CN107556492B - Graphene-containing waterborne epoxy resin emulsion and preparation method thereof - Google Patents
Graphene-containing waterborne epoxy resin emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene-containing waterborne epoxy resin emulsion and a preparation method thereof, wherein the preparation method of the waterborne epoxy resin emulsion comprises the following specific steps: preparing a polyethylene glycol/graphene composite material, preparing a water-based epoxy resin emulsifier, and preparing a water-based epoxy resin emulsion. The polyethylene glycol/graphene composite material is prepared through an in-situ polymerization method, graphene can be uniformly dispersed and anchored in a polyethylene glycol matrix, hydroxyl on the surface of the polyethylene glycol reacts with epoxy resin under the action of a catalyst during preparation of an emulsifier, connection among the polyethylene glycol, the graphene and the epoxy resin is achieved, in the process of preparing an emulsion, the graphene enters the emulsion along with the emulsifier, the problems that the graphene is difficult to disperse in the emulsion, the compatibility is poor and the like are solved, and the uniformly dispersed graphene-containing aqueous epoxy resin emulsion is obtained. The graphene-containing waterborne epoxy resin emulsion prepared by the invention has the advantages of good centrifugal, dilution and storage stability, lower cost, safety, environmental protection and no toxicity compared with the traditional epoxy resin; the paint has the advantages of stronger corrosion resistance and adhesive force, good impact resistance and easy construction when being applied to anticorrosive paint.
Description
Technical Field
The invention belongs to the technical field of epoxy resin water-based paint, and particularly relates to graphene-containing water-based epoxy resin emulsion and a preparation method thereof.
Background
The epoxy resin has good physical and chemical properties, excellent bonding strength to the surfaces of metal and non-metal materials, good dielectric property, small shrinkage after curing, high hardness and stability to alkali and most solvents, and is one of synthetic resin varieties with large consumption in the coating industry. With the enhancement of the consciousness of the society on environmental protection, the coating industry is developing from the traditional solvent-based coating to the environment-friendly coatings such as water-based coating, high-solid coating, powder coating, photocureable coating and the like, and the common epoxy resin is insoluble in water and only soluble in organic solvent, so that the application of the epoxy resin is greatly limited, and the water-based epoxy resin is applied and developed. The existing water-based epoxy emulsion has the defects of low corrosion resistance, poor emulsion stability, slow drying, high VOC content and the like, which also limits the application of the emulsion in anticorrosive paint.
Polyethylene glycol is a water-soluble polyether with low molecular weight obtained by gradually adding and polymerizing ethylene oxide and water or ethylene glycol, has many ether bonds and good hydrophilicity, can be dissolved in water but not in a nonpolar solvent at room temperature, and is often used as a nonionic surfactant. The surface activity of the modified polyethylene glycol is greatly improved after the terminal hydroxyl group is substituted by hydrophobic groups such as ester group and the like, and in addition, the polyethylene glycol is a chemical inert substance at normal temperature and normal pressure, so that the unique chemical structure of the modified polyethylene glycol is ensured not to be easily changed. The excellent characteristics of the polyethylene glycol are utilized to react with the epoxy resin to prepare the water-based epoxy resin emulsifier, so that the problem of precipitation of the emulsifier on the surface of a paint film in use can be avoided, and the emulsion with better stability can be prepared.
Graphene is a monolayer of carbon atoms in sp2The novel carbon nanomaterial with a two-dimensional honeycomb lattice structure formed by hybrid tracks has a very large specific surface area and is alternately and randomly arranged in a coating, so that the diffusion path of a corrosive medium can be effectively prolonged, the shielding performance of the coating is enhanced, the corrosion resistance of the coating can be greatly improved by being used as an additive, but due to strong interaction between lamellar structures of the novel carbon nanomaterial, graphene is easy to agglomerate, and the large-scale application of the novel carbon nanomaterial in a coating is limited.
