CN109456678B - Graphene modification preparation method suitable for epoxy resin - Google Patents
Graphene modification preparation method suitable for epoxy resin Download PDFInfo
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- CN109456678B CN109456678B CN201811378394.9A CN201811378394A CN109456678B CN 109456678 B CN109456678 B CN 109456678B CN 201811378394 A CN201811378394 A CN 201811378394A CN 109456678 B CN109456678 B CN 109456678B
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- epoxy resin
- graphene
- urushiol
- epoxidized
- cardanol
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Abstract
The invention discloses a graphene modification preparation method suitable for epoxy resin. The method takes green and renewable urushiol extracted from Chinese lacquer trees or cardanol extracted from cashew shells as a main raw material, and obtains urushiol glycidyl ether or cardanol glycidyl ether with phenolic hydroxyl by using the epoxidation reaction of unsaturated double bonds on long side chains and fatty acid; the modified graphene is used as a reducing agent and a modifier of graphene oxide, and the modified graphene which contains a large number of long carbon chains and epoxy groups on the surface and has good dispersibility in epoxy resin is obtained. The invention takes natural renewable compounds of urushiol and cardanol as main raw materials, has the characteristics of environmental protection, simple process, low production cost and the like, and is easy to popularize and use. The modified graphene prepared by the method has good compatibility in epoxy resin, improves the interface bonding force of the graphene/epoxy resin composite material, and can obviously improve the mechanical property and corrosion resistance of the epoxy resin.
Description
Technical Field
The invention belongs to the field of preparation of nano composite materials, and particularly relates to a modified preparation method of graphene and preparation of a modified graphene/epoxy resin composite material.
Background
The epoxy resin coating has the advantages of excellent chemical corrosion resistance, excellent adhesion, low shrinkage rate, low price and the like, and is a type of anticorrosive coating which is widely applied at present. However, the pure epoxy resin coating has the defects of large internal stress, hard and brittle texture, no impact resistance and the like due to high crosslinking density after curing, and meanwhile, a plurality of microchannels are formed in the coating due to solvent volatilization in the curing process, so that the corrosion resistance of the coating is reduced, and the epoxy coating is difficult to meet the requirements of practical application of engineering technology. The traditional modification method mainly comprises the steps of rubber modification, inorganic filler (such as Zn powder) filling, expansion monomer and the like. With the development of the new-age oceanic chemical industry, the corrosion-resistant coating not only has higher requirements on corrosion resistance and durability, but also has new requirements on light weight, energy conservation, environmental friendliness, high performance and the like. The development of novel epoxy resin-based anticorrosive functional coating not only has challenging research work but also has wide market prospect by searching a novel green, energy-saving and efficient modifier and a modification method.
Graphene is a new carbonaceous material with a single-layer two-dimensional honeycomb crystal structure formed by tightly packing carbon atoms. The high hardness, the light degree and the toughness of the coating are difficult to reach by common rigid materials, and simultaneously, the coating is applied to the anticorrosive coating as a filler due to the high specific surface area and the special lamellar structure, plays a role of a physical barrier to block the permeation of oxygen and corrosive media, and improves the corrosion resistance of the coating. However, the surface of the graphene is inert, is not oleophilic, is not hydrophilic, has a large specific surface area, has strong van der Waals acting force between sheets, and is easy to agglomerate. In order to fully exert the excellent performance of graphene, the dispersibility and composite interface effect of graphene in a coating polymer matrix need to be improved. At present, starting from graphene oxide, a reducing agent is applied to obtain functionalized graphene with better dispersibility in the presence of a stabilizer and a protective agent. However, the stabilizer, the protective agent and the modifier are generally expensive, the reducing agent is generally toxic, a large amount of complicated graphene modification work cannot meet the actual needs of industrial production, and the performance of the polymer matrix is influenced to a certain extent.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a simple, convenient and green method for modifying graphene by using an intrinsic corrosion resistant monomer, which is suitable for large-scale application. The obtained modified graphene/epoxy resin composite material integrates the comprehensive properties of graphene, intrinsic corrosion resistance functional monomer and epoxy resin, and the toughness and corrosion resistance are obviously improved.
