mg of HBTU, and 330 microliters of DIEA were dissolved in DMF and then added to the product from Step 1 and reacted for 2 h. After the reaction was completed, it was washed with DMF three times.

[0216] Step 3: 20 mL of blocking agent (DCM:MeOH:DIEA = 17:2:1 (volume ratio)) was added to the product from Step 2 and blocked for 30 min. After the reaction was completed, it was washed with DCM, DMF three times, respectively.

[0217] Step 4: 20 mL of Fmoc removal agent (diethylamine: DMF = 3:7 (volume ratio)) was added to the product from Step 3 and reacted for 30 min. After the reaction was completed, it was washed with DMF three times.

[0218] Step 5: 154 mg of 6,6 ， dithiodinic acid, 379.2 mg of HBTU, and 165 microliters of DIEA were condensed in DMF for 2 h. After the reaction was completed, it was washed with DMF three times.

[0219] Step 6: 154 mg of DL-dithiothreitol was added to the product from Step 5 in DMF as the reaction solvent. After the reaction was completed, it was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was removed by drying to constant weight of the sample.

[0220] Step 7: 760 mg of DBU was added to the product obtained in Step 6 to react for 12 h in DMF. After the reaction was completed, the product was washed with DMF, DCM for 3 times, respectively, and the dichloromethane solvent was extracted to constant weight of the sample to obtain the heterogeneous catalyst 6; 550 mg was weighed. The active site content of the heterogeneous catalyst 6 was 0.55 mmol / mg.

[0221] The active site content calculation formula is: Wherein, m is the mass, and M is the molar mass.

[0222] Example 7

[0223] Step 1: 500 mg of Rink Amide resin was swelled with dichloromethane for 10 min, and then dichloromethane was removed, and then 20 mL of Fmoc removing agent (diethylamine: DMF = 3:7 (volume ratio)) was added to react for 30 min. After the reaction was completed, the product was washed with DMF for 3 times.

[0224] Step 2: 139 mg of bromoacetic acid and 114 mg of DIC were dissolved in DMF and then added to the product obtained in Step 1 to react for 2 h. After the reaction was completed, the product was washed with DMF for 3 times.

[0225] Step 3: 20 mL of blocking agent (DCM:MeOH:DIEA = 17:2:1 (volume ratio)) was added to the product obtained in Step 2 to block for 30 min. After the reaction was completed, the product was washed with DCM, DMF for 3 times, respectively.

[0226] Step 4: 2 g of tri-n-butyl phosphine was added to the product obtained in Step 3 to react for 12 h at 120°C. After the reaction was completed, the product was washed with DMF, DCM for 3 times, respectively, and the dichloromethane solvent was extracted to constant weight of the sample.

[0227] Step 5: 111 mg of dimercapto pyridine was dissolved in DMF and then added to the product obtained in Step 4 to react for 12 h. After the reaction was completed, the product was washed with DMF, DCM for 3 times, respectively, and the dichloromethane solvent was extracted to constant weight of the sample to obtain the heterogeneous catalyst 7; 504.6 mg was weighed. The active site content of the heterogeneous catalyst 7 was 0.30 mmol / mg.

[0228] The active site content calculation formula is: Wherein, m is the mass, and M is the molar mass.

[0229] Example 8

[0230] Step 1: 500 mg of Rink Amide resin was swelled with dichloromethane for 10 min, and then dichloromethane was removed, and then 20 mL of Fmoc removing agent (diethylamine: DMF = 3:7 (volume ratio)) was added to react for 30 min. After the reaction was completed, the product was washed with DMF for 3 times.

[0231] Step 2: 297.3 mg Fmoc-Gly, 379.2 mg HBTU, 330 microliters DIEA were dissolved in DMF and added to the product from Step 1 and reacted for 2 h. After the reaction was completed, it was washed with DMF three times.

[0232] Step 3: To the product from Step 2, 20 mL of a capping reagent (DCM:MeOH:DIEA = 17:2:1 (volume ratio)) was added and reacted for 30 min. After the reaction was completed, it was washed with DCM, DMF three times, respectively.

[0233] Step 4: To the product from Step 3, 20 mL of a Fmoc removal reagent (diethylamine:DMF = 3:7 (volume ratio)) was added and reacted for 30 min. After the reaction was completed, it was washed with DMF three times.