At present, most of graphene modified waterborne epoxy resin coatings are prepared by blending a waterborne epoxy resin emulsion and graphene or blending the modified graphene surface with the waterborne epoxy resin emulsion. Chinese patent No. CN106085133A discloses a novel water-based epoxy graphene anticorrosive paint, which is a two-component anticorrosive paint, wherein the component A consists of a water-based epoxy emulsion without any cosolvent and a defoaming agent; the component B consists of a water-based epoxy curing agent with a self-emulsifying function, graphene, zinc phosphate, titanium dioxide, a flatting agent and water; A. the component B is uniformly mixed according to a certain proportion and then diluted by adding water according to the construction viscosity, and the prepared water-based epoxy graphene anticorrosive paint can be only used for spraying but is not suitable for brushing. Chinese patent No. CN106928810A discloses a polypyrrole/graphene/epoxy emulsion ternary composite water-based anticorrosive paint, a preparation method and application thereof, wherein the paint is a two-component paint, and the component A comprises a water-based epoxy resin emulsion, a polypyrrole @ graphene composite auxiliary agent, a dispersing agent, polyphosphate, titanium dioxide, a defoaming agent, a thickening agent, a leveling agent, a microorganism killing inhibitor and deionized water; the component B is a water-based epoxy curing agent; when the coating is used, the component A and the component B are uniformly mixed and coated on the surface of a substrate with the surface treated, and the coating is prepared after curing.
So far, no report of adding graphene in the initial synthesis stage of preparing the aqueous epoxy resin emulsion is found, which opens up a new path for modifying the epoxy resin emulsion by the graphene.
Disclosure of Invention
The invention aims to prepare a polyethylene glycol/graphene composite material by adopting an in-situ polymerization method, so that graphene can be uniformly dispersed and anchored in a polyethylene glycol matrix, when an emulsifier is prepared, hydroxyl on the surface of the polyethylene glycol reacts with epoxy resin under the action of a catalyst, the connection among the polyethylene glycol, the graphene and the epoxy resin is realized, and in the process of preparing an emulsion, the graphene enters the emulsion along with the emulsifier, so that the problems of difficult dispersion, poor compatibility and the like of the graphene in the emulsion are solved, and the uniformly dispersed graphene-containing waterborne epoxy resin emulsion is obtained.
In order to achieve the above object, the solution of the present invention is:
a preparation method of a graphene-containing waterborne epoxy resin emulsion comprises the following steps:
(1) preparing a polyethylene glycol/graphene composite material: introducing ethylene glycol, graphene and a catalyst A into a high-pressure reaction kettle, mixing and stirring uniformly, introducing high-purity nitrogen for 3-5 times, then pumping to-0.1 MPa under negative pressure, heating to 110-115 ℃, slowly introducing ethylene oxide into the reaction kettle, keeping the temperature in the reaction kettle at 130-140 ℃, controlling the reaction pressure at 0.2-0.5 MPa, and completely introducing the ethylene oxide. Keeping the reaction temperature, reducing the pressure, curing, degassing, neutralizing with citric acid, adsorbing, dehydrating, filtering and drying to obtain the polyethylene glycol/graphene composite material; (2) preparation of the waterborne epoxy resin emulsifier: mixing the polyethylene glycol/graphene composite material obtained in the step (1) with epoxy resin, uniformly mixing at 70-80 ℃, adding a catalyst B, heating to 170-180 ℃, and reacting at constant temperature for 2-4 h to obtain a graphene-containing water-based epoxy resin emulsifier; (3) preparation of aqueous epoxy resin emulsion: and (3) mixing the graphene-containing waterborne epoxy resin emulsifier prepared in the step (2) with epoxy resin, stirring for 0.5h at 50-60 ℃, slowly adding deionized water after uniformly stirring, and stirring for 0.1-0.5 h at a high speed to prepare the graphene-containing waterborne epoxy resin emulsion.
In the step (1), the mass ratio of ethylene glycol to ethylene oxide is 1: 90-470, the amount of graphene is 0.5-10% of the weight of ethylene glycol, and the amount of catalyst A is 10-20% of the amount of ethylene glycol.
In the step (1), the graphene can be replaced by functionalized graphene or oxidized graphene, and the catalyst A is one of sodium hydroxide and potassium hydroxide.
The graphene comprises functionalized graphene. Preferably, the functionalized graphene can be well dispersed in a solvent, and specifically grafted polar groups such as hydroxyl, amino, carboxyl, mercapto, sulfonic group, fluorine group, chlorine group and bromine group; further preferably grafted with a modified substance containing a carbon-carbon double bond.
