CN113717499A - Preparation method of poly-dopamine nano-layer coated graphene oxide filling resin - Google Patents
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Abstract
The invention discloses a preparation method of a polydopamine nano-layer-coated graphene oxide-filled epoxy resin composite material, which comprises the following steps: 1) preparing natural crystalline flake graphite into graphene oxide; 2) coating oxidized graphene by self-polymerization of polydopamine; 3) and coating the polydopamine nano-layer with graphene oxide filled epoxy resin. The graphene oxide adopted by the invention has good insulating property and mechanical property, the interface compatibility with epoxy is improved through dopamine coating, and the interface stress between the graphene oxide and epoxy resin is reduced; meanwhile, through three-stage curing, the internal stress in the epoxy resin curing process is reduced as much as possible, so that the epoxy resin composite material with both insulating property and mechanical property is obtained.
Description
Technical Field
The invention relates to a preparation method of epoxy resin, in particular to a preparation method of a polydopamine nano-layer coated graphene oxide filled epoxy resin composite.
Background
Epoxy resin has many advantages such as good dimensional stability, corrosion resistance, heat resistance, insulating property and small curing shrinkage, and is widely used in the fields of high-voltage insulation, aerospace, building, agriculture and the like. However, since epoxy resin is a thermosetting polymer material, there is a large internal stress in the epoxy resin during curing, resulting in poor mechanical properties and low impact resistance. Meanwhile, the performances of different types of epoxy resin are different, and bisphenol A epoxy resin has a longer molecular chain, better mechanical property than alicyclic epoxy resin, higher viscosity and weaker insulating property than alicyclic epoxy resin. In industrial application, in order to improve the mechanical properties of epoxy resin, the epoxy resin is mostly mixed with other materials (such as glass fiber and carbon fiber) to prepare composite materials for use, but the interfacial properties of a resin matrix and other materials still need to be solved.
Graphene has extremely high mechanical strength, is often used as a filling material to improve the mechanical strength of an organic polymer material, but has extremely excellent conductivity, which can destroy the insulation property of the polymer material such as epoxy resin, and graphene oxide has a pi-pi structure in the graphene due to a large amount of oxygen-containing functional groups in the graphene oxide, so that the graphene oxide has good insulation property while maintaining high mechanical property, and meanwhile, the oxygen-containing active groups on the surface of the graphene oxide can greatly improve the hydrophilicity and facilitate surface modification of the graphene oxide. However, as with other filling particles, the graphene oxide is used to directly fill the epoxy resin, and the graphene oxide of the inorganic filler has poor interface compatibility with the organic polymer epoxy resin, so that a large number of interface defects are introduced to reduce the dielectric properties of the epoxy resin. In addition, the dopamine has extremely strong physical adsorption capacity, so that the interface performance of the epoxy resin and other materials can be effectively improved, the mechanical property of the epoxy resin is enhanced, the interface defect in the matrix is reduced, and the good dielectric and breakdown characteristics of the epoxy resin are ensured. .
Disclosure of Invention
The invention provides a preparation method of a polydopamine nano-layer-coated graphene oxide-filled epoxy resin composite material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a polydopamine nano-layer coated graphene oxide filled epoxy resin composite material comprises the following steps: 1) preparing natural crystalline flake graphite into graphene oxide; 2) coating oxidized graphene by self-polymerization of polydopamine; 3) and coating the polydopamine nano-layer with graphene oxide filled epoxy resin.
Preferably, the specific steps of preparing the natural crystalline flake graphite into the graphene oxide are as follows: 1) adding concentrated H2SO4With concentrated H3PO4The mixed solution is subjected to ice bath; 2) weighing natural crystalline flake graphite, adding the mixed solution after ice bath, stirring, and adding KMnO while stirring4Fully reacting; 3) heating in water bath, continuously stirring for reaction, and repeating; stirring in ice bath; 4) addition of H2O2Until the reaction is complete; 5) diluting the obtained product in distilled water, performing suction filtration, and repeatedly washing; 6) and fully dissolving the product obtained in the last step into distilled water, and performing ultrasonic filtration to obtain the graphene oxide.
