A graphene oxide membrane material and method for selectively catalyzing the ammonolysis reaction of epoxy compounds

Abstract

The present invention provides a graphene oxide film material and a method for selectively catalyzing the ammonolysis reaction of epoxy compounds. The present invention promotes the mixing of sp 2 ‑sp 3 The hybrid GO phase is transformed into different oxidation regions and graphite regions to achieve the ordering of graphite domains. The heat treatment temperature is regulated to adjust the degree of ordering, corresponding to graphite domains of different numbers and sizes, thereby achieving the regulation of graphite domain content. By utilizing the two-dimensional nanoconfined channels provided by graphene oxide nanosheets between membrane layers and the stabilizing effect of graphite domains on the surface of interlayer nanosheets on intermediates, combined with the synergistic catalytic effect of acidic catalytic sites, the efficient catalysis of the ammonolysis reaction of epoxy compounds is achieved at room temperature in a continuous mobile phase reaction mode. The reactant conversion rate can reach up to 100%, and the reaction regioselectivity can reach up to 100:0. The configuration of the main product obtained is opposite to that of the raw material. The product does not need to be separated and purified and is environmentally friendly.

Description

Technical Field

[0001] The invention relates to a graphene oxide membrane material with adjustable graphite domain content and interlayer spacing and a method thereof for catalyzing the ammonolysis reaction of epoxy compounds with high conversion rate and high regional selectivity at room temperature, belonging to the technical field of membrane catalytic materials and applications. Background Art

[0002] The ammonolysis reaction of epoxy compounds refers to the reaction in which epoxy compounds (i.e. compounds containing a three-membered oxygen heterocyclic structure) break the epoxy bond under the action of ammonia or amine compounds to generate amino alcohol compounds. It is one of the key reactions in organic chemistry to build complex molecular structures. Under the action of acidic or basic catalysts, ammonia or amines act as nucleophiles to attack the carbon cations in epoxy compounds, and the generated intermediates are protonated or deprotonated to generate stable amino alcohol products.

[0003] The ammonolysis reaction of epoxy compounds has a wide range of applications in the field of organic synthesis. Through the reaction of epoxy compounds with ammonia or amines, a series of amino alcohol compounds can be synthesized, which are widely used in the preparation of medicines, pesticides, surfactants and functional materials, especially the synthesis of β-amino alcohol drugs such as β-blockers. The ammonolysis reaction of epoxy compounds is generally carried out under the action of a catalyst. The existing catalyst systems mostly use Lewis acids such as aluminum chloride, Brønsted acids such as sulfuric acid, and organic bases such as triethylamine and pyridine. There are many problems such as the need for heating (50~100°C), long reaction time (>1h), low conversion rate (5~99%), and low reaction regioselectivity (53:47~95:5). Low regioselectivity leads to increased complexity and separation difficulty of the product mixture; while higher reaction temperature increases energy consumption, which is not conducive to the development of green chemistry; homogeneous catalysts are difficult to recover after the reaction, and commonly used acidic and alkaline catalysts are corrosive and toxic, resulting in resource waste and environmental pollution. Summary of the invention

[0004] In order to solve the problems of high reaction temperature, long reaction time, low conversion rate, poor regioselectivity and complex separation and purification of products in the prior art, the present invention provides a graphene oxide film catalytic material with adjustable graphite domain content and interlayer spacing for catalyzing the ammonolysis reaction of epoxy compounds and a preparation method and use thereof. The graphene oxide film catalytic material not only retains the inherent acidic catalytic sites of graphene oxide nanosheets, but also has adjustable graphite domain content and interlayer spacing. Through a mild heat treatment procedure, the mixed sp 2 -sp 3The hybrid GO phase is transformed into different oxidation regions and graphite regions to achieve the ordering of graphite domains. The heat treatment temperature is regulated to adjust the degree of ordering, corresponding to graphite domains of different numbers and sizes, thereby achieving the regulation of graphite domain content. By utilizing the two-dimensional nanoconfined channels provided by graphene oxide nanosheets between membrane layers and the stabilizing effect of graphite domains on the surface of interlayer nanosheets on intermediates, combined with the synergistic catalytic effect of acidic catalytic sites, the efficient catalysis of the ammonolysis reaction of epoxy compounds is achieved at room temperature in a continuous mobile phase reaction mode. The reactant conversion rate can reach up to 100%, and the reaction regioselectivity can reach up to 100:0. The configuration of the main product obtained is opposite to that of the raw material. The enantioselectivity of the reaction can be as high as 100:0. The product does not need to be separated and purified and is environmentally friendly.

[0005] The technical solution of the present invention is as follows:

[0006] A graphene oxide film material, wherein the graphite domain size is 1.2-2.0 nm, the interlayer spacing is 0.6-1.5 nm, and the atomic ratio of carbon to oxygen is 2.0-2.5.

[0007] According to an embodiment of the present invention, the cross-sectional thickness of the graphene oxide film material is 1.0-3 μm, for example, 1.5-2.5 μm.

[0008] According to an embodiment of the present invention, the graphene oxide membrane material, when used as a catalytic material, can provide an ordered two-dimensional confined channel for the reactants and stabilize the reaction intermediates. By regulating the graphite domain content and interlayer spacing, the reaction conversion rate, reaction regioselectivity and product enantioselectivity can be regulated, thereby optimizing its catalytic performance.

[0009] According to an embodiment of the present invention, the graphite domain size L of the graphene oxide film material is a It is 1.2 nm, 1.3 nm, 1.4 nm, 1.5 nm, 1.6 nm, 1.7 nm, 1.8 nm, 1.9 nm or 2.0 nm.

[0010] Wherein, the graphite domain size L a It is calculated by the following formula:

[0011]

[0012] in, is the intensity ratio of the D peak to the G peak in the Raman spectrum of graphene oxide film material, and C(λ) is a constant.

[0013] According to an embodiment of the present invention, the interlayer spacing of the graphene oxide film material is 0.6 nm, 0.7 nm, 0.8 nm, 0.9 nm, 1 nm, 1.1 nm, 1.2 nm, 1.3 nm, 1.4 nm or 1.5 nm.

[0014] According to an embodiment of the present invention, the atomic ratio of carbon to oxygen in the graphene oxide film material is 2.0, 2.1, 2.2, 2.3, 2.4 or 2.5.

[0015] The present invention also provides a method for preparing the graphene oxide film material as described above, comprising the following steps:

[0016] (1) Assembling the graphene oxide dispersion into a graphene oxide membrane by vacuum filtration;

[0017] (2) The graphene oxide film of step (1) is heat treated at 25-180°C.

[0018] According to an embodiment of the present invention, in step (1), the graphene oxide dispersion is subjected to ultrasonic treatment before vacuum filtration; the ultrasonic treatment time is 5 to 120 min. The ultrasonic treatment is performed in an ice water bath. The ultrasonic power is 100 to 300 W. The ultrasonic method can obtain a dispersion of uniformly dispersed graphene oxide nanosheets without destroying the structure of the graphene oxide nanosheets.