[0234] Step 5: To the product from Step 4, 139 mg bromoacetic acid, 114 mg DIC condensing reagent were dissolved in DMF and reacted for 2 h. After the reaction was completed, it was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was removed to constant weight.

[0235] Step 6: To the product from Step 5, 2 g tri-n-butylphosphine was added and reacted at 100°C for 12 h. After the reaction was completed, it was washed with DMF, DCM three times, respectively, and the dichloromethane solvent was removed to constant weight.

[0236] Step 7: 111 mg dimercaptopyridine was dissolved in DMF and added to the product from Step 6 and reacted for 12 h. After the reaction was completed, it was washed with DMF, DCM three times, and then the solvent was removed to obtain the heterogeneous catalyst 8; the weight was 541 mg. The active site content of the heterogeneous catalyst 8 was 0.50 mmol / mg.

[0237] The formula for calculating the active site content is: wherein m is the mass and M is the molar mass.

[0238] Example 9

[0239] Step 1: 500 mg Rink Amide resin was swelled with dichloromethane for 10 min, and then the dichloromethane was removed, and then 20 mL of a Fmoc removal reagent (diethylamine:DMF = 3:7 (volume ratio)) was added and reacted for 30 min. After the reaction was completed, it was washed with DMF three times.

[0240] Step 2: 206 mg lipoic acid, 297.3 mg HBTU were dissolved in DMF and added to the product from Step 1 and reacted for 2 h. After the reaction was completed, it was washed with DMF three times.

[0241] Step 3: To the product obtained in step 2, 20 mL of capping reagent (DCM:MeOH:DIEA = 17:2:1 (volume ratio)) was added and capped for 30 min. After the reaction was completed, it was washed with DCM, DMF for 3 times, respectively.

[0242] Step 4: To the product obtained in step 3, 154 mg of DL-dithiothreitol was added and reacted for 4 h. After the reaction was completed, it was washed with DMF, DCM for 3 times, respectively, and the dichloromethane solvent was removed to constant weight of the sample.

[0243] Step 5: To the product obtained in step 4, 760 mg of DBU (1,8-diazabicyclo-undecane-7-ene) was added and reacted for 12 h in DMF. After the reaction was completed, it was washed with DMF, DCM for 3 times, respectively, and the dichloromethane solvent was removed to constant weight of the sample to obtain the heterogeneous catalyst 9; the weight was 518 mg. The active site content of the heterogeneous catalyst 1 was 0.386 mmol / mg.

[0244] The active site content calculation formula is: wherein m is the mass and M is the molar mass.

[0245] Unless otherwise specified, all steps of Examples 1-9 were carried out at 25°C under normal pressure.

[0246] Example 10

[0247] The heterogeneous catalyst 1 catalyzes the conversion of epichlorohydrin and CO2 to chloromethyl-1, 3-dioxolane-2-ketone.

[0248]

[0249] Into a 15 mL stainless steel autoclave equipped with a magnetic stirrer, 6.0 mol% of the heterogeneous catalyst 1, 1 mmol of epichlorohydrin and 2 mL of DMF solvent were sequentially added, and preheated to 120°C under the condition of stirring at 400 r / min, and 1 MPa of CO2 was introduced into the autoclave. After the gas was filled, the reaction was carried out at 120°C under the condition of stirring at 400 r / min for 15 h. After the reaction was completed, the autoclave was naturally cooled to room temperature, then the remaining gas in the autoclave was released, and the reaction liquid was transferred and purified by column chromatography. The yield was calculated by quantitative nuclear magnetic resonance, and the yield of chloromethyl-1, 3-dioxolane-2-ketone was 99% with a purity of more than 99% in the form of colorless oil.

[0250] “6.0 mol% of the heterogeneous catalyst 1” refers to the molar content of the active sites in the heterogeneous catalyst 1 is 6.0% of the molar amount of epichlorohydrin.

[0251] The nuclear magnetic resonance characterization data is 1H NMR (500 MHz, CDCl3) δ (ppm) 4.99 - 4.94 (m, 1H),4.59 (t, J = 9.0 Hz, 1H), 4.42 - 4.39 (m, 1H), 3.80 - 3.71 (m, 2H). 13 C NMR (125MHz, CDCl3) δ (ppm) 154.26, 74.36, 67.09, 43.75.

[0252] Example 11

[0253] Heterogeneous catalyst 2 catalyzing the conversion of epichlorohydrin and CO2 to chloromethyl-1, 3-dioxolane-2-one.