Preferably, the graphene oxide coated by polydopamine through self-polymerization comprises the following specific steps: 1) weighing Tris buffer solution with the pH value of 8.5; 2) adding graphene oxide into a Tris buffer solution, and performing ultrasonic dispersion; 3) adding dopamine hydrochloride, dissolving in ultrasonic dispersion, and placing in a water bath for full reaction; 4) and carrying out suction filtration on the solution after reaction, repeatedly washing, and drying the obtained product to obtain the poly-dopamine-coated graphene oxide.
Preferably, the specific steps of coating the polydopamine nano-layer with the graphene oxide filled epoxy resin are as follows: 1) dissolving polydopamine-coated graphene oxide in a diluent, and performing ultrasonic dispersion; 2) adding epoxy resin into the dispersion liquid obtained in the last step, completely mixing, and heating in a water bath for full reaction; 3) adding a curing agent and an accelerant, reacting at room temperature, and putting in a vacuum box to remove bubbles; 4) and injecting the mixed solution into a mold, curing and demolding to obtain the poly-dopamine nano-layer coated graphene oxide filled epoxy resin.
Preferably, the concentration of H is2SO4Concentration 98%, concentrated H3PO4Concentrated H with a concentration of 85%2SO4With concentrated H3PO4The volume ratio of (1) to (7) to (3).
Preferably, after the dopamine hydrochloride is dissolved in the ultrasonic dispersion liquid, the final concentration of the dopamine hydrochloride is 0.6-1.2 mg/mL.
Preferably, the diluent is ethanol or acetone.
Preferably, the epoxy resin is a bisphenol a type or a cycloaliphatic epoxy resin.
Preferably, the curing agent is methyl tetrahydrophthalic anhydride or methyl hexahydrophthalic anhydride.
Preferably, the promoter is 2-ethyl-4-methylimidazole.
The invention has the beneficial effects that: 1. the method strips graphite to obtain the graphene oxide with a large number of active functional groups. The subsequent reaction effect with dopamine is increased by a large number of active groups, so that the dopamine layer and graphene are chemically bonded, and the recovery effect of dopamine is improved.
2. According to the method, a dopamine autopolymerization technology is adopted, graphene oxide is subjected to surface functionalization, and the extremely strong physical adsorption capacity of dopamine and the bonding effect of active amino groups and graphene oxide are utilized, so that the interface compatibility of graphene oxide and epoxy resin is greatly improved, and the dispersion of graphene oxide in epoxy resin is improved.
3. The graphene oxide adopted by the invention has good insulating property and mechanical property, the interface compatibility with epoxy is improved through dopamine coating, and the interface stress between the graphene oxide and epoxy resin is reduced; meanwhile, through three-stage curing, the internal stress in the epoxy resin curing process is reduced as much as possible, so that the epoxy resin composite material with both insulating property and mechanical property is obtained.
4. The graphene oxide and the dopamine prepared by the method belong to green and environment-friendly products, and the pollution harm to the natural environment cannot be increased due to the use of the product.
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In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows the preparation process of nano-filled epoxy resin
FIG. 2 shows the electrical and mechanical properties of the nano-filled epoxy resin
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or equipment used in the examples are, unless otherwise specified, either conventionally commercially available or may be obtained by methods known in the art. Unless otherwise indicated, the testing or testing methods are conventional in the art.
In the following examples, the cellulose resin used was Istman nitrocellulose resin.
Example 1
The method comprises the following steps: preparation of graphene oxide
1. 200mL of concentrated H2SO4With concentrated H3PO4The mixed solution is poured into a flask, placed in an ice bath reaction tank, and concentrated with H2SO4Concentration 98%, concentrated H3PO4The concentration is 85%, and the mixing volume ratio of the two mixed solutions is 9: 1;
2. weighing 1.5g of natural crystalline flake graphite, adding the natural crystalline flake graphite into a reaction flask, and starting stirring by using a magnetic stirring device;
3. 3g of KMnO was slowly added with stirring4Keeping ice bath and stirring for reaction for 1 h;
4. putting the flask into a 50 ℃ water bath heating device, and continuously stirring for reaction for 12 hours;
5. placing the flask in ice bath again, stirring for 20min to ensure that the temperature of the solution is reduced;
6. suction H2O2The solution was slowly dropped into the reaction flask until the color of the solution turned to a golden yellow.