[0019] According to an embodiment of the present invention, in step (1), the graphene oxide dispersion is an aqueous dispersion of graphene oxide.

[0020] According to an embodiment of the present invention, in step (1), the concentration of graphene oxide in the graphene oxide dispersion is 0.01-2 mg / mL, for example, 0.5 mg / mL, 1 mg / mL, 1.5 mg / mL or 2 mg / mL.

[0021] According to an embodiment of the present invention, in step (1), the graphene oxide film is a layered structure formed by stacking graphene oxide nanosheets; preferably, a layered structure formed by stacking multiple single-layer graphene oxide nanosheets. The single-layer graphene oxide nanosheet has a sheet diameter of >500 nm.

[0022] According to an embodiment of the present invention, in step (1), a vacuum filtration method is used to prepare a membrane formed by stacking multiple single-layer graphene oxide nanosheets of a certain thickness on a porous substrate.

[0023] The porous substrate may be made of an organic filter membrane such as nylon 66, polyvinylidene fluoride, or polytetrafluoroethylene.

[0024] The pore size of the porous substrate is 0.1-0.3 μm, for example, 0.22 μm.

[0025] According to an embodiment of the present invention, in step (1), a graphene oxide dispersion is added to a filter cup provided with a vacuum filtration device, and a vacuum pump is started to perform vacuum filtration, with a vacuum degree of 1 to 5 Pa. As the filtration proceeds, the graphene oxide nanosheets in the graphene oxide dispersion are assembled into a layered structure under the action of water flow, and after the filtration is completed, a graphene oxide film is obtained.

[0026] According to an embodiment of the present invention, in step (1), after the filtration is completed, a constant temperature and humidity treatment is performed; the constant temperature and humidity treatment is performed, for example, under constant temperature and constant humidity conditions, such as in a constant temperature and humidity chamber. Exemplarily, the mixture is allowed to stand at 20-30°C and 10-20 RH% for 6-12 hours.

[0027] According to an embodiment of the present invention, in step (1), the constant temperature and humidity static treatment can achieve the removal of part of the free water in the graphene oxide membrane after the filtration is completed.

[0028] According to an embodiment of the present invention, in step (2), the heat treatment time is 8 to 15 hours; the heat treatment temperature is 25 to 180°C, preferably 25 to 120°C, for example, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C. Too low a treatment temperature is not conducive to promoting the phase change and water loss process of the graphene oxide film, thereby regulating the graphite domain content and interlayer spacing, resulting in a low graphite domain content and a large interlayer spacing in the system, so that the stabilizing effect on the reaction intermediates and the confinement effect on the reactant molecules are not obvious enough. Too high a treatment temperature will cause thermal decomposition of the graphene oxide film, easily destroying the intrinsic chemical structure of the graphene oxide film, resulting in increased mass transfer resistance and affecting the fluidity of the reactant molecules.

[0029] According to an embodiment of the present invention, in step (2), the heat treatment is performed under vacuum conditions, for example, in a vacuum oven.

[0030] According to an embodiment of the present invention, the graphene oxide film is placed in a vacuum oven for heat treatment to remove some of the bound water between the graphene oxide film layers, promote the slow phase transition of the metastable graphene oxide film, and the graphene oxide nanosheets sp 2 The degree of hybrid conjugation increases, and a graphene oxide film material with adjustable graphite domain content and continuously adjustable interlayer spacing is obtained.

[0031] The present invention also provides a use of the graphene oxide film material, which is used for catalyzing the aminolysis reaction of epoxy compounds.

[0032] According to an embodiment of the present invention, the epoxy compound is C 2~4 The alkylene oxide; the C 2~4 The alkylene oxide is optionally substituted by a substituent that does not participate in the aminolysis reaction; and the epoxy compound is a chiral structure, which has at least one chiral center; preferably, the carbon atom that the amino group mainly attacks during the aminolysis reaction is a chiral carbon.

[0033] According to an embodiment of the present invention, the C 2~4 The alkylene oxide is ethylene oxide substituted by a substituent which does not participate in the aminolysis reaction, propylene oxide or butylene oxide which is optionally substituted by a substituent which does not participate in the aminolysis reaction.

[0034] According to an embodiment of the present invention, the substituent not participating in the aminolysis is a halogen, unsubstituted or optionally substituted by one, two or more Ra groups: C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 Alkylthio, halogenated C1- 12 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 Aryl or 5-20 membered heteroaryl;

[0035] Said Ra is selected from halogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 Alkylthio, halogenated C1- 12 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 Aryl or 5-20 membered heteroaryl.

[0036] For example, the epoxy compound is styrene oxide, 4-fluoro-styrene oxide, 4-chloro-styrene oxide, epichlorohydrin, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether.

[0037] According to an embodiment of the present invention, the ammonia or amine participating in the aminolysis reaction is an aliphatic amine or an aromatic amine.

[0038] In some embodiments of the present invention, the aromatic amine is at least one of aniline, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-cyanoaniline, 3-cyanoaniline, 4-cyanoaniline, 2-nitroaniline, 3-nitroaniline, and 4-nitroaniline.

[0039] According to an embodiment of the present invention, the reaction is carried out at room temperature.

[0040] According to an embodiment of the present invention, the room temperature refers to a temperature range of 0-30°C, or 20-30°C.

[0041] According to an embodiment of the present invention, the reaction time is 2 to 60 s, for example, 5 to 40 s, such as 4 s, 4.5 s, 5 s, 6 s, 7 s, 8 s, 9 s, 10 s, 12 s, 15 s, 18 s, 20 s, 25 s, 30 s, 35 s, 40 s, 45 s, 50 s, 55 s or 60 s.

[0042] According to an embodiment of the present invention, the conversion rate of the reaction is 60-100%, for example, 60%, 70%, 80%, 90% or 100%.

[0043] According to an embodiment of the present invention, the regioselectivity of the reaction is 90:10-100:0, for example, 90:10, 92:8, 94:6, 98:2, 100:0.

[0044] According to an embodiment of the present invention, the chirality of the main product obtained in the reaction is 100% reversed relative to the chirality of the carbon atom attacked by the amino group in the alkylene oxide raw material.

[0045] According to an embodiment of the present invention, the raw materials for the epoxy compound ammonolysis reaction include epoxy compound molecules and nucleophilic reagent ammonia or amine.

[0046] The present invention also provides a method for performing an ammonolysis reaction on an epoxy compound using the graphene oxide film material as described above, comprising the following steps:

[0047] a) mixing an epoxy compound with a nucleophilic reagent ammonia or amine to obtain a permeabilized reaction solution;

[0048] b) driving the cross-membrane reaction solution through the graphene oxide membrane material as described above by pressure difference to carry out the ammonolysis reaction of the epoxy compound.

[0049] According to an embodiment of the present invention, in step a), the molar ratio of the epoxy compound to the nucleophilic reagent ammonia or amine is 1:0.1-1:10, for example, 1:0.5-1:2 or 1:0.8-1:1.2, such as 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2.