[0254] Into a 15 mL stainless steel autoclave equipped with a magnetic stirrer, 6.0 mol% heterogeneous catalyst 2, 1 mmol epichlorohydrin and 2 mL DMF solvent were sequentially added. The reactor was preheated to 120 °C with stirring at 400 r / min, and 1 MPa CO2 was introduced into the reactor. After the gas was charged, the reaction was carried out at 120 °C with stirring at 400 r / min for 15 h. After the reaction was completed, the reactor was naturally cooled to room temperature, and the remaining gas in the reactor was released. The reaction solution was transferred and purified by column chromatography. The yield was calculated by quantitative nuclear magnetic resonance, and 99% yield of colorless oil chloromethyl-1, 3-dioxolane-2-one with a purity greater than 99% was obtained.

[0255] “6.0 mol% heterogeneous catalyst 2” refers to the molar content of active sites in heterogeneous catalyst 2 is 6.0% of the molar amount of epichlorohydrin.

[0256] The nuclear magnetic resonance characterization data are 1 H NMR (500 MHz, CDCl3) δ (ppm) 4.99 - 4.94 (m, 1H),4.59 (t, J = 9.0 Hz, 1H), 4.42 - 4.39 (m, 1H), 3.80 - 3.71 (m, 2H). 13 C NMR (125MHz, CDCl3) δ (ppm) 154.26, 74.36, 67.09, 43.75.

[0257] Example 12

[0258] Heterogeneous catalyst 3 catalyzing the conversion of epichlorohydrin and CO2 to chloromethyl-1, 3-dioxolane-2-one.

[0259] Into a 15 mL stainless steel autoclave equipped with a magnetic stirrer, 6.0 mol% of heterogeneous catalyst 3, 1 mmol of epichlorohydrin and 2 mL of DMF solvent were sequentially added. The reactor was heated to 120 °C under stirring at 400 r / min. Then, 1 MPa of CO2 was introduced into the reactor. After the completion of the gas charging, the reaction was carried out at 120 °C under stirring at 400 r / min for 15 h. After the reaction, the reactor was naturally cooled to room temperature, and then the remaining gas in the reactor was released. The reaction solution was transferred and purified by column chromatography. The yield was calculated by quantitative nuclear magnetic resonance, and 99% yield of colorless oil chloromethyl-1, 3-dioxolane-2-one with a purity of more than 99% was obtained.

[0260] “6.0 mol% of heterogeneous catalyst 3” refers to the molar content of active sites in the heterogeneous catalyst 3 is 6.0% of the molar amount of epichlorohydrin.

[0261] The nuclear magnetic resonance characterization data are 1 H NMR (500 MHz, CDCl3) δ (ppm) 4.99 - 4.94 (m, 1H),4.59 (t, J = 9.0 Hz, 1H), 4.42 - 4.39 (m, 1H), 3.80 - 3.71 (m, 2H). 13 C NMR (125MHz, CDCl3) δ (ppm) 154.26, 74.36, 67.09, 43.75.

[0262] Example 13

[0263] Heterogeneous catalyst 4 catalyzing the conversion of epichlorohydrin and CO2 to generate chloromethyl-1, 3-dioxolane-2-one.

[0264] Into a 15 mL stainless steel autoclave equipped with a magnetic stirrer, 10 mol% of heterogeneous catalyst 4, 1 mmol of epichlorohydrin and 2 mL of DMF solvent were sequentially added. The reactor was heated to 120 °C under stirring at 400 r / min. Then, 1 MPa of CO2 was introduced into the reactor. After the completion of the gas charging, the reaction was carried out at 120 °C under stirring at 400 r / min for 15 h. After the reaction, the reactor was naturally cooled to room temperature, and then the remaining gas in the reactor was released. The reaction solution was transferred and purified by column chromatography. The yield was calculated by quantitative nuclear magnetic resonance, and 99% yield of colorless oil chloromethyl-1, 3-dioxolane-2-one with a purity of more than 99% was obtained.

[0265] “10.0 mol% of heterogeneous catalyst 4” refers to the molar content of active sites in the heterogeneous catalyst 4 is 10.0% of the molar amount of epichlorohydrin.