7. Slowly adding the obtained product into 3L of distilled water for dilution, then carrying out suction filtration, and washing the product with distilled water for 5 times;
8. and dissolving the obtained product in 200mL of distilled water, performing ultrasonic treatment for 12h, filtering, finally drying the product in a drying oven at 80 ℃ for 24h, and collecting the product to obtain the graphene oxide.
Step two: polydopamine self-polymerization coated graphene oxide
1. Weighing a certain amount of Tris (hydroxymethyl) aminomethane (Tris) to dissolve in 500mL of distilled water, and slowly dropwise adding a concentrated HCl solution until the pH value of the solution is 8.5 to obtain a Tris buffer solution with the pH value of 8.5;
2. weighing 1g of graphene oxide prepared in the first step, dissolving in a Tris buffer solution, and performing ultrasonic dispersion for 1 h;
3. weighing dopamine hydrochloride, dissolving the dopamine hydrochloride in the reaction solution, placing the solution in a water bath kettle at the temperature of 60 ℃, and stirring for reaction for 48 hours, wherein the final concentration of the dopamine hydrochloride is 0.6 mg/mL;
4. and (3) carrying out suction filtration on the solution after reaction, washing the solution for 5 times by using distilled water, and drying the obtained product for 12 hours by using a vacuum freezing device to obtain the poly-dopamine-coated graphene oxide.
Step three: preparation of poly-dopamine nano-layer coated graphene oxide filled epoxy resin composite material
1. Weighing 3g of the polydopamine coated graphene oxide obtained in the second step, dissolving in 200mL of ethanol, and performing ultrasonic dispersion for 1 h;
2. weighing 100g of bisphenol A epoxy resin, placing the bisphenol A epoxy resin into a beaker, pouring the ethanol mixed solution into the beaker, stirring the mixture by using a glass rod until the ethanol solution and the epoxy resin solution are completely mixed, and placing the mixed solution into a water bath kettle to be heated and stirred for 6 hours at the temperature of 60 ℃;
3. weighing 50g of methyl tetrahydrophthalic anhydride and 0.5g of 2-ethyl-4-methylimidazole, adding into the epoxy resin mixture, stirring at room temperature for 30min, and placing in a vacuum box to remove bubbles;
4. and injecting the epoxy resin mixed solution subjected to defoaming into a mold, placing the mold into a heating box for low-temperature precuring for 1-2h, heating to medium temperature for curing for 1-2h, finally curing at high temperature for 0.5-1 h, and demolding to obtain the poly-dopamine nano-layer coated graphene oxide filled epoxy resin.
Example 2
The method comprises the following steps: preparation of graphene oxide
1. 200mL of concentrated H2SO4With concentrated H3PO4The mixed solution is poured into a flask, placed in an ice bath reaction tank, and concentrated with H2SO4Concentration 98%, concentrated H3PO4The concentration is 85%, and the mixing volume ratio of the two mixed solutions is 8: 2;
2. weighing 1.5g of natural crystalline flake graphite, adding the natural crystalline flake graphite into a reaction flask, and starting stirring by using a magnetic stirring device;
3. 3g of KMnO was slowly added with stirring4Keeping ice bath and stirring for reaction for 1 h;
4. putting the flask into a 50 ℃ water bath heating device, and continuously stirring for reaction for 12 hours;
5. placing the flask in ice bath again, stirring for 20min to ensure that the temperature of the solution is reduced;
6. suction H2O2The solution was slowly dropped into the reaction flask until the color of the solution turned to a golden yellow.
7. Slowly adding the obtained product into 3L of distilled water for dilution, then carrying out suction filtration, and washing the product with distilled water for 5 times;
8. and dissolving the obtained product in 200mL of distilled water, performing ultrasonic treatment for 12h, filtering, finally drying the product in a drying oven at 80 ℃ for 24h, and collecting the product to obtain the graphene oxide.