[0050] According to an embodiment of the present invention, in step a), the epoxy compound is selected from at least one of styrene oxide, 4-fluoro-styrene oxide, 4-chloro-styrene oxide, epichlorohydrin, allyl glycidyl ether, benzyl glycidyl ether, and glycidyl phenyl ether.

[0051] According to an embodiment of the present invention, in step a), the nucleophilic reagent ammonia or amine is selected from at least one of aniline, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-cyanoaniline, 3-cyanoaniline, 4-cyanoaniline, 2-nitroaniline, 3-nitroaniline or 4-nitroaniline.

[0052] According to an embodiment of the present invention, the reaction in step a) is carried out in an organic solvent, which is a polar solvent, such as at least one of acetonitrile, ethanol, methanol, ethyl acetate, acetone, dichloromethane, tetrahydrofuran, 1,4-dioxane or acetic acid.

[0053] According to an embodiment of the present invention, in step b), the reaction time is 2 to 60 seconds.

[0054] According to an embodiment of the present invention, in step b), the reaction temperature is in the range of 0-30°C, or 20-30°C.

[0055] According to an embodiment of the present invention, in the step b), the method for generating the pressure difference is not particularly limited, for example, negative pressure may be generated on the lower surface of the graphene oxide membrane catalytic material by vacuum filtration, and / or positive pressure may be generated on the upper surface of the graphene oxide membrane catalytic material by applying external pressure;

[0056] Exemplarily, the pressure difference is achieved by vacuum filtration, for example, adding the transmembrane reaction solution to a vacuum filtration device provided with a graphene oxide membrane catalytic material, starting a vacuum pump, and performing vacuum filtration to generate a pressure difference between the upper surface and the lower surface of the graphene oxide membrane catalytic membrane material.

[0057] Exemplarily, the pressure difference is achieved by applying external pressure, for example, adding the transmembrane reaction solution to a device provided with a graphene oxide membrane catalytic material, applying pressure above the transmembrane reaction solution to create a pressure difference between the upper and lower surfaces of the graphene oxide membrane catalytic material.

[0058] According to an embodiment of the present invention, in step b), the pressure difference is not particularly limited, such as being greater than 0.4 atm. Exemplarily, the pressure difference is 0.4-1.0 atm, such as 0.8-1.0 atm, such as 0.4 atm, 0.5 atm, 0.6 atm, 0.7 atm, 0.8 atm, 0.9 atm or 1 atm.

[0059] According to an embodiment of the present invention, in step b), the conversion rate of the reaction can reach 60-100%.

[0060] According to an embodiment of the present invention, in step b), the regioselectivity of the reaction can reach 92:2-100:0.

[0061] According to an embodiment of the present invention, in the step b), the configuration of the main product obtained by the aminolysis reaction is opposite to that of the alkylene oxide reactant, and the enantioselectivity of the reaction can reach 100:0.

[0062] According to an embodiment of the present invention, the ammonolysis reaction of the epoxy compound is carried out in a continuous mobile phase reaction driven by pressure difference, and the epoxy compound and the nucleophilic reagent ammonia or amine react efficiently under the catalysis of carboxyl acid in the interlayer confined channel of the membrane catalytic material, and the product flows out with the mobile phase and leaves the system, and the reaction time is less than 1 minute. By regulating the interlayer spacing and graphite domain size content of the confined channel, the frontier molecular orbitals of reactants with different reactivity and different sizes are matched, the molecular freedom is reduced, the molecules break bonds and form bonds in a specific orientation and are arranged in order between layers, and the reaction activation energy is reduced, thereby realizing a rapid (less than 1 minute) ammonolysis reaction of epoxy compounds with multiple reactivity and reactants of different sizes at room temperature (20-30°C), and the reactant conversion rate can reach up to 100%, the reaction regioselectivity can reach up to 100%, the configuration of the obtained main product is opposite to that of the alkylene oxide reactant, and the reaction enantioselectivity can reach 100:0.

[0063] Beneficial effects of the present invention:

[0064] Based on the inherent acidic catalytic sites of two-dimensional nano-element materials such as graphene oxide nanosheets and the interlayer confinement environment provided after they are assembled into macroscopic films, the present invention prepares a graphene oxide film catalytic material with adjustable graphite domain content and interlayer spacing, which is used to catalyze the ammonolysis reaction of epoxy compounds with high conversion rate and high regional selectivity at room temperature.

[0065] Specifically, a graphene oxide film catalytic material with adjustable thickness is prepared by vacuum filtration. The interlayer confinement effect reduces the freedom of reactant molecules in the channel, reduces disordered diffusion, enhances the matching of the frontier molecular orbitals of reactant molecules, and the stabilizing effect of the interlayer graphite domain on the reaction intermediates reduces the reaction activation energy, thereby greatly improving the catalytic effect.

[0066] The graphite domain content and interlayer spacing of the graphene oxide membrane catalytic material can be regulated by heat treatment at different temperatures. The reduction in interlayer spacing increases the orderliness of the molecular arrangement between the layers, and the molecules break and form bonds in a specific orientation. Combined with the expansion of the graphite domain range, the compatibility of the catalyst system and the reactant molecules is enhanced, and the catalytic effect is significantly improved. Furthermore, the interlayer spacing of the graphene oxide membrane catalytic material is regulated to be smaller than the molecular size of the by-product in the lowest energy state, thereby forcing the by-product molecules to pass through the confined channel at a smaller size, corresponding to the increase in the energy of the intermediates and transition states in the generation path.

[0067] In summary, the present invention prepares a graphene oxide membrane catalytic material with adjustable graphite domain content and continuously adjustable interlayer spacing for catalyzing the ammonolysis reaction of epoxy compounds at room temperature with rapid, high conversion rate and high regioselectivity. The reactants react in the two-dimensional confined channel between the layers in the form of a continuous mobile phase reaction, and the products flow out with the mobile phase. Rapid (reactant residence time is less than one minute) ammonolysis of epoxy compounds is achieved at room temperature. The reactant conversion rate can reach up to 100%, the reaction regioselectivity can reach up to 100%, the configuration of the obtained main product is opposite to that of the alkylene oxide reactant, the reaction enantioselectivity can reach 100:0, and the separation and purification process is simplified. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1 : Schematic diagram of the preparation of the graphene oxide film catalytic material of the present invention and its catalytic ammonolysis reaction process of epoxy compounds.