[0266] The nuclear magnetic resonance characterization data are 1H NMR (500 MHz, CDCl3) δ (ppm) 4.99 - 4.94 (m, 1H),4.59 (t, J = 9.0 Hz, 1H), 4.42 - 4.39 (m, 1H), 3.80 - 3.71 (m, 2H). 13 C NMR (125MHz, CDCl3) δ (ppm) 154.26, 74.36, 67.09, 43.75.

[0267] Example 14

[0268] Heterogeneous catalyst 5 catalyzing conversion of epichlorohydrin and CO2 to chloromethyl-1, 3-dioxolane-2-one.

[0269] Into a 15 mL stainless steel autoclave equipped with a magnet, 10 mol% heterogeneous catalyst 5, 1 mmol epichlorohydrin and 2 mL DMF solvent were sequentially added. The reactor was preheated to 120 °C with stirring at 400 r / min. Then 1 MPa CO2 was introduced into the reactor. After the completion of the gas charging, the reaction was carried out at 120 °C with stirring at 400 r / min for 15 h. After the reaction, the reactor was naturally cooled to room temperature, and then the remaining gas in the reactor was released. The reaction solution was transferred and purified by column chromatography. The yield was calculated by quantitative nuclear magnetic resonance, and 38% of chloromethyl-1, 3-dioxolane-2-one with a purity of more than 99% was obtained as a colorless oil.

[0270] “10.0 mol% heterogeneous catalyst 5” refers to the molar content of active sites in heterogeneous catalyst 5 is 10.0% of the molar amount of epichlorohydrin.

[0271] The nuclear magnetic resonance characterization data are 1 H NMR (500 MHz, CDCl3) δ (ppm) 4.99 - 4.94 (m, 1H),4.59 (t, J = 9.0 Hz, 1H), 4.42 - 4.39 (m, 1H), 3.80 - 3.71 (m, 2H). 13 C NMR (125MHz, CDCl3) δ (ppm) 154.26, 74.36, 67.09, 43.75.

[0272] Example 15

[0273] Heterogeneous catalyst 1 catalyzing conversion of N- (oxan-2-ylmethyl) aniline and CO2 to 5- (hydroxymethyl) -3-phenyl-2-oxazolidinone.

[0274]

[0275] Into a 15 mL stainless steel autoclave equipped with a magnet, 10 mol% of heterogeneous catalyst 1, 1 mmol of N-(oxiran-2-ylmethyl)aniline and 2 mL of MeCN solvent were sequentially added, and preheated to 110 °C under stirring at 400 r / min. Then 1 MPa of CO2 was introduced into the reactor. After the completion of the gas charging, the reaction was carried out at 110 °C under stirring at 400 r / min for 15 h. After the completion of the reaction, the reactor was naturally cooled to room temperature, and then the remaining gas in the reactor was released. The reaction solution was transferred and purified by column chromatography. The yield was calculated by quantitative nuclear magnetic resonance, and white powder 5-(hydroxymethyl)-3-phenyl-2-oxazolidinone with a yield of 99% and a purity of more than 99% was obtained.

[0276] “10.0 mol% heterogeneous catalyst 1” refers to the molar content of active sites in heterogeneous catalyst 1 is 10.0% of the molar amount of N-(oxiran-2-ylmethyl)aniline.

[0277] The nuclear magnetic resonance characterization data are 1 H NMR (500 MHz, CDCl3) δ (ppm) 7.55 - 7.53 (m, 2H),7.39 - 7.35 (m, 2H), 7.15 - 7.12 (m, 1H), 4.76 - 4.71 (m, 1H), 4.05 - 3.95(m, 3H), 3.76 - 3.72 (m, 1H), 2.58(s, O H ). 13 C NMR (125 MHz, CDCl3) δ (ppm)155.02, 138.22, 129.21, 124.33, 118.48, 73.05, 62.89, 46.48.

[0278] Example 16

[0279] Heterogeneous catalyst 1 catalyzing the conversion of N-methylaniline and CO2 to N-methyl-N-phenylcarboxamide.

[0280]

[0281] Into a 15 mL stainless steel autoclave equipped with a magnetic stirrer, 8.0 mol% of heterogeneous catalyst 1, 1 mmol of N-methylaniline and 2 mL of MeCN solvent were sequentially added, and the reactor was preheated to 90 °C under stirring at 400 r / min. Then, 1 MPa of CO2 was introduced into the reactor. After the completion of the gas charging, the reaction was carried out at 90 °C under stirring at 400 r / min for 15 h. After the completion of the reaction, the reactor was naturally cooled to room temperature, and then the remaining gas in the reactor was released. The reaction solution was transferred, purified by column chromatography, and the yield was calculated by quantitative nuclear magnetic resonance to obtain N-methyl-N-phenylformamide in the form of a yellow oily liquid with a yield of 93% and a purity of more than 99%.