Step two: polydopamine self-polymerization coated graphene oxide
1. Weighing a certain amount of Tris (hydroxymethyl) aminomethane (Tris) to dissolve in 500mL of distilled water, and slowly dropwise adding a concentrated HCl solution until the pH value of the solution is 8.5 to obtain a Tris buffer solution with the pH value of 8.5;
2. weighing 1g of graphene oxide prepared in the first step, dissolving in a Tris buffer solution, and performing ultrasonic dispersion for 1 h;
3. weighing dopamine hydrochloride, dissolving the dopamine hydrochloride in the reaction solution, placing the solution in a water bath kettle at the temperature of 60 ℃, and stirring for reaction for 48 hours, wherein the final concentration of the dopamine hydrochloride is 0.6 mg/mL;
4. and (3) carrying out suction filtration on the solution after reaction, washing the solution for 5 times by using distilled water, and drying the obtained product for 12 hours by using a vacuum freezing device to obtain the poly-dopamine-coated graphene oxide.
Step three: preparation of poly-dopamine nano-layer coated graphene oxide filled epoxy resin composite material
1. Weighing 3g of the polydopamine coated graphene oxide obtained in the second step, dissolving the polydopamine coated graphene oxide in 200mL of acetone, and performing ultrasonic dispersion for 1 h;
2. weighing 100g of bisphenol A epoxy resin, placing the bisphenol A epoxy resin into a beaker, pouring the acetone mixed solution into the beaker, stirring the acetone mixed solution by using a glass rod until the acetone solution and the epoxy resin solution are completely mixed, and placing the mixed solution into a water bath kettle to be heated and stirred for 6 hours at the temperature of 60 ℃;
3. weighing 50g of methyl hexahydrophthalic anhydride and 0.5g of 2-ethyl-4-methylimidazole, adding into the epoxy resin mixture, stirring at room temperature for 30min, and placing in a vacuum box to remove bubbles;
4. and injecting the epoxy resin mixed solution subjected to defoaming into a mold, placing the mold into a heating box for low-temperature precuring for 1-2h, heating to medium temperature for curing for 1-2h, finally curing at high temperature for 0.5-1 h, and demolding to obtain the poly-dopamine nano-layer coated graphene oxide filled epoxy resin.
Example 3
The method comprises the following steps: preparation of graphene oxide
1. 200mL of concentrated H2SO4With concentrated H3PO4The mixed solution is poured into a flask, placed in an ice bath reaction tank, and concentrated with H2SO4Concentration 98%, concentrated H3PO4The concentration is 85%, and the mixing volume of the mixed solution of the two is 7: 3;
2. weighing 1.5g of natural crystalline flake graphite, adding the natural crystalline flake graphite into a reaction flask, and starting stirring by using a magnetic stirring device;
3. 3g of KMnO was slowly added with stirring4Keeping ice bath and stirring for reaction for 1 h;
4. putting the flask into a 50 ℃ water bath heating device, and continuously stirring for reaction for 12 hours;
5. placing the flask in ice bath again, stirring for 20min to ensure that the temperature of the solution is reduced;
6. suction H2O2The solution was slowly dropped into the reaction flask until the color of the solution turned to a golden yellow.
7. Slowly adding the obtained product into 3L of distilled water for dilution, then carrying out suction filtration, and washing the product with distilled water for 5 times;
8. and dissolving the obtained product in 200mL of distilled water, performing ultrasonic treatment for 12h, filtering, finally drying the product in a drying oven at 80 ℃ for 24h, and collecting the product to obtain the graphene oxide.