In order to achieve the purpose, the invention adopts the following technical scheme: a graphene modification preparation method suitable for epoxy resin is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving urushiol or cardanol in organic solvent, adding acetic acid or formic acid, and H2O2Reacting the solution and a catalyst at 30-50 ℃ for 6-24h, cooling to room temperature, adding NaOH aqueous solution for washing until the pH is =7, removing a water layer, and performing rotary evaporation on an organic phase to obtain a product, namely epoxidized urushiol or epoxidized cardanol;
(2) dissolving the epoxidized urushiol or epoxidized cardanol obtained in the step (1) in at least one solvent selected from water, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), ethanol or methanol to prepare a solution with the concentration of 0.01-2.5 wt%; dispersing graphene oxide in at least one solvent selected from water, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), ethanol or methanol to form a graphene oxide dispersion liquid with the concentration of 0.03-10 mg/mL;
(3) and (3) mixing the two liquids prepared in the step (2) according to the mass ratio of the epoxidized urushiol or the epoxidized cardanol to the oxidized graphene of 1: 1-10: 1, uniformly mixing, and reacting for 2-48 hours at the temperature of 60-120 ℃; the reaction atmosphere is at least one selected from nitrogen, helium, argon or hydrogen, preferably nitrogen; and filtering and repeatedly washing to obtain the graphene oxide reduced and modified by the epoxidized urushiol or the epoxidized cardanol.
The urushiol or cardanol, acetic acid or formic acid and H in the step (1)2O2The ratio of the amounts of substances of (a) to (b) is 1: (5-20): (5-10); the concentration of the NaOH aqueous solution is 0.1-1 mol/L.
The modified graphene prepared by the method disclosed by the invention is applied to preparation of a modified graphene/epoxy resin composite material.
The application is characterized by comprising the following steps:
(1) the method comprises the following steps of reducing and modifying the epoxidized urushiol or epoxidized cardanol prepared by the method, liquid glycidyl epoxy resin and a diluent in a weight ratio of (0.5-5): 100: (10-300), stirring and mixing at the speed of 800-1200 rpm for 40-80 min to obtain modified epoxy resin;
(2) adding a curing agent into the modified epoxy resin, stirring and mixing at the speed of 800-1200 rpm for 10-20min, brushing on the processed rectangular tinplate, curing at normal temperature for 24h, and curing at 60 ℃ for 2h to obtain the modified graphene/epoxy resin composite coating.
The diluent is at least one of ketones, alcohols, esters and hydrocarbons.
The diluent is at least one of acetone, cyclohexanone, methanol, ethanol, butanol, xylene and ethyl acetate.
The curing agent is an amine curing agent and is selected from one or more of polyamide 650, polyamide 300, 4-diaminodiphenylmethane, phenol aldehyde amine HDT-31 and T-31.
The liquid glycidyl epoxy resin is selected from epoxy resin bisphenol A E-12, E-20, E-44, E-51, E-54 and E-55.
Compared with the prior art, the invention has the following advantages:
(1) the adopted raw material urushiol or cardanol is an extracting solution of lacquer trees and cashew shells, is a green natural product, is natural and renewable, and has rich resources.
(2) The epoxidized urushiol or epoxidized cardanol obtained by modifying urushiol or cardanol retains phenolic hydroxyl groups of urushiol and cardanol, namely the reducing capability of urushiol or cardanol on graphene oxide; meanwhile, the epoxy group is added on the molecular structure, so that the epoxy group with a long carbon chain is modified on the surface of the obtained modified graphene, good dispersion and compatibility can be realized in an epoxy resin matrix, and the toughening effect of the graphene is favorably exerted.
(3) The modified graphene is prepared by applying the inherent urushiol or cardanol with the corrosion resistance, and then the graphene/epoxy resin composite material is prepared, so that the excellent performances of the graphene and the inherent urushiol or cardanol with the corrosion resistance are integrated, and the corrosion resistance of the epoxy resin is obviously improved.
Drawings
Fig. 1 is a FT-IR spectrum of graphene prepared in example 1 of the present invention.
Fig. 2 is an AFM image of graphene prepared in example 1 of the present invention.
Fig. 3 is an XPS spectrum of graphene prepared in example 1 of the present invention.
Fig. 4 is a tafel plot of the coating of example 1 of the present invention and the coating without graphene epoxy added.
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative only and not to limit the scope of the invention.
The graphene oxide in the following examples can be prepared by a method reported in the literature or can be a commercially available product.