[0069] Figure 2 :Characterization of the structure and catalytic performance of graphene oxide film catalytic materials. Among them, Figure 2 Figure A is a schematic diagram of a scanning electron microscope cross section of the graphene oxide film catalyst material GO-IV of Example 1; Figure B is an X-ray diffraction (XRD) diagram of the graphene oxide film catalyst material of Examples 1-4 in a wet state (the solvent is acetonitrile); Figure C is an atomic ratio of carbon and oxygen elements and an intensity ratio of the D band to the G band (I D / I G ); D is the nuclear magnetic resonance hydrogen spectrum of the product obtained by the ammonolysis reaction of styrene oxide and aniline catalyzed by the graphene oxide membrane catalyst material GO-IV confined in Example 1; E is the high performance liquid chromatogram of the product obtained by the ammonolysis reaction of styrene oxide and aniline catalyzed by the membrane catalyst material GO-IV confined in Example 1 and the catalyst material GO powder in Comparative Example 1.

[0070] Terms and Definitions

[0071] Unless otherwise defined, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.

[0072] "More" means three or more.

[0073] The term "C 1-12 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms. Preferably, "C 1-6 Alkyl". "C 1-6The term "alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2-dimethylbutyl, or the like or isomers thereof.

[0074] The term "C 1-12 "Alkoxy" is understood to mean -OC 1-12 Alkyl, where C 1-12 Alkyl has the above definition.

[0075] The term "C 1-12 "Alkylthio" is understood to mean -SC 1-12 Alkyl, where C 1-12 Alkyl has the above definition.

[0076] The term "C 3-20 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic or polycyclic hydrocarbon ring (also called condensed hydrocarbon ring) having 3 to 20 carbon atoms, preferably "C 3-14 Cycloalkyl". Bicyclic or polycyclic cycloalkyl includes paracyclic cycloalkyl, bridged cycloalkyl, and spirocyclic alkyl; the paracyclic refers to a condensed ring structure formed by two or more cyclic structures sharing two adjacent ring atoms (i.e., sharing one bond). The bridged ring refers to a condensed ring structure formed by two or more cyclic structures sharing two non-adjacent ring atoms. The spirocyclic refers to a condensed ring structure formed by two or more cyclic structures sharing one ring atom. For example, the C 3-20 The cycloalkyl group may be C 3-8 Monocyclic cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or C 7-12 Cycloalkyl, such as decahydronaphthalene; it can also be C 7-12 Bridged ring cycloalkyl, such as norbornane, adamantane, bicyclo[2,2,2]octane.

[0077] The term "3-20 membered heterocyclyl" means a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O and S, preferably a "3-14 membered heterocyclyl". The term "3-14 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclyl may be attached to the rest of the molecule via any of the carbon atoms or the nitrogen atom (if present). In particular, the heterocyclyl may include, but is not limited to, a 4-membered ring such as azetidinyl, oxetanyl; a 5-membered ring such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, such as, but not limited to, a 5,5-membered ring, such as a hexahydrocyclopenta[c]pyrrole-2(1H)-yl ring, or a 5,6-membered bicyclic ring, such as a hexahydropyrrolo[1,2-a]pyrazine-2(1H)-yl ring. The ring containing nitrogen atoms may be partially unsaturated, i.e., it may contain one, two or more double bonds, such as, but not limited to, 2,5-dihydro-1H-pyrrolyl, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl or 4H-[1,4]thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolyl, 1,3-benzoxazolyl, 1,3-benzodioxolyl. According to the present invention, the heterocyclic group is non-aromatic.

[0078] The term "C 6-20 "Aryl" is understood to mean a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-14 The term "C 6-14 "Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl"), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl"), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl"), such as anthracenyl. When the C 6-20When the aryl group is substituted, it may be monosubstituted or polysubstituted. Also, there is no limitation on the substitution position, for example, it may be substituted at the ortho position, para position or meta position.

[0079] The term "5-20 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, for example "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O and S and, in addition, in each case may be benzo-fused. In particular, the heteroaryl group is selected from thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and benzo derivatives thereof, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or azinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like.

[0080] The above term “C 1-12 The definition of "alkyl" also applies to other C-containing 1-12 Alkyl groups, such as halogenated C1- 12 Alkyl, etc. DETAILED DESCRIPTION

[0081] The present invention will be described in further detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0082] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, materials, etc. used in the following examples, unless otherwise specified, can be obtained from commercial channels.

[0083] In the following examples and comparative examples, unless otherwise specified, "GO dispersion" refers to "graphene oxide dispersion".

[0084] In the following embodiments and comparative examples, unless otherwise specified, "GO membrane" refers to "graphene oxide membrane catalytic material".

[0085] The collected liquid after the membrane was quantitatively analyzed by nuclear magnetic resonance hydrogen spectrum and high performance liquid chromatography, and the reaction conversion rate and regioselectivity were calculated. The specific steps include the following: after the reaction is completed, acetonitrile is added to the filter bottle to dissolve the product to obtain the product collected liquid, a part of the collected liquid is taken into a 10 mL round-bottom flask, and the acetonitrile solvent is removed by rotary evaporation at 50 °C under appropriate vacuum, and a deuterated reagent (CDCl3) is used to prepare the nuclear magnetic sample. There are characteristic hydrogens in both the reactant and product molecules. There is a corresponding relationship between the characteristic hydrogen and the number of molecules. The integral area of ​​the single peaks at different chemical shifts is compared by single peak fitting calculation, the corresponding molecular number ratio is calculated, and then the reaction conversion rate is calculated.

[0086] The collected liquid through the membrane is quantitatively analyzed by ultra-high performance liquid chromatography to calculate the reaction regioselectivity and reaction enantioselectivity, which specifically includes the following steps: after the reaction is completed, acetonitrile is added to the filter bottle to dissolve the product to obtain the product collected liquid, and a portion of the collected liquid is taken into a liquid phase injection bottle to prepare a liquid chromatography sample. The integral area of ​​the single peak at different elution times is compared by single peak fitting calculation, and the corresponding molecular area ratio is calculated, and then the reaction regioselectivity and reaction enantioselectivity are calculated.

[0087] Example 1

[0088] (1) Preparation of 0.15 mg / mL GO aqueous solution: 6 mg of GO was added to 40 mL of deionized water, mechanically stirred for 10 min, and ultrasonically dispersed in an ice water bath (200 W) for 5 min to obtain a brown transparent solution;

[0089] Prepare 0.15 mol / L aniline solution: Dissolve 547 μL aniline in 40 mL acetonitrile and stir mechanically for 10 min.

[0090] (2) The GO dispersion prepared above was assembled into a GO membrane by vacuum filtration. After the water on the membrane was drained, the membrane was removed from the filtration device, placed in a watch glass, and placed in a constant temperature and humidity chamber at 25.0°C and 15RH% for drying for 12 hours. The GO membrane was then transferred to a vacuum oven and heat treated at 100°C for 12 hours before being taken out for use. The membrane was named GO-IV. Scanning electron microscopy showed that the cross-sectional thickness of the GO-IV membrane was 1.68±0.03 μm. Raman characterization showed that the intensity ratio of the D band to the G band of the GO-IV membrane (I D / I G ) is about 1.31, which is determined by I D / I GThe calculated graphite domain size is about 1.6 nm; X-ray diffraction data show that the interlayer spacing of GO-IV membrane in acetonitrile solution is about 0.90 nm; X-ray photoelectron spectroscopy shows that the atomic ratio of carbon and oxygen in GO-IV membrane is about 2.47.