Step two: polydopamine self-polymerization coated graphene oxide
1. Weighing a certain amount of Tris (hydroxymethyl) aminomethane (Tris) to dissolve in 500mL of distilled water, and slowly dropwise adding a concentrated HCl solution until the pH value of the solution is 8.5 to obtain a Tris buffer solution with the pH value of 8.5;
2. weighing 1g of graphene oxide prepared in the first step, dissolving in a Tris buffer solution, and performing ultrasonic dispersion for 1 h;
3. weighing dopamine hydrochloride, dissolving the dopamine hydrochloride in a reaction solution, placing the solution in a water bath kettle at the temperature of 60 ℃, and stirring for reaction for 48 hours, wherein the final concentration of the dopamine hydrochloride is 1.2 mg/mL;
4. and (3) carrying out suction filtration on the solution after reaction, washing the solution for 5 times by using distilled water, and drying the obtained product for 12 hours by using a vacuum freezing device to obtain the poly-dopamine-coated graphene oxide.
Step three: preparation of poly-dopamine nano-layer coated graphene oxide filled epoxy resin composite material
1. Weighing 3g of the polydopamine coated graphene oxide obtained in the second step, dissolving the polydopamine coated graphene oxide in 200mL of acetone, and performing ultrasonic dispersion for 1 h;
2. weighing 100g of aliphatic epoxy resin, placing the aliphatic epoxy resin in a beaker, pouring the acetone mixed solution into the beaker, stirring the acetone mixed solution with a glass rod until the acetone solution and the epoxy resin solution are completely mixed, and placing the mixed solution in a water bath kettle to be heated and stirred for 6 hours at the temperature of 60 ℃;
3. weighing 50g of methyl hexahydrophthalic anhydride and 0.5g of 2-ethyl-4-methylimidazole, adding into the epoxy resin mixture, stirring at room temperature for 30min, and placing in a vacuum box to remove bubbles;
4. and injecting the epoxy resin mixed solution subjected to defoaming into a mold, placing the mold into a heating box for low-temperature precuring for 1-2h, heating to medium temperature for curing for 1-2h, finally curing at high temperature for 0.5-1 h, and demolding to obtain the poly-dopamine nano-layer coated graphene oxide filled epoxy resin.
Examples of the experiments
The breakdown test and the tensile test are performed on the epoxy resin prepared in example 1, the test results are shown in fig. 2, a weibull distribution is adopted to fit the breakdown results, and a value of 63.2% probability distribution is taken as a sample breakdown field strength (that is, y in fig. 2a is taken as a value at 0), so that the breakdown strengths of the pure epoxy resin, the 0.1% wt GO filled epoxy resin, the 0.2% wt GO filled epoxy resin, and the 0.2% wt GO @ PDA filled epoxy resin are respectively as follows: 17.13kV/mm, 14.88kV/mm, 14.24kV/mm and 16.64kV/mm, and as can be seen from FIG. 2b, the tensile strength of each sample is: 52.21MPa, 57.43MPa, 60.42MPa and 64.81 MPa. According to the result, the tensile strength of the epoxy resin can be better improved by simply filling GO, but as the filling amount is increased, the breakdown strength of the epoxy resin can be obviously reduced due to the existence of a large number of polar groups and a small number of conjugated pi-pi structures in GO. The breakdown strength of the coated polydopamine is improved to a certain extent and is close to that of pure epoxy resin, and meanwhile, the tensile strength of the coated polydopamine is further improved due to the physical adsorption capacity of the dopamine and the good interface compatibility of the dopamine serving as an organic matter and the epoxy resin, so that the GO coated with the polydopamine can inhibit the reduction of the insulating property of the epoxy resin and can also obviously improve the tensile strength of the epoxy resin.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a polydopamine nano-layer coated graphene oxide filled epoxy resin composite material comprises the following steps: 1) preparing natural crystalline flake graphite into graphene oxide; 2) coating oxidized graphene by self-polymerization of polydopamine; 3) and coating the polydopamine nano-layer with graphene oxide filled epoxy resin.
2. The preparation method according to claim 1, wherein the specific steps of preparing the natural crystalline flake graphite into the graphene oxide are as follows: 1) adding concentrated H2SO4With concentrated H3PO4The mixed solution is subjected to ice bath; 2) weighing natural crystalline flake graphite, adding the mixed solution after ice bath, stirring, and adding KMnO while stirring4Fully reacting; 3) heating in water bath, continuously stirring for reaction, and repeating; stirring in ice bath; 4) addition of H2O2Until the reaction is complete; 5) diluting the obtained product in distilled water, performing suction filtration, and repeatedly washing; 6) and fully dissolving the product obtained in the last step into distilled water, and performing ultrasonic filtration to obtain the graphene oxide.