[0282] “8.0 mol% heterogeneous catalyst 1” refers to the molar content of active sites in the heterogeneous catalyst 1 being 8.0% of the molar amount of N-methylaniline.

[0283] The nuclear magnetic resonance characterization data are 1 H NMR (500 MHz, CDCl3) δ (ppm) 8.47 (s, 1H), 7.41 (t, J= 7.8 Hz, 2H), 7.28 (t, J = 7.4 Hz, 1H), 7.17 (d, J = 7.7 Hz, 2H), 3.32 (s,3H). 13 C NMR (125 MHz, CDCl3) δ (ppm) 162.39, 142.24, 129.68, 126.45, 122.42,32.11.

[0284] Example 17

[0285] Heterogeneous catalyst 6 catalyzing the conversion of N-(oxiran-2-ylmethyl)aniline and CO2 to 5-(hydroxymethyl)-3-phenyl-2-oxazolidinone.

[0286]

[0287] Into a 15 mL stainless steel autoclave equipped with a magnetic stirrer, 10.0 mol% of heterogeneous catalyst 6, 1 mmol of N-(oxiran-2-ylmethyl)aniline and 2 mL of MeCN solvent were sequentially added, and the reactor was preheated to 90 °C under stirring at 400 r / min. Then, 1 MPa of CO2 was introduced into the reactor. After the completion of the gas charging, the reaction was carried out at 90 °C under stirring at 400 r / min for 15 h. After the completion of the reaction, the reactor was naturally cooled to room temperature, and then the remaining gas in the reactor was released. The reaction solution was transferred, purified by column chromatography, and the yield was calculated by quantitative nuclear magnetic resonance to obtain 5-(hydroxymethyl)-3-phenyl-2-oxazolidinone in the form of a white powder with a yield of 99% and a purity of more than 99%.

[0288] “10.0 mol% heterogeneous catalyst 6” refers to the molar content of active sites in heterogeneous catalyst 6 is 10.0% of the molar amount of N-(oxiran-2-ylmethyl).

[0289] NMR characterization data are 1 H NMR (500 MHz, CDCl3) δ (ppm) 7.55 - 7.53 (m, 2H),7.39 - 7.35 (m, 2H), 7.15 - 7.12 (m, 1H), 4.76 - 4.71 (m, 1H), 4.05 - 3.95(m, 3H), 3.76 - 3.72 (m, 1H), 2.58(s, OH). 13 C NMR (125 MHz, CDCl3) δ (ppm)155.02, 138.22, 129.21, 124.33, 118.48, 73.05, 62.89, 46.48.

[0290] Example 18

[0291] Heterogeneous catalyst 7 catalyzes the conversion of n-butyl glycidyl ether and CO2 to generate 4-(butyloxymethyl)-1,3-dioxolane-2-one.

[0292]

[0293] Into a 15 mL stainless steel autoclave equipped with a magnetic stirrer, 10.0 mol% heterogeneous catalyst 7, 1 mmol n-butyl glycidyl ether and 2 mL DMF solvent were sequentially added, and preheated to 90°C under the condition of 400 r / min stirring, and 1 MPa CO2 was introduced into the reactor. After the gas was filled, the reaction was carried out at 90°C under the condition of 400 r / min stirring for 15 h. After the reaction was completed, the reactor was naturally cooled to room temperature, then the remaining gas in the reactor was released, the reaction liquid was transferred, purified by column chromatography, and the yield was calculated by quantitative NMR to obtain 99% yield of liquid 4-(butyloxymethyl)-1,3-dioxolane-2-one with a purity of more than 99%.

[0294] “10.0 mol% heterogeneous catalyst 7” refers to the molar content of active sites in heterogeneous catalyst 7 is 10.0% of the molar amount of n-butyl glycidyl ether.