Example 1
Dissolving 18.8 g of urushiol, 40g of acetic acid and 1 g of concentrated sulfuric acid in 30mL of dimethylbenzene, reacting at 30-50 ℃ for 12h, cooling to room temperature, adding 0.1mol/L of NaOH aqueous solution, washing until the pH is =7, separating, removing a water layer, taking an organic phase, performing rotary evaporation, and removing redundant acetic acid to obtain the product, namely the epoxidized urushiol. Respectively dissolving and dispersing the obtained epoxidized urushiol and the graphene oxide prepared by the Hummer method in an N, N-Dimethylformamide (DMF) solvent to prepare epoxidized urushiol with the concentration of 50mg/mL and graphene oxide dispersion liquid with the concentration of 10 mg/mL. Mixing the two solutions in equal mass, reacting for 8 hours at 100 ℃ in nitrogen atmosphere, filtering and repeatedly washing to obtain the oxidized graphene reduced and modified by the epoxidized urushiol. Dispersing 0.3g of the epoxidized urushiol modified reduced graphene oxide in 100g of bisphenol A epoxy resin with the label number of 601-75, adding 50g of acetone and 100g of xylene, fully stirring for 80min, adding 50g of polyamide 650 curing agent, uniformly stirring, and brushing the coating on the surface of a tinplate. Curing at room temperature for 24h and curing at 60 ℃ for 2 h. The epoxy coating with the same mass and without modified graphene is used as a reference.
As shown in FIG. 1, the XPS spectrum of the sample modified graphene is assigned to graphene oxide C-O near 286 eV and the characteristic peak of C = O is greatly weakened, and the characteristic peak of C = C at 284.8eV is mainly retained, which indicates that the graphene oxide is reduced by the reaction with the epoxy urushiol.
As shown in FIG. 2, the absorption peak of hydroxyl (-OH) at 3410cm-1 of the infrared spectrum of the graphene oxide after reduction modification is obviously weakened, stretching vibration belonging to urushiol alkyl chain occurs at 2927 and 2850 cm-1, and the characteristic peak of urushiol unsaturated double bond does not occur at 3016cm-1, which proves that the double bond of the urushiol side chain is oxidized; characteristic peaks ascribed to epoxy groups (C-O-C) appeared at 1030 and 906cm-1, indicating that the epoxidized urushiol has been modified on the surface of the reduced graphene oxide.
As shown in fig. 3, it can be seen from the atomic force microscope photograph that the graphene is monodispersed and distributed after being reduced and modified by the epoxidized urushiol, the thickness of the graphene is about 3nm, and the surface of the graphene is uniformly modified with particles of 20nm, which is the epoxidized urushiol modified on the surface of the graphene.
Fig. 4 shows a tafel plot of 0.5% modified graphene/epoxy composite coating in 3.5% NaCl saline. From the results of fig. 4 and table 1, it can be seen that, compared with the pure epoxy resin coating, the corrosion resistance voltage and polarization resistance of the coating are significantly increased after the graphene is added, the corrosion current is reduced by 2 orders of magnitude, the corrosion resistance efficiency reaches 99.4%, and the coating has good corrosion resistance.
TABLE 1 electrochemical corrosion parameters obtained for potentiodynamic potential polarization test results
Example 2
Reacting 18.8 g of cardanol and 40g of formic acid in 30mL of dimethylbenzene at 30-50 ℃ for 12h, cooling to room temperature, adding 0.1mol/L of NaOH aqueous solution for washing until the pH is =7, separating, removing a water layer, taking an organic phase for rotary evaporation, and removing redundant acetic acid to obtain the product, namely the epoxidized urushiol. Respectively dissolving and dispersing the obtained epoxidized cardanol and graphene oxide prepared by a Hummer method in an N, N-Dimethylformamide (DMF) solvent to prepare an epoxidized cardanol dispersion liquid with the concentration of 50mg/mL and a graphene oxide dispersion liquid with the concentration of 10 mg/mL. Mixing the two solutions in equal mass, reacting for 8 hours at 100 ℃ in nitrogen atmosphere, filtering and repeatedly washing to obtain the epoxidized cardanol reduced and modified graphene oxide. Dispersing 0.3g of epoxidized cardanol modified reduced graphene oxide in 100g of bisphenol A epoxy resin with the label number of 601-75, adding 50g of acetone and 100g of xylene, fully stirring for 80min, adding 50g of polyamide 650 curing agent, uniformly stirring, and brushing the coating on the surface of a tinplate. Curing at room temperature for 24h and curing at 60 ℃ for 2 h. The epoxy coating with the same mass and without modified graphene is used as a reference. The characterization results are similar to the synthesized product of example 1.
The above description is only a preferred embodiment, and all equivalent changes and modifications made in accordance with the protection scope of the present invention should be covered by the present invention.