[0091] (3) GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and aniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), and then purged with nitrogen again. It was fixed and a sealing gasket was installed to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared aniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 minutes to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device. Driven by the pressure difference (~1atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor. The reactants reacted in the interlayer and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0092] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 31 s, the conversion rate was 100%, the regioselectivity was 100:0, and the obtained product was S configuration, R:S=0:100.

[0093] Comparative Example 1

[0094] Prepare 0.15 mg / mL GO aqueous solution in advance: take 6 mg GO in 40 mL deionized water, stir mechanically for 10 min, disperse by ultrasound (200 W) in an ice water bath for 5 min to obtain a brown transparent solution, transfer it to a glass watch glass, place it in a vacuum oven at 100 ° C for 12 h to obtain GO powder, and then place it in a constant temperature and humidity chamber to maintain 25 ° C, 15 RH% for storage;

[0095] Prepare 0.15 mol / L aniline solution: take 547 μL aniline in 40 mL acetonitrile and stir mechanically for 10 min; then prepare the reaction solution: take the above 40 mL aniline solution prepared in advance, add 570 μL R-styrene oxide, stir mechanically for 10 min to obtain the required reaction solution, which is prepared immediately; take 20 mL of the above reaction solution, add the above GO powder, and stir mechanically in an oil bath at 60 °C for 72 h;

[0096] Reaction results: The reaction temperature was 60 °C, the reaction time was 72 h, the reaction conversion rate was 35.8%, the reaction regioselectivity was 90.4:9.6, and the main product was S configuration, R:S=0:100.

[0097] Comparative Example 2

[0098] Prepare 0.15 mg / mL GO aqueous solution in advance: take 6 mg GO in 40 mL deionized water, stir mechanically for 10 min, disperse by ultrasound (200 W) in an ice water bath for 5 min to obtain a brown transparent solution, transfer it to a glass watch glass, place it in a vacuum oven at 100 ° C for 12 h to obtain GO powder, and then place it in a constant temperature and humidity chamber to maintain 25 ° C, 15 RH% for storage;

[0099] Prepare 0.15 mol / L aniline solution: take 547 μL aniline in 40 mL acetonitrile and stir mechanically for 10 min; then prepare the reaction solution: take 40 mL of the above-prepared aniline solution, add 570 μL R-styrene oxide, stir mechanically for 10 min to obtain the required reaction solution, which is prepared immediately; take 20 mL of the above reaction solution, add the above GO powder, and stir mechanically for 72 h at room temperature;

[0100] Reaction results: The reaction temperature was 25 °C, the reaction time was 72 h, the reaction conversion rate was 8.0%, the reaction regioselectivity was 93.9:6.1, and the main product was S configuration, R:S=0:100.

[0101] Example 2

[0102] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and aniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared aniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0103] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 31 s, the conversion rate was 100%, the regioselectivity was 100:0, and the obtained product was R configuration, R:S=100:0.

[0104] Example 3

[0105] (1) Preparation of 0.15 mg / mL GO aqueous solution: 6 mg of GO was added to 40 mL of deionized water, mechanically stirred for 10 min, and ultrasonically dispersed in an ice water bath (200 W) for 5 min to obtain a brown transparent solution;

[0106] Prepare 0.15 mol / L aniline solution: Dissolve 547 μL aniline in 40 mL acetonitrile and stir mechanically for 10 min.

[0107] (2) The GO dispersion prepared above was assembled into a GO membrane by vacuum filtration. After the water on the membrane was drained, the membrane was removed from the filtration device, placed in a watch glass, and placed in a constant temperature and humidity chamber at 25.0°C and 15RH% for drying for 12 hours. The GO membrane was then transferred to a vacuum oven for vacuum heat treatment at 25°C for 12 hours and then taken out for use. The membrane was named GO-I. Scanning electron microscopy showed that the cross-sectional thickness of the GO-I membrane was 2.03±0.04 μm. Raman characterization showed that the intensity ratio of the D band to the G band of the GO-I membrane (I D / I G ) is about 1.07, which is determined by I D / I G The calculated graphite domain size is about 1.3 nm; X-ray diffraction data show that the interlayer spacing of GO-I membrane in acetonitrile solution is about 1.12 nm; X-ray photoelectron spectroscopy shows that the atomic ratio of carbon and oxygen in GO-IV membrane is about 2.13.

[0108] (3) The GO-I membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and aniline. The specific operation was as follows: the GO-I membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), and then purged with nitrogen again. It was fixed and a sealing gasket was installed to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared aniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 minutes to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device. Driven by the pressure difference (~1atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-I membrane reactor. The reactants reacted in the interlayer and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0109] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 18.0 s, the conversion rate was 70.8%, the regioselectivity was 93.6:6.4, and the main product was S configuration, R:S=0:100.

[0110] Example 4

[0111] The above GO-I membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and aniline. The specific operation was as follows: the GO-I membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared aniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was carried out for 10 minutes to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-I membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0112] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 18.0 s, the conversion rate was 68.0%, the regioselectivity was 94.0:6.0, and the main product was R configuration, R:S=100:0.

[0113] Example 5

[0114] (1) Preparation of 0.15 mg / mL GO aqueous solution: 6 mg of GO was added to 40 mL of deionized water, mechanically stirred for 10 min, and ultrasonically dispersed in an ice water bath (200 W) for 5 min to obtain a brown transparent solution;

[0115] Prepare 0.15 mol / L aniline solution: take 547 μL of aniline in 40 mL of acetonitrile and stir mechanically for 10 min;

[0116] (2) The GO dispersion prepared above was assembled into a GO membrane by vacuum filtration. After the water on the membrane was drained, the membrane was removed from the filtration device, placed in a watch glass, and placed in a constant temperature and humidity chamber at 25.0°C and 15RH% for drying for 12 hours. The GO membrane was then transferred to a vacuum oven for vacuum heat treatment at 60°C for 12 hours and then taken out for use. The membrane was named GO-II. Scanning electron microscopy showed that the cross-sectional thickness of the GO-II membrane was 1.86±0.08 μm. Raman characterization showed that the intensity ratio of the D band to the G band of the GO-II membrane (I D / I G ) is about 1.14, which is determined by I D / I G The calculated graphite domain size is about 1.4 nm; X-ray diffraction data show that the interlayer spacing of GO-II membrane in acetonitrile solution is about 1.04 nm; X-ray photoelectron spectroscopy shows that the atomic ratio of carbon and oxygen in GO-II membrane is about 2.26.

[0117] (3) GO-II membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and aniline. The specific operation was as follows: the GO-II membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), and then purged with nitrogen again. It was fixed and a sealing gasket was installed to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared aniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 minutes to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device. Driven by the pressure difference (~1atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-II membrane reactor. The reactants reacted in the interlayer and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0118] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 18.8 s, the conversion rate was 80.4%, the regioselectivity was 96.3:3.7, and the main product was S configuration, R:S=0:100.