[0295] NMR characterization data are 1H NMR (500 MHz, CDCl3) δ (ppm) 4.80-4.77 (m, 1H), 4.48-4.34 (m, 2H), 3.66-3.56 (m, 2H), 3.48 (t, J = 6.3 Hz, 2H), 1.54-1.50 (m, 2H),1.35-1.30 (m, 2H), 0.88 (t, J = 7.4 Hz, 3H). 13 C NMR (125 MHz, CDCl3) δ (ppm)155.10, 75.24, 71.90, 69.68, 66.36, 31.56, 19.19, 13.87.

[0296] Example 19

[0297] Heterogeneous catalyst 8 catalyzing the conversion of o-phenylenediamine and CO2 to benzimidazole.

[0298]

[0299] Into a 15 mL stainless steel autoclave equipped with a magnetic stirrer, 10.0 mol% heterogeneous catalyst 8, 1 mmol o-phenylenediamine and 2 mL MeCN solvent were added successively, and preheated to 90 °C under stirring at 400 r / min. 1 MPa CO2 was introduced into the reactor. After the completion of the gas charging, the reaction was carried out at 90 °C under stirring at 400 r / min for 15 h. After the completion of the reaction, the reactor was naturally cooled to room temperature, and then the residual gas in the reactor was released. The reaction solution was transferred and purified by column chromatography. The yield was calculated by quantitative nuclear magnetic resonance, and benzimidazole with a yield of 67% and a purity of more than 99% was obtained.

[0300] “10.0 mol% heterogeneous catalyst 8” refers to the molar content of active sites in heterogeneous catalyst 8 is 10.0% of the molar amount of o-phenylenediamine.

[0301] The nuclear magnetic resonance characterization data are 1 H NMR (500 MHz, DMSO- d 6) δ 12.40 (s, 1H), 8.18 (d, J =2.5 Hz, 1H), 7.70 – 7.43 (m, 2H), 7.17 (t, J = 9.2 Hz, 2H). 13 C NMR (126 MHz,DMSO- d 6) δ 142.53, 122.05, 115.76.