The molecular weight of the polyethylene glycol prepared in the step (1) is 4000-20000.
In the step (2), the weight ratio of the polyethylene glycol/graphene composite material to the epoxy resin is 1: 1-5, and the amount of the catalyst B is 0.5-2% of the weight of the epoxy resin.
The weight ratio of the graphene-containing waterborne epoxy resin emulsifier to the epoxy resin in the step (3) is 1: 2-6, and the mass fraction of the deionized water is 40-60%.
The epoxy resin is one of bisphenol A type E-12, E-20, E-44, E-51, E-54 and E-55, and the catalyst B is any one of potassium persulfate, boron trifluoride diethyl etherate, aluminum trichloride and triphenyl phosphine.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) the polyethylene glycol is a common raw material for preparing the waterborne epoxy resin emulsifier, and the graphene is introduced in the preparation process of the polyethylene glycol, so that the preparation method has the advantages that: firstly, preparing a polyethylene glycol/graphene composite material by adopting an in-situ polymerization method, so that graphene can be uniformly dispersed and anchored in a polyethylene glycol matrix; secondly, when the emulsifier is prepared, hydroxyl on the surface of the polyethylene glycol reacts with epoxy resin under the action of a catalyst, the epoxy resin is subjected to ring opening, the hydroxyl is introduced to epoxy resin molecules, connection among the polyethylene glycol, the graphene and the epoxy resin is realized, and the emulsifier containing the graphene is uniformly dispersed; thirdly, in the process of preparing the aqueous epoxy resin emulsion, the graphene enters the emulsion along with the emulsifier, so that the problems of difficult dispersion, poor compatibility and the like of the graphene are avoided, and the graphene is seamlessly combined with the epoxy resin.
(2) Compared with the method for directly dispersing graphene in the aqueous epoxy resin emulsion, the preparation method has the advantages that: firstly, as graphene is extremely easy to agglomerate and can be dispersed generally only by long-time high-shear treatment, under the condition, emulsion breaking is extremely easy to cause failure, and the method disclosed by the invention avoids the technical problem; secondly, since graphene is neither hydrophilic nor oleophilic, when graphene is directly dispersed in the emulsion, the probability that graphene is dispersed in the epoxy resin phase and the aqueous phase is the same, which causes the problems that the amount of graphene actually entering the epoxy resin cannot be controlled and graphene in the aqueous phase is wasted; thirdly, as the surface of the graphene is inert and the viscosity of the aqueous emulsion is low, the graphene needs to be prepared when being directly dispersed in the emulsion, otherwise, the graphene is easy to settle and agglomerate.
(3) The preparation method disclosed by the invention not only overcomes the problems of difficult charging of graphene powder, uneven dispersion, dust pollution and the like, but also the prepared graphene-containing waterborne epoxy resin emulsion has good centrifugation, dilution and storage stability, and is lower in cost, safe, environment-friendly and nontoxic compared with the traditional epoxy resin; the paint has the advantages of stronger corrosion resistance and adhesive force, good impact resistance and easy construction when being applied to anticorrosive paint.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.
Example 1
(1) Preparation of polyethylene glycol/graphene composite material
Introducing 0.1mol of ethylene glycol, 0.2g of graphene powder and 0.02mol of sodium hydroxide into a high-pressure reaction kettle, mixing and stirring uniformly, introducing high-purity nitrogen for replacement for 3-5 times, then pumping to-0.1 MPa under negative pressure, heating to 110 ℃, slowly introducing 9mol of ethylene oxide into the reaction kettle, keeping the temperature in the reaction kettle at 130 ℃, controlling the reaction pressure at 0.35MPa, and completely introducing the ethylene oxide. Keeping the reaction temperature, reducing the pressure, curing, degassing, neutralizing with citric acid, adsorbing, dehydrating, filtering and drying to obtain the polyethylene glycol/graphene composite material with the molecular weight of about 4000;
(2) preparation of aqueous epoxy resin emulsifier
Uniformly mixing 400g of polyethylene glycol/graphene composite material and 400g of epoxy resin E-44 at 70 ℃, adding 2g of potassium persulfate, heating to 170 ℃, and reacting at constant temperature for 4 hours to obtain a graphene-containing waterborne epoxy resin emulsifier;
(3) preparation of aqueous epoxy resin emulsion
And (2) mixing 100g of graphene-containing waterborne epoxy resin emulsifier with 200g of epoxy resin, stirring at 50 ℃ for 0.5h, uniformly stirring, slowly adding 200g of deionized water, and stirring at a high speed for 0.5h to obtain the graphene-containing waterborne epoxy resin emulsion.