[0119] Example 6

[0120] The above GO-II membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and aniline. The specific operation was as follows: the GO-II membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared aniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-II membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0121] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 18.8 s, the conversion rate was 81.3%, the regioselectivity was 96.2:3.8, and the main product was R configuration, R:S=100:0.

[0122] Example 7

[0123] (1) Preparation of 0.15 mg / mL GO aqueous solution: 6 mg of GO was added to 40 mL of deionized water, mechanically stirred for 10 min, and ultrasonically dispersed in an ice water bath (200 W) for 5 min to obtain a brown transparent solution;

[0124] Prepare 0.15 mol / L aniline solution: Dissolve 547 μL aniline in 40 mL acetonitrile and stir mechanically for 10 min.

[0125] (2) The GO dispersion prepared above was assembled into a GO membrane by vacuum filtration. After the water on the membrane was drained, the membrane was removed from the filtration device, placed in a watch glass, and placed in a constant temperature and humidity chamber at 25.0°C and 15RH% for drying for 12 hours. The GO membrane was then transferred to a vacuum oven for vacuum heat treatment at 80°C for 12 hours and then taken out for use. The membrane was named GO-III. Scanning electron microscopy showed that the cross-sectional thickness of the GO-III membrane was 1.75±0.03 μm. Raman characterization showed that the intensity ratio of the D band to the G band of the GO-III membrane (I D / I G ) is about 1.21, which is determined by I D / I G The calculated graphite domain size is about 1.5 nm; X-ray diffraction data show that the interlayer spacing of GO-III membrane in acetonitrile solution is about 0.92 nm; X-ray photoelectron spectroscopy shows that the atomic ratio of carbon and oxygen in GO-III membrane is about 2.36.

[0126] (3) The GO-III membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and aniline. The specific operation was as follows: the GO-III membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), and then purged with nitrogen again. It was fixed and a sealing gasket was installed to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared aniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device. Driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-III membrane reactor. The reactants reacted in the interlayer and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0127] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 20.8 s, the conversion rate was 92.5%, the regioselectivity was 97.2:2.8, and the main product was S configuration, R:S=0:100.

[0128] Example 8

[0129] The above GO-III membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and aniline. The specific operation was as follows: the GO-III membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared aniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-III membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0130] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 20.8 s, the conversion rate was 92.6%, the regioselectivity was 97.6:2.4, and the main product was R configuration, R:S=100:0.

[0131] Example 9

[0132] (1) Preparation of 0.15 mg / mL GO aqueous solution: 6 mg of GO was added to 40 mL of deionized water, mechanically stirred for 10 min, and ultrasonically dispersed in an ice water bath (200 W) for 5 min to obtain a brown transparent solution;

[0133] Prepare 0.15 mol / L 2-methoxyaniline solution: Dissolve 739 mg 2-methoxyaniline in 40 mL acetonitrile and stir mechanically for 10 min.

[0134] (2) The GO dispersion prepared above was assembled into a GO membrane by vacuum filtration. After the water on the membrane was drained, the membrane was removed from the filtration device, placed in a watch glass, and placed in a constant temperature and humidity chamber at 25.0°C and 15RH% for drying for 12 hours. The GO membrane was then transferred to a vacuum oven and heat treated at 100°C for 12 hours before being taken out for use. The membrane was named GO-IV. Scanning electron microscopy showed that the cross-sectional thickness of the GO-IV membrane was 1.68±0.03 μm. Raman characterization showed that the intensity ratio of the D band to the G band of the GO-IV membrane (I D / I G ) is about 1.31, which is determined by I D / I G The calculated graphite domain size is about 1.6 nm; X-ray diffraction data show that the interlayer spacing of GO-IV membrane in acetonitrile solution is about 0.90 nm; X-ray photoelectron spectroscopy shows that the atomic ratio of carbon and oxygen in GO-IV membrane is about 2.47.

[0135] (3) GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 2-methoxyaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), and then purged with nitrogen again. It was fixed and a sealing gasket was installed to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 2-methoxyaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device. Driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor. The reactants reacted in the interlayer and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0136] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 35 s, the conversion rate was 98.3%, the regioselectivity was 97.6:2.4, and the main product was S configuration, R:S=0:100.

[0137] Example 10

[0138] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 2-methoxyaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 2-methoxyaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0139] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 35 s, the conversion rate was 100%, the regioselectivity was 98.1:1.9, and the main product was R configuration, R:S=100:0.

[0140] Embodiment 11

[0141] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 3-methoxyaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 3-methoxyaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0142] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 19 s, the conversion rate was 100%, the regioselectivity was 95.2:4.8, and the main product was S configuration, R:S=0:100.

[0143] Example 12

[0144] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 3-methoxyaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 3-methoxyaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0145] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 19 s, the conversion rate was 100%, the regioselectivity was 95.4:4.6, and the main product was R configuration, R:S=100:0.

[0146] Example 13

[0147] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 4-methoxyaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 4-methoxyaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0148] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 59 s, the conversion rate was 100%, the regioselectivity was 96.5:3.5, and the main product was S configuration, R:S=0:100.

[0149] Embodiment 14

[0150] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 4-methoxyaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 4-methoxyaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0151] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 59 s, the conversion rate was 100%, the regioselectivity was 96.9:3.1, and the main product was R configuration, R:S=100:0.

[0152] Embodiment 15

[0153] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 2-methylaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 2-methylaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0154] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 33 s, the conversion rate was 95.3%, the regioselectivity was 97.2:2.8, and the main product was S configuration, R:S=0:100.

[0155] Example 16

[0156] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 2-methylaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 2-methylaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was performed for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0157] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 33 s, the conversion rate was 97.7%, the regioselectivity was 97.4:2.6, and the main product was R configuration, R:S=100:0.

[0158] Embodiment 17

[0159] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 3-methylaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 3-methylaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0160] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 30 s, the conversion rate was 99.3%, the regioselectivity was 96.3:3.7, and the main product was S configuration, R:S=0:100.

[0161] Embodiment 18

[0162] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 3-methylaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 3-methylaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was performed for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0163] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 30 s, the conversion rate was 99.4%, the regioselectivity was 96.0:4.0, and the main product was R configuration, R:S=100:0.

[0164] Embodiment 19

[0165] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 4-methylaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 4-methylaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0166] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 26 s, the conversion rate was 98.8%, the regioselectivity was 96.1:3.9, and the main product was S configuration, R:S=0:100.

[0167] Embodiment 20

[0168] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 4-methylaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 4-methylaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0169] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 26 s, the conversion rate was 100%, the regioselectivity was 96.6:3.4, and the main product was R configuration, R:S=100:0.

[0170] Embodiment 21

[0171] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 2-cyanoaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 2-cyanoaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0172] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 31 s, the conversion rate was 77.6%, the regioselectivity was 95.1:4.9, and the main product was S configuration, R:S=0:100.