3. The preparation method according to claim 1, wherein the graphene oxide is coated by self-polymerization of polydopamine by the following specific steps: 1) weighing Tris buffer solution with the pH value of 8.5; 2) adding graphene oxide into a Tris buffer solution, and performing ultrasonic dispersion; 3) adding dopamine hydrochloride, dissolving in ultrasonic dispersion, and placing in a water bath for full reaction; 4) and carrying out suction filtration on the solution after reaction, repeatedly washing, and drying the obtained product to obtain the poly-dopamine-coated graphene oxide.
4. The preparation method according to claim 1, wherein the step of coating the poly-dopamine nano-layer with the graphene oxide filled epoxy resin comprises the following specific steps: 1) dissolving polydopamine-coated graphene oxide in a diluent, and performing ultrasonic dispersion; 2) adding epoxy resin into the dispersion liquid obtained in the last step, completely mixing, and heating in a water bath for full reaction; 3) adding a curing agent and an accelerant, reacting at room temperature, and putting in a vacuum box to remove bubbles; 4) and injecting the mixed solution into a mold, curing and demolding to obtain the poly-dopamine nano-layer coated graphene oxide filled epoxy resin.
5. The method of claim 2, wherein the concentrated H is2SO4Concentration of (2) is 98%, concentrated H3PO4 ofConcentrated H with a concentration of 85%2SO4With concentrated H3PO4The volume ratio of (1) to (7) to (3).
6. The preparation method according to claim 3, wherein the dopamine hydrochloride is dissolved in the ultrasonic dispersion liquid, and the final concentration of the dopamine hydrochloride is 0.6-1.2 mg/mL.
7. The method according to claim 4, wherein the diluent is ethanol or acetone.
8. The method according to claim 4, wherein the epoxy resin is a bisphenol A type or a cycloaliphatic epoxy resin.
9. The method according to claim 4, wherein the curing agent is methyl tetrahydrophthalic anhydride or methyl hexahydrophthalic anhydride.
10. The method of claim 4, wherein the promoter is 2-ethyl-4-methylimidazole.
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| CN115010995A (en) * | 2022-06-13 | 2022-09-06 | 广西博世科环保科技股份有限公司 | Modified overhaul slag based on dopamine, and preparation method and application thereof |
| CN115305042A (en) * | 2022-08-24 | 2022-11-08 | 杭州福斯特应用材料股份有限公司 | Black adhesive and aluminum plastic film |
| CN116023755A (en) * | 2023-02-24 | 2023-04-28 | 广东科悦新材料有限公司 | Permanent antistatic thermoplastic elastomer material and preparation method thereof |
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| CN114714708A (en) * | 2022-05-09 | 2022-07-08 | 江苏耀鸿电子有限公司 | High-frequency copper-clad plate with PPO resin base material and preparation method thereof |
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| CN115010995A (en) * | 2022-06-13 | 2022-09-06 | 广西博世科环保科技股份有限公司 | Modified overhaul slag based on dopamine, and preparation method and application thereof |
| CN115010995B (en) * | 2022-06-13 | 2023-07-04 | 广西博世科环保科技股份有限公司 | Dopamine-based modified overhaul slag and preparation method and application thereof |
| CN115305042A (en) * | 2022-08-24 | 2022-11-08 | 杭州福斯特应用材料股份有限公司 | Black adhesive and aluminum plastic film |
| CN115305042B (en) * | 2022-08-24 | 2024-04-09 | 杭州福斯特功能膜材料有限公司 | Black adhesive and aluminum plastic film |
| CN116023755A (en) * | 2023-02-24 | 2023-04-28 | 广东科悦新材料有限公司 | Permanent antistatic thermoplastic elastomer material and preparation method thereof |
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