Example 2
(1) Preparation of polyethylene glycol/graphene composite material
Introducing 0.1mol of ethylene glycol, 0.2g of graphene oxide powder and 0.02mol of sodium hydroxide into a high-pressure reaction kettle, mixing and stirring uniformly, introducing high-purity nitrogen for replacement for 3-5 times, then pumping to-0.1 MPa under negative pressure, heating to 110 ℃, slowly introducing 9mol of ethylene oxide into the reaction kettle, keeping the temperature in the reaction kettle at 130 ℃, controlling the reaction pressure at 0.35MPa, and completely introducing the ethylene oxide. Keeping the reaction temperature, reducing the pressure, curing, degassing, neutralizing with citric acid, adsorbing, dehydrating, filtering and drying to obtain the polyethylene glycol/graphene oxide composite material with the molecular weight of about 4000;
(2) preparation of aqueous epoxy resin emulsifier
Uniformly mixing 400g of polyethylene glycol/graphene oxide composite material and 400g of epoxy resin E-44 at 70 ℃, adding 2g of potassium persulfate, heating to 170 ℃, and reacting at constant temperature for 4 hours to obtain a water-based epoxy resin emulsifier containing graphene oxide;
(3) preparation of aqueous epoxy resin emulsion
And (2) mixing 100g of the graphene oxide-containing waterborne epoxy resin emulsifier with 200g of epoxy resin, stirring at 50 ℃ for 0.5h, uniformly stirring, slowly adding 200g of deionized water, and stirring at a high speed for 0.5h to obtain the graphene oxide-containing waterborne epoxy resin emulsion.
Example 3
(1) Preparation of polyethylene glycol/graphene composite material
Introducing 0.1mol of ethylene glycol, 0.2g of functionalized graphene powder and 0.02mol of sodium hydroxide into a high-pressure reaction kettle, mixing and stirring uniformly, introducing high-purity nitrogen for replacement for 3-5 times, then pumping to-0.1 MPa under negative pressure, heating to 110 ℃, slowly introducing 9mol of ethylene oxide into the reaction kettle, keeping the temperature in the reaction kettle at 130 ℃, controlling the reaction pressure at 0.35MPa, and completely introducing the ethylene oxide. Keeping the reaction temperature, reducing the pressure, curing, degassing, neutralizing with citric acid, adsorbing, dehydrating, filtering and drying to obtain the polyethylene glycol/functionalized graphene composite material with the molecular weight of about 4000;
(2) preparation of aqueous epoxy resin emulsifier
Uniformly mixing 400g of polyethylene glycol/functionalized graphene composite material and 400g of epoxy resin E-44 at 70 ℃, adding 2g of potassium persulfate, heating to 170 ℃, and reacting at constant temperature for 4 hours to obtain a water-based epoxy resin emulsifier containing functionalized graphene;
(3) preparation of aqueous epoxy resin emulsion
And (2) mixing 100g of the graphene oxide-containing waterborne epoxy resin emulsifier with 200g of epoxy resin, stirring at 50 ℃ for 0.5h, uniformly stirring, slowly adding 200g of deionized water, and stirring at a high speed for 0.5h to obtain the functionalized graphene-containing waterborne epoxy resin emulsion.