Claims

1. A heterogeneous catalyst for catalyzing the conversion of CO2, selected from at least one of the compounds shown in Formula 1, Formula 3, Formula 6, Formula 8; Formula 1, 3, 6, 8: wherein: R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50, R51, R52, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63, R64, R65, R66, R67, R68, R69, R70, R71, R72, R73, R74, R75, R76, R77, R78, R79, R80, R81, R82, R83, R84, R85, R86, R87, R88, R89, R90, R91, R92, R93, R94, R95, R96, R97, R98, R99, R100, R101, R102, R103, R104, R105, R106, R107, R108, R109, R110, R111, R112, R113, R114, R115, R116, R117, R118, R119, R120, R121, R122, R123, R124, R125, R126, R127, R128, R129, R130, R131, R132, R133, R134, R135, R136, R137, R138, R139, R140, R141, R142, R143, R144, R145, R146, R147, R148, R149, R150, R151, R152, R153, R154, R155, R156, R157, R158, R159, R160, R161, R162, R163, R164, R165, R166, R167, R168, R169, R170, R171, R172, R173, R174, R175, R176, R177, R178, R179, R180, R181, R182, R183, R184, R185, R186, R187, R188, R189, R190, R191, R192, R193, R194, R195, R196, R197, R198, R199, R200, R201, R202, R203, R204, R205, R206, R207, R208, R209, R210, R211, R212, R213, R214, R215, R216, R217, R218, R219, R220, R221, R222, R223, R224, R225, R226, R227, R228, R229, R230, R231, R232, R233, R234, R235, R236, R237, R238, R239, R240, R241, R242, R243, R244, R245, R246, R247, R248, R249, R250, R251, R252, R253, R254, R255, R256, R257, R258, R259, R260, R261, R262, R263, R264, R265, R266, R267, R268, R269, R270, R271, R272, R273, R274, R275, R276, R277, R278, R279, R280, R281, R282, R283, R284, R285, R286, R287, R288, R289, R290, R291, R292, R293, R294, R295, R296, R297, R298, R299, R300, R301, R302, R303, R304, R305, R306, R307, R308, R309, R310, R311, R312, R313, R314, R315, R316, R317, R318, R319, R320, R321, R322, R323, R324, R325, R326, R327, R328, R329, R330, R331, R332, R333, R334, R335, R336, R337, R338, R339, R340, R341, R342, R343, R344, R345, R346, R347, R348, R349, R350, R351, R352, R353, R354, R355, R356, R357, R358, R359, R360, R361, R362, R363, R364, R365, R366, R367, R368, R369, R370, R371, R372, R373, R374, R375, R376, R377, R378, R379, R380, R381, R382, R383, R384, R385, R386, R387, R388, R389, R390, R391, R392, R393, R394, R395, R396, R397, R398, R399, R400, R401, R402, R403, R404, R405, R406, R407, R408, R409, R410, R411, R412, R413, R414, R415, R416, R417, R418, R419, R420, R421, R422, R423, R424, R425, R426, R427, R428, R429, R430, R431, R432, R433, R434, R435, R436, R437, R438, R439, R440, R441, R442, R443, R444, R445, R446, R447, R448, R449, R450, R451, R452, R453, R454, R455, R456, R457, R458, R459, R460, R461, R462, R463, R464, R465, R466, R467, R468, R469, R470, R471, R472, R473, R474, R475, R476, R477, R478, R479, R480, R481, R482, R483, R484, R485, R486, R487, R488, R489, R490, R491, R492, R493, R494, R495, R496, R497, R498, R499, R500, R501, R502, R503, R504, R505, R506, R507, R508, R509, R510, R511, R512, R513, R514, R515, R516, R517, R518, R519, R520, R521, R522, R523, R524, R525, R526, R527, R528, R529, R530, R531, R532, R533, R534, R535, R536, R537, R538, R539, R540, R541, R542, R543, R544, R545, R546, R547, R548, R549, R550, R551, R552, R553, R554, R555, R556, R557, R558, R559, R560, R561, R562, R563, R564, R565, R566, R567, R568, R569, R570, R571, R572, R573, R574, R575, R576, R577, R578, R579, R580, R581, R582, R583, R584, R585, R586, R587, R588, R589, R590, R591, R592, R593, R594, R595, R596, R597, R598, R599, R600, R601, R602, R603, R604, R605, R606, R607, R608, R609, R610, R611, R612, R613, R614, R615, R616, R617, R618, R619, R620, R621, R622, R623, R624, R625, R626, R627, R628, R629, R630, R631, R632, R633, R634, R635, R636, R637, R638, R639, R640, R641, R642, R643, R644, R645, R646, R647, R648, R649, R650, R651, R652, R653, R654, R655, R656, R657, R658, R659, R660, R661, R662, R663, R664, Formula 1, Formula 3, Formula 6, Formula 8; In formulae 1, 3, R is derived from a resin having a modifying group attached to the surface; the modifying group is selected from , wherein represents the position of attachment to the resin; in formulae 6, 8, is a polystyrene-divinylbenzene crosslinked resin; ​ derived from amino acids; Sulfur source - S - derived from a sulfur-containing small molecule selected from at least one of benzenethiol or a dimer thereof, substituted benzenethiol or a dimer thereof, a mercapto-containing heterocyclic compound or a dimer thereof, a substituted mercapto-containing heterocyclic compound or a dimer thereof, lipoic acid, wherein the molecular weight of the sulfur-containing small molecule is less than 500, and ​ E + derived from compound A, said compound A being at least one of an organic salt or an organic base capable of providing cations; X + derived from a compound B selected from at least one of a trialkylphosphine, a triarylphosphine, a trialkylamine, a triarylamine; n=0-10。 ​ ​ ​ ​ ​ ​ ​ The sulfur-containing small molecule is selected from at least one of 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercaptonicotinic acid, 6,6 ， - dithioninic acid, 5-mercaptonicotinic acid, 4-mercaptonicotinic acid, 3-mercaptoisonicotinic acid, 2-mercaptonicotinic acid, 6-mercaptopyridinecarboxylic acid, 2-mercaptopyridine, 4-thiolpyridine, 2-thiopyrimidine, 4-methylthiophenol, 4-bromothiophenol, 4-nitrothiophenol, 4-methoxythiophenol, and sodium hydrosulfide.