[0173] Embodiment 22

[0174] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 2-cyanoaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 2-cyanoaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was performed for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0175] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 31 s, the conversion rate was 84.0%, the regioselectivity was 96.9:3.1, and the main product was R configuration, R:S=100:0.

[0176] Embodiment 23

[0177] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 3-cyanoaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 3-cyanoaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0178] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 22 s, the conversion rate was 82.0%, the regioselectivity was 97.2:2.8, and the main product was S configuration, R:S=0:100.

[0179] Embodiment 24

[0180] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 3-cyanoaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 3-cyanoaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was performed for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0181] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 22 s, the conversion rate was 88.9%, the regioselectivity was 97.5:2.5, and the main product was R configuration, R:S=100:0.

[0182] Embodiment 25

[0183] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 4-cyanoaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 4-cyanoaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0184] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 33 s, the conversion rate was 79.5%, the regioselectivity was 98.7:1.3, and the main product was S configuration, R:S=0:100.

[0185] Embodiment 26

[0186] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 4-cyanoaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 4-cyanoaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was performed for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0187] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 33 s, the conversion rate was 79.7%, the regioselectivity was 98.3:1.7, and the main product was R configuration, R:S=100:0

[0188] Embodiment 27

[0189] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 2-nitroaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 2-nitroaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0190] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 21 s, the conversion rate was 83.0%, the regioselectivity was 100:0, and the obtained product was S configuration, R:S=0:100.

[0191] Embodiment 28

[0192] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 2-nitroaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 2-nitroaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was performed for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0193] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 21 s, the conversion rate was 83.0%, the regioselectivity was 100:0, and the obtained product was R configuration, R:S=100:0.

[0194] Embodiment 29

[0195] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 3-nitroaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 3-nitroaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0196] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 26 s, the conversion rate was 89.1%, the regioselectivity was 97.7:2.3, and the main product was S configuration, R:S=0:100.

[0197] Embodiment 30

[0198] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 3-nitroaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 3-nitroaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0199] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 26 s, the conversion rate was 89.4%, the regioselectivity was 97.9:2.1, and the main product was R configuration, R:S=100:0.

[0200] Embodiment 31

[0201] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of R-styrene oxide and 4-nitroaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 4-nitroaniline solution was taken, 570 μL of R-styrene oxide was added, and mechanical stirring was carried out for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0202] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 12 s, the conversion rate was 82.9%, the regioselectivity was 100:0, and the obtained product was S configuration, R:S=0:100.

[0203] Embodiment 32

[0204] The above GO-IV membrane was used as a catalyst to catalyze the aminolysis reaction of S-styrene oxide and 4-nitroaniline. The specific operation was as follows: the GO-IV membrane was purged with nitrogen to remove the dust on the surface, and then the flat and smooth part was selected and cut into a regular octagon (side length 0.8 cm), purged with nitrogen again, fixed and installed with a sealing gasket to ensure that it was sealed in the micro-filtration device; then the reaction solution was prepared: 40 mL of the above-prepared 4-nitroaniline solution was taken, 570 μL of S-styrene oxide was added, and mechanical stirring was performed for 10 min to obtain the required reaction solution, which was prepared immediately; 15 mL of the above reaction solution was added above the micro-filtration device, and driven by the pressure difference (~1 atm), the reaction solution passed through the interlayer two-dimensional nano-confined channel of the GO-IV membrane reactor, the reactants reacted in the interlayer, and the products flowed out with the acetonitrile solvent; acetonitrile was added to the bottom triangular liquid collection filter bottle to dissolve the product, and 1 mL of collected liquid was placed in a liquid injection bottle, and the components were analyzed by high performance liquid chromatography to calculate the reaction regioselectivity and enantioselectivity; the remaining collected liquid was rotary evaporated to remove the acetonitrile solvent, and the obtained solid was dissolved with CDCl3 and then 1 H NMR spectroscopy was used to analyze the components and calculate the reaction conversion rate;

[0205] Reaction results: The reaction temperature was 25 °C, the residence time of the reactants was about 12 s, the conversion rate was 82.9%, the regioselectivity was 100:0, and the obtained product was R configuration, R:S=100:0.

[0206] The schematic diagram of the graphene oxide film catalytic material prepared by the present invention and the process of its catalytic ammonolysis of epoxy compounds is as follows: Figure 1 The prepared GO dispersion was assembled into a GO film by vacuum filtration, and a mild heat treatment process was performed to promote a slow phase transition of the metastable GO, which lost some of the bound water and expanded the GO two-dimensional carbon plane sp 2 The hybridized graphite region is used to obtain the GO membrane catalytic material. By changing the heat treatment temperature, the interlayer spacing and graphite domain content of the GO membrane catalytic material are regulated to optimize the catalytic performance of the membrane material. The GO membrane catalytic material is used as a membrane reactor to catalyze the aminolysis reaction of epoxy compounds and amines. The reaction liquid passes through the GO membrane in a directional flow driven by the pressure difference. The intrinsic acidic functional groups of the GO nanosheets catalyze the reaction of epoxy compounds and amines in the two-dimensional nano-confined channels between the membrane layers, and the products flow out with the solvent.

[0207] Specifically, GO nanosheets provide intrinsic acidic catalytic sites, and the nano-confinement between GO layers reduces the molecular freedom of the reactants and enhances their order; the interlayer graphene domains are used to stabilize the reaction intermediates, reduce the reaction activation energy, and change the reaction path, thereby greatly improving the performance of the ammonolysis reaction.

[0208] like Figure 2 As shown in Figure A, the cross-sectional scanning electron microscope image of the GO-IV membrane shows that the prepared GO membrane catalytic material has a dense multilayer structure. Figure 2 As shown in Figure B, the wet interlayer spacings of GO-I, GO-II, GO-III, and GO-IV in acetonitrile are 1.12 nm, 1.04 nm, 0.92 nm, and 0.90 nm, respectively. As the heat treatment temperature increases, the interlayer spacing of the GO membrane catalytic material decreases. Figure 2 As shown in C, the X-ray photoelectron spectroscopy characterization results show that with the increase of heat treatment temperature, the carbon / oxygen atomic ratio of the GO film catalytic material increases, indicating the generation of π-conjugated domains; at the same time, the Raman characterization results show that with the increase of heat treatment temperature, I D / I G The increase indicates the ordering and aggregation of graphite domains. = C(λ)L a 2 , where L a represents the graphite domain size, which is related to I D / I G Proportional to I D / I G The increase indicates that the graphite domain size of the membrane increases and the graphite domain content increases.