Example 4
(1) Preparation of polyethylene glycol/graphene composite material
Introducing 0.1mol of ethylene glycol, 0.05g of graphene powder and 0.01mol of sodium hydroxide into a high-pressure reaction kettle, mixing and stirring uniformly, introducing high-purity nitrogen for replacement for 3-5 times, then pumping to-0.1 MPa under negative pressure, heating to 110 ℃, slowly introducing 13.5mol of ethylene oxide into the reaction kettle, keeping the temperature in the reaction kettle at 130 ℃, controlling the reaction pressure at 0.35MPa, and completely introducing the ethylene oxide. Keeping the reaction temperature, reducing the pressure, curing, degassing, neutralizing with citric acid, adsorbing, dehydrating, filtering and drying to obtain the polyethylene glycol/graphene composite material with the molecular weight of about 6000;
(2) preparation of aqueous epoxy resin emulsifier
Uniformly mixing 500g of polyethylene glycol/graphene composite material and 1000g of epoxy resin E-51 at 80 ℃, adding 5g of boron trifluoride diethyl etherate, heating to 180 ℃, and reacting at constant temperature for 2 hours to obtain a graphene-containing waterborne epoxy resin emulsifier;
(3) preparation of aqueous epoxy resin emulsion
And (2) mixing 100g of graphene-containing waterborne epoxy resin emulsifier with 400g of epoxy resin, stirring at 60 ℃ for 0.5h, uniformly stirring, slowly adding 500g of deionized water, and stirring at a high speed for 0.4h to obtain the graphene-containing waterborne epoxy resin emulsion.
Example 5
(1) Preparation of polyethylene glycol/graphene composite material
Introducing 0.1mol of ethylene glycol, 0.3g of graphene powder and 0.02mol of sodium hydroxide into a high-pressure reaction kettle, mixing and stirring uniformly, introducing high-purity nitrogen for replacement for 3-5 times, then pumping to-0.1 MPa under negative pressure, heating to 110 ℃, slowly introducing 22.5mol of ethylene oxide into the reaction kettle, keeping the temperature in the reaction kettle at 130 ℃, controlling the reaction pressure at 0.35MPa, and completely introducing the ethylene oxide. Keeping the reaction temperature, reducing the pressure, curing, degassing, neutralizing with citric acid, adsorbing, dehydrating, filtering, and drying to obtain a polyethylene glycol/graphene composite material with a molecular weight of about 10000;
(2) preparation of aqueous epoxy resin emulsifier
Uniformly mixing 100g of polyethylene glycol/graphene composite material and 300g of epoxy resin E-12 at 80 ℃, adding 3g of triphenyl phosphine, heating to 180 ℃, and reacting at constant temperature for 2 hours to obtain a graphene-containing waterborne epoxy resin emulsifier;
(3) preparation of aqueous epoxy resin emulsion
And (2) mixing 100g of graphene-containing waterborne epoxy resin emulsifier with 600g of epoxy resin, stirring at 60 ℃ for 0.5h, uniformly stirring, slowly adding 1050g of deionized water, and stirring at a high speed for 0.4h to obtain the graphene-containing waterborne epoxy resin emulsion.
Example 6
(1) Preparation of polyethylene glycol/graphene composite material
Introducing 0.1mol of ethylene glycol, 0.6g of graphene powder and 0.15mol of sodium hydroxide into a high-pressure reaction kettle, mixing and stirring uniformly, introducing high-purity nitrogen for replacement for 3-5 times, then pumping to-0.1 MPa under negative pressure, heating to 110 ℃, slowly introducing 45mol of ethylene oxide into the reaction kettle, keeping the temperature in the reaction kettle at 130 ℃, controlling the reaction pressure at 0.35MPa, and completely introducing the ethylene oxide. Keeping the reaction temperature for decompression and curing, performing degassing treatment after curing, neutralizing with citric acid after degassing, adsorbing, dehydrating, filtering and drying to obtain a polyethylene glycol/graphene composite material with the molecular weight of about 20000;
(2) preparation of aqueous epoxy resin emulsifier
Uniformly mixing 200g of polyethylene glycol/graphene composite material and 600g of epoxy resin E-55 at 75 ℃, adding 6g of aluminum trichloride, heating to 175 ℃, and reacting for 3 hours at constant temperature to obtain a graphene-containing water-based epoxy resin emulsifier;
(3) preparation of aqueous epoxy resin emulsion
And (2) mixing 200g of the graphene-containing waterborne epoxy resin emulsifier with 800g of epoxy resin, stirring at 55 ℃ for 0.5h, uniformly stirring, slowly adding 1000g of deionized water, and stirring at a high speed for 0.3h to obtain the graphene-containing waterborne epoxy resin emulsion.