Claims (8)
1. A graphene modification preparation method suitable for epoxy resin is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving urushiol or cardanol in organic solvent, adding acetic acid or formic acid, and H2O2Reacting the solution and a catalyst at 30-50 ℃ for 6-24h, cooling to room temperature, adding NaOH aqueous solution for washing until the pH is =7, removing a water layer, and performing rotary evaporation on an organic phase to obtain a product, namely epoxidized urushiol or epoxidized cardanol;
(2) dissolving the epoxidized urushiol or epoxidized cardanol obtained in the step (1) in at least one solvent selected from water, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), ethanol or methanol to prepare a solution with the concentration of 0.01-2.5 wt%; dispersing graphene oxide in at least one solvent selected from water, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), ethanol or methanol to form a graphene oxide dispersion liquid with the concentration of 0.03-10 mg/mL;
(3) and (3) mixing the two liquids prepared in the step (2) according to the mass ratio of the epoxidized urushiol or the epoxidized cardanol to the oxidized graphene of 1: 1-10: 1, uniformly mixing, and reacting for 2-48 hours at the temperature of 60-120 ℃; the reaction atmosphere is at least one selected from nitrogen, helium and argon; and filtering and repeatedly washing to obtain the graphene oxide reduced and modified by the epoxidized urushiol or the epoxidized cardanol.
2. The method of claim 1, wherein: the urushiol or cardanol, acetic acid or formic acid, and H in the step (1)2O2The ratio of the amounts of substances of (a) to (b) is 1: (5-20): (5-10); the concentration of the NaOH aqueous solution is 0.1-1 mol/L.
3. Use of the modified graphene prepared by the method of claim 1 or 2 in the preparation of a modified graphene/epoxy resin composite.
4. Use according to claim 3, characterized in that it comprises the following steps:
(1) the method comprises the following steps of reducing and modifying the epoxidized urushiol or epoxidized cardanol prepared by the method of claim 1 or 2, liquid glycidyl epoxy resin and a diluent in a weight ratio of (0.5-5): 100: (10-300), stirring and mixing at the speed of 800-1200 rpm for 40-80 min to obtain modified epoxy resin;
(2) adding a curing agent into the modified epoxy resin, stirring and mixing at the speed of 800-1200 rpm for 10-20min, brushing on the processed rectangular tinplate, curing at normal temperature for 24h, and curing at 60 ℃ for 2h to obtain the modified graphene/epoxy resin composite coating.
5. Use according to claim 4, characterized in that: the diluent is at least one of ketones, alcohols, esters and hydrocarbons.
6. Use according to claim 4, characterized in that: the diluent is at least one of acetone, cyclohexanone, methanol, ethanol, butanol, xylene and ethyl acetate.
7. Use according to claim 4, characterized in that: the curing agent is an amine curing agent and is selected from one or more of polyamide 650, polyamide 300, 4-diaminodiphenylmethane, phenol aldehyde amine HDT-31 and T-31.
8. Use according to claim 4, characterized in that: the liquid glycidyl epoxy resin is selected from epoxy resin bisphenol A E-12, E-20, E-44, E-51, E-54 and E-55.
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| CN111978771B (en) * | 2019-05-21 | 2022-03-01 | 中车唐山机车车辆有限公司 | Modified graphene oxide, preparation method thereof, anticorrosive paint containing modified graphene oxide and preparation method |
| CN113025155A (en) * | 2021-02-07 | 2021-06-25 | 南京工业大学 | Preparation method of bio-based coating with high anti-corrosion property |
| CN113248738B (en) * | 2021-06-24 | 2022-07-01 | 西南科技大学 | Two-dimensional material modified epoxy resin composite material and preparation method thereof |
| CN113698848B (en) * | 2021-08-10 | 2022-04-29 | 中山大学 | Water-based nanosheet composite coating and preparation method and application thereof |
| CN114316745B (en) * | 2022-01-05 | 2022-11-08 | 南京工业大学 | Composite coating containing cardanol-based active diluent modified graphene oxide filler and preparation method and application thereof |
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| CN103554063A (en) * | 2013-11-06 | 2014-02-05 | 河南省化工研究所有限责任公司 | Preparation method of cardanol glycidyl ether with high epoxy value |
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| CN103627139A (en) * | 2013-09-25 | 2014-03-12 | 杭州师范大学 | Preparation method of functionalized graphene oxide/epoxy resin nanocomposite |
| CN103554063A (en) * | 2013-11-06 | 2014-02-05 | 河南省化工研究所有限责任公司 | Preparation method of cardanol glycidyl ether with high epoxy value |
| CN103641109A (en) * | 2013-12-14 | 2014-03-19 | 福建师范大学 | Method for synchronously reducing and modifying graphene oxide |
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