[0209] As shown in Example 1, the aminolysis reaction of styrene oxide and aniline was carried out in a GO-IV membrane reactor, and the nuclear magnetic resonance hydrogen spectrum of the product was collected. Figure 2 As shown in D in the figure, the chemical shifts of the benzene ring hydrogen are located at 7.40-7.20 (5H), 7.12 (2H), 6.75 (1H), 6.66 (2H) ppm, combined with the characteristic peaks at 4.53, 3.97 and 3.87 ppm in the non-benzene ring region, which correspond to the product peaks one by one; in addition, the characteristic peaks of the reactant styrene oxide completely disappear, and the reaction conversion rate is calculated to be 100%. Figure 2E in the figure is the HPLC chromatogram of the products obtained by the ammonialysis reaction of styrene oxide and aniline catalyzed by the GO-IV membrane catalytic material in Example 1 and the GO powder in Comparative Example 1; the chromatographic peaks with retention times of 10.630 and 12.422 min correspond to two products at different reaction positions. The confined catalysis of the GO-IV membrane catalyst can obtain the ammonialysis product at a specific reaction site, while the bulk reaction catalyzed by the GO powder obtains a mixture of the two products. Compared with the bulk catalysis of GO powder, the GO-IV membrane catalytic material achieves a fast (reactant residence time <60 s), mild (room temperature), high conversion rate (conversion rate is 100%), and high regioselectivity (regioselectivity is 100:0) ammonialysis reaction of epoxy compounds.

[0210] As shown in Table 1 below, the reaction temperature, reaction time, yield or conversion rate and regioselectivity of the GO-IV membrane catalyst are compared with other catalysts reported in the literature for catalyzing the ammonolysis reaction of epoxy compounds. Among them, Cat. (Catalyst) represents the catalyst, and RT is room temperature. Currently, the catalysts for the ammonolysis reaction of epoxy compounds reported in the literature are mostly Lewis acids such as aluminum chloride, Brønsted acids such as sulfuric acid, organic bases such as triethylamine and pyridine, and other materials such as zeolites and molecular sieves. Compared with other catalysts in the literature, the method of the present invention greatly improves the reaction efficiency, shortens the reaction time, and achieves a 100% conversion rate and a 100:0 regioselectivity at room temperature.

[0211] Table 1

[0212]

[0213] In summary, the present invention provides a graphene oxide membrane catalytic material with graphite domains and adjustable interlayer spacing for catalyzing the ammonolysis reaction of epoxy compounds, as well as a preparation method and use thereof. The prepared graphene oxide membrane has adjustable graphite domain content, continuously adjustable interlayer spacing and inherent acidic catalytic sites. By utilizing the synergistic catalytic effect of the two-dimensional nano-confined channels provided by the graphene oxide nanosheets between the membrane layers, the surface graphite domains for stabilizing the intermediates and the acidic catalytic sites, efficient catalysis of the ammonolysis reaction of epoxy compounds is achieved at room temperature. The catalysis is carried out in a continuous mobile phase reaction mode, the reactant conversion rate can reach up to 100%, the reaction regioselectivity can reach up to 100:0, the configuration of the obtained main product is opposite to that of the alkylene oxide reactant, the reaction enantioselectivity can reach 100:0, and the product flows out with the mobile phase and leaves the system, simplifying the separation and purification process.

[0214] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. Use of graphene oxide film material for catalyzing the ammonolysis reaction of epoxy compounds; The graphite domain size of the graphene oxide film material is 1.2-2.0 nm, the interlayer spacing is 0.6-1.5 nm, and the atomic ratio of carbon to oxygen is 2.0-2.5; The preparation method of the graphene oxide film material comprises: (1) Assembling the graphene oxide dispersion into a graphene oxide membrane by vacuum filtration; (2) heat treating the graphene oxide film of step (1) at 25-180°C; The aminolysis reaction is carried out by the following steps: a) mixing an epoxy compound with a nucleophilic reagent ammonia or amine to obtain a permeabilized reaction solution; b) driving the cross-membrane reaction solution through the graphene oxide membrane material by pressure difference to perform an ammonolysis reaction of the epoxy compound.

2. The use according to claim 1, characterized in that The graphene oxide film material satisfies at least one of the following characteristics: Feature 1: Section thickness is 1.0~3μm; Feature 2: Graphite domain size L a 1.2 nm, 1.3 nm, 1.4 nm, 1.5 nm, 1.6 nm, 1.7 nm, 1.8 nm, 1.9 nm or 2.0 nm; Feature 3: interlayer spacing is 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm, 1.1nm, 1.2nm, 1.3nm, 1.4nm or 1.5nm; Feature 4: The atomic ratio of carbon to oxygen is 2.0, 2.1, 2.2, 2.3, 2.4 or 2.

5.

3. The use according to claim 1, characterized in that The epoxy compound is C 2~4 The alkylene oxide; the C 2~4 The alkylene oxide is unsubstituted or substituted by a substituent that does not participate in the aminolysis reaction; and the epoxy compound is a chiral structure with at least one chiral center.

4. The use according to claim 3, characterized in that The substituent not participating in the aminolysis is halogen, unsubstituted or substituted by one, two or more Ra as follows: 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 Alkylthio, halogenated C1- 12 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 Aryl or 5-20 membered heteroaryl; Said Ra is selected from halogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 Alkylthio, halogenated C1- 12 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 Aryl or 5-20 membered heteroaryl.

5. The use according to claim 3, characterized in that: The epoxy compound is selected from styrene oxide, 4-fluoro-styrene oxide, 4-chloro-styrene oxide, epichlorohydrin, allyl glycidyl ether, benzyl glycidyl ether, and glycidyl phenyl ether.

6. The use according to claim 1, characterized in that: The ammonia or amine involved in the aminolysis reaction is an aliphatic amine or an aromatic amine.

7. The use according to claim 6, characterized in that The aromatic amine is at least one of aniline, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-cyanoaniline, 3-cyanoaniline, 4-cyanoaniline, 2-nitroaniline, 3-nitroaniline and 4-nitroaniline.

8. The use according to claim 1, characterized in that In step (1), the concentration of graphene oxide in the graphene oxide dispersion is 0.01-2 mg / mL.

9. The use according to claim 1, characterized in that In step (2), the heat treatment time is 8 to 15 hours; the heat treatment temperature is 25 to 120°C.

10. The use according to any one of claims 1 to 9, characterized in that: The aminolysis reaction satisfies at least one of the following conditions: Condition 1: In step a), the molar ratio of the epoxy compound to the nucleophilic reagent ammonia or amine is 1:0.1 to 1:10; Condition 2: In step a), the epoxy compound is selected from at least one of styrene oxide, 4-fluoro-styrene oxide, 4-chloro-styrene oxide, epichlorohydrin, allyl glycidyl ether, benzyl glycidyl ether, and glycidyl phenyl ether; In step a), the nucleophilic agent ammonia or amine is selected from at least one of aniline, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-cyanoaniline, 3-cyanoaniline, 4-cyanoaniline, 2-nitroaniline, 3-nitroaniline or 4-nitroaniline; Condition 3: The reaction in step a) is carried out in an organic solvent, which is a polar solvent; Condition 4: In step b), the reaction temperature is 0-30 °C; Condition 5: In the step b), the pressure difference is 0.4-1.0 atm.

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