The embodiments selected above are exemplary embodiments and the above description is only intended to help understand the method of the present invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (7)
1. A preparation method of graphene-containing waterborne epoxy resin emulsion is characterized by comprising the following steps:
(1) preparing a polyethylene glycol/graphene composite material: introducing ethylene glycol, graphene and a catalyst A into a high-pressure reaction kettle, mixing and stirring uniformly, introducing high-purity nitrogen for 3-5 times, then pumping to-0.1 MPa under negative pressure, heating to 110-115 ℃, slowly introducing ethylene oxide into the reaction kettle, keeping the temperature in the reaction kettle at 130-140 ℃, controlling the reaction pressure at 0.2-0.5 MPa, completely introducing the ethylene oxide, keeping the reaction temperature for decompression and curing, degassing after curing, neutralizing with citric acid, adsorbing, dehydrating, filtering and drying after degassing to obtain a polyethylene glycol/graphene composite material, wherein the catalyst A is one of sodium hydroxide and potassium hydroxide;
(2) preparation of the waterborne epoxy resin emulsifier: mixing the polyethylene glycol/graphene composite material obtained in the step (1) with epoxy resin, uniformly mixing at 70-80 ℃, adding a catalyst B, heating to 170-180 ℃, and reacting at constant temperature for 2-4 h to obtain a graphene-containing aqueous epoxy resin emulsifier, wherein the catalyst B is any one of potassium persulfate, boron trifluoride ether, aluminum trichloride and triphenylphosphine;
(3) preparation of aqueous epoxy resin emulsion: and (3) mixing the graphene-containing waterborne epoxy resin emulsifier prepared in the step (2) with epoxy resin, stirring for 0.5h at 50-60 ℃, slowly adding deionized water after uniformly stirring, and stirring for 0.1-0.5 h at a high speed to prepare the graphene-containing waterborne epoxy resin emulsion.
2. The method for preparing the graphene-containing aqueous epoxy resin emulsion according to claim 1, wherein the amount ratio of the ethylene glycol to the ethylene oxide in the step (1) is 1: 90-470, the amount of the graphene is 0.5-10% of the weight of the ethylene glycol, and the amount of the catalyst A is 10-20% of the amount of the ethylene glycol.
3. The method for preparing the graphene-containing aqueous epoxy resin emulsion according to claim 1, wherein in the step (1), the graphene can be replaced by functionalized graphene or graphene oxide.
4. The method for preparing the graphene-containing aqueous epoxy resin emulsion according to claim 1, wherein the molecular weight of the polyethylene glycol prepared in the step (1) is 4000 to 20000.
5. The method for preparing the graphene-containing aqueous epoxy resin emulsion according to claim 1, wherein the ratio of the polyethylene glycol/graphene composite material to the epoxy resin in the step (2) is 1: 1-5, and the amount of the catalyst B is 0.5-2% of the weight of the epoxy resin.
6. The method for preparing the graphene-containing aqueous epoxy resin emulsion according to claim 1, wherein the weight ratio of the graphene-containing aqueous epoxy resin emulsifier to the epoxy resin in the step (3) is 1: 2-6, and the mass fraction of the deionized water is 40-60%.
7. The method for preparing the graphene-containing aqueous epoxy resin emulsion according to claim 1, wherein the epoxy resin is one of bisphenol A type E-12, E-20, E-44, E-51, E-54 and E-55.
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| CN109881486B (en) * | 2019-02-19 | 2020-06-09 | 北京化工大学 | Hyperbranched emulsifier and preparation method thereof |
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| CN111675883B (en) * | 2020-07-08 | 2022-08-12 | 邦弗特新材料股份有限公司 | Water-based epoxy emulsion and preparation method thereof |
| KR20230167012A (en) * | 2021-04-08 | 2023-12-07 | 세키스이가가쿠 고교가부시키가이샤 | Curable resin composition, adhesive for optical reception and light emitting module, sealant for optical receiving and light emitting module, and member for optical receiving and light emitting module |
| CN113174183B (en) * | 2021-04-27 | 2022-07-22 | 福州大学 | Organic solvent-free graphene-reinforced waterborne epoxy resin coating and preparation method thereof |
| CN113683938B (en) * | 2021-08-23 | 2023-05-02 | 亚士创能科技(上海)股份有限公司 | Epoxy graphene intermediate and preparation method and application thereof |
| CN113800978A (en) * | 2021-10-19 | 2021-12-17 | 何艳琴 | Foliar fertilizer suitable for tea trees and preparation method thereof |
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