4. The heterogeneous catalyst according to claim 1, characterized in that, ​ Formula 5 Formula 7 in formulae 5, 7, is a polystyrene-divinylbenzene crosslinked resin, n = 0-10. ​ ​ ​ ​ ​ ​ ​ ​ ​ adding a sulfur-containing small molecule, a basic auxiliary agent and optionally a condensing agent A to the resin dissolved in a solvent A to perform a condensation reaction, adding a blocking agent to perform a blocking reaction, adding a disulfide bond cleavage reagent to perform a disulfide bond cleavage reaction, and adding a compound A to perform a salt formation reaction; or, when n = 1-10, the method one comprises: adding an amino acid, a basic auxiliary agent and optionally a condensing agent A to the resin dissolved in a solvent B to perform a condensation reaction, adding a blocking agent to perform a blocking reaction, adding a Fmoc removing agent to perform a Fmoc removing reaction, and performing 0-9 times of "adding an amino acid, a condensing agent A and a basic auxiliary agent to perform a condensation reaction, adding a Fmoc removing agent to perform a Fmoc removing reaction" operation, adding a halogenated aliphatic acid and a condensing agent B to perform a condensation reaction, adding a compound B to perform a substitution reaction, and adding a sulfur-containing small molecule to perform a substitution reaction. when n = 0, the method two comprises: adding a halogenated aliphatic acid and optionally a condensing agent B to the resin swelled in a solvent B to perform a condensation reaction, adding a blocking agent to perform a blocking reaction, adding a compound B to perform a substitution reaction, and adding a sulfur-containing small molecule to perform a substitution reaction; or, when n = 1-10, the method two comprises: adding an amino acid, a basic auxiliary agent and optionally a condensing agent A to the resin dissolved in a solvent B to perform a condensation reaction, adding a blocking agent to perform a blocking reaction, adding a Fmoc removing agent to perform a Fmoc removing reaction, and performing 0-9 times of "adding an amino acid, a condensing agent A and a basic auxiliary agent to perform a condensation reaction, adding a Fmoc removing agent to perform a Fmoc removing reaction" operation, adding a halogenated aliphatic acid and a condensing agent B to perform a condensation reaction, adding a compound B to perform a substitution reaction, and adding a sulfur-containing small molecule to perform a substitution reaction.

8. The preparation method of claim 7, wherein, the feeding ratio of the resin to the amino acid is 500 mg: (1-1.5) mmol; or / and, the feeding ratio of the resin to the sulfur-containing small molecule is 500 mg: (1-1.5) mmol; or / and, the feeding ratio of the resin to the halogenated aliphatic acid is 500 mg: (1-1.5) mmol; or / and, the feeding ratio of the resin to the compound A is 500 mg: (1-10) mmol; or / and, the feeding ratio of the resin to the compound B is 500 mg: (1-10) mmol; or / and, the basic auxiliary agent is selected from at least one of N,N-diisopropylethylamine and triethylamine; or / and, the condensing agent A is selected from 2-(7-azabenzotriazol)-N,N,N',N'-tetramethyluronium hexafluorophosphate, O-benzotriazol-tetramethyluronium hexafluorophosphate, 6-chlorobenzotriazol-1,1,3,3-tetramethyluronium hexafluorophosphate, 2-succinimidyl-1,1,3,3-tetramethyluronium tetrafluoroborate, O-benzotriazol-N,N,N',N'-tetramethyluronium tetrafluoroborate; or / and, the solvent A is selected from N,N-dimethylformamide and dichloromethane; or / and, the blocking agent is composed of dichloromethane, an alcohol and a basic auxiliary agent; or / and, The disulfide bond breaking reagent is selected from at least one of sodium bisulfite, DL-dithiothreitol; or / and, The Fmoc removing reagent consists of diethylamine and N,N-dimethylformamide or consists of piperidine and N,N-dimethylformamide; or / and, The halogenated aliphatic acid is selected from halogenated aliphatic acid with carbon atoms 2-6; or / and, The condensing agent B is selected from N,N'-diisopropylcarbodiimide; or / and, The solvent B is selected from N,N-dimethylformamide, dichloromethane.

9. A method for catalytic conversion of CO2, comprising: The reaction raw material is reacted with CO2 under the catalysis of a catalyst; The raw material is selected from at least one of o-phenylenediamine compounds, oxirane compounds, nitrogen aryl epoxy amine compounds and N-methylaniline compounds; The catalyst is selected from the heterogeneous catalyst as claimed in any one of claims 1-5 or the heterogeneous catalyst prepared by the preparation method as claimed in any one of claims 6-8.

10. The CO2 catalytic conversion method of claim 9, wherein, The reaction temperature is 70.0-140.0℃; or / and, The reaction pressure is 0.5-3.0 MPa; or / and, The reaction time is 0.5-36.0 h; or / and, The molar ratio of the active site of the heterogeneous catalyst to the raw material is (0.01-0.5):1; or / and, The reaction is carried out in a solvent.

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