CN115724425A - Preparation and use methods of functionalized graphene for modified cathode electrophoretic coating - Google Patents
Preparation and use methods of functionalized graphene for modified cathode electrophoretic coating Download PDFInfo
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Abstract
The invention discloses a preparation method and a use method of functionalized graphene for a modified cathode electrophoretic coating, and the functionalized graphene is modified by an efficient and safe method. Successfully dispersing the functionalized graphene into the cathode electrophoretic paint color paste to prepare the functionalized graphene modified cathode electrophoretic paint color paste. And mixing and curing the prepared functional graphene modified cathode electrophoretic paint color paste, the epoxy resin emulsion and deionized water according to a reasonable proportion for 24 hours, and then carrying out electrophoretic coating. Due to the functionalized treatment of the surface of the graphene, the graphene can be co-deposited on a base material with the cationic coating under the action of an electric field force, so that various performances of a coating film are improved. After the electrophoretic coating is cured, the hardness of a paint film reaches 5H, and the neutral salt spray time is more than 1500H.
Description
Technical Field
The invention relates to the field of cathode electrophoretic coatings, in particular to a preparation method and a use method of functionalized graphene for a modified cathode electrophoretic coating.
Background
The cathodic electrophoretic coating is widely applied to the anticorrosion protection of metal substrates, and automobile primers and parts are the largest market for the application of the cathodic electrophoretic coating. At present, more than 90 percent of automobile production in the world adopts cathode electrophoretic coating. With the continuous development of the automobile industry, huge market demands are brought to the cathode electrophoretic coating industry. However, the domestic middle-high cathode electrophoretic coating market is almost monopolized by foreign enterprises such as PPG, duPont, pasf, guanxi, and RiPont. The development of cathode electrophoretic coatings in China starts late, most of domestic enterprises are concentrated in low-end markets, so that the problems of monopoly of foreign resources and neck blockage are overcome, and the independent development of cathode electrophoretic coatings with excellent corrosion resistance and high strength is a problem which needs to be solved as soon as possible at present.
Due to the intrinsic excellent performance of the graphene, for example, the Young modulus is as high as 1.0TPa, the orderly stacking of the graphene can effectively prevent the corrosion of water, air and the like to a base material, the corrosion resistance of the coating is greatly improved, and the preparation of the cathode electrophoretic coating color paste by taking the graphene as one of the fillers is the key for solving the problem.
However, graphene has no charged group in the intrinsic structure, and is difficult to co-deposit with a coating film through an electrophoresis process to improve the performance of the coating film, so that the application of graphene in electrophoretic coating is restricted. And the graphene is extremely easy to agglomerate due to the huge specific surface area, and a large amount of solvent is often required to be added for dispersion, so that the environmental pollution and the resource waste are caused.
In order to solve the above problems, in patent CN 106832183B, reduced graphene oxide and polyurethane are covalently grafted to introduce graphene into resin, and the graphene and polyurethane are successfully co-deposited on a substrate through an electrophoresis process to obtain an electrophoretic coating film with good electrical conductivity. However, the preparation process of the reduced graphene oxide is dangerous; the surface graftable functional group is less, and the compatibility with the polymer resin is poor; the prepared coating film has poor corrosion resistance and is difficult to be practically applied.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method and a use method of functionalized graphene for a modified cathode electrophoretic coating. According to the invention, a microreactor is used for carrying out functionalization treatment on the graphene two-dimensional nanomaterial, and the prepared functionalized graphene and the cathode electrophoretic paint color paste are subjected to homogenization treatment by a homogenizer, so that the graphene is successfully and uniformly dispersed in the cathode electrophoretic paint color paste. In the subsequent electrophoretic deposition process, the functionalized graphene and the cathode electrophoretic coating are successfully co-deposited on the substrate through the electrophoretic process due to the surface distributed charges. According to the research, the cathode electrophoretic coating is subjected to nano modification by using the high strength and physical barrier effect of the graphene, so that the corrosion resistance and strength of the prepared coating film are further improved.
The technical purpose of the invention is realized by the following technical scheme.
A preparation method of functionalized graphene for a modified cathode electrophoretic coating comprises the following steps:
(1) Mixing the graphene oxide dispersion liquid with an amination reagent, pumping the mixture into a microchannel reactor for amination reaction to obtain aminated graphene;
(2) Mixing aminated graphene and organic acid, performing ultrasonic dispersion, washing for multiple times, filtering, and re-dispersing a filter cake in a weak acid solution with pH =5-6.5 to obtain a functionalized graphene dispersion liquid.
(3) And finally, homogenizing the functionalized graphene and the cathode electrophoretic paint color paste by a homogenizer, mixing the cathode electrophoretic paint emulsion, the functionalized graphene modified electrophoretic paint color paste and deionized water in proportion to obtain a working solution of the functionalized graphene modified cathode electrophoretic paint, and carrying out electrophoretic coating and filming by using the working solution, wherein after the working solution is baked and cured at high temperature, the thickness of a paint film is 18-22 mu m, the hardness reaches 5H, and the neutral salt spray time reaches 1500H.
The graphene oxide used in the invention is: hydroxylated graphene, carboxylated graphene and epoxidized graphene or a mixture of a plurality of hydroxylated graphene, carboxylated graphene and epoxidized graphene.
The amination reagent used in the present invention is an activating agent and an aminating agent.
The activating agent used in the invention is: n-propyl phosphoric anhydride, phosphonium hexafluorophosphate, nitrobenzene sulfonyl chloride, carbodiimide hydrochloride, tin tetrachloride, diphenyl phosphoryl chloride, concentrated sulfuric acid, boron trifluoride etherate and the like.
The aminating agent used in the invention is: one or more amine compounds such as dimethyl phenylenediamine, o-amino azotoluene, diaminodiphenyl ether, triamino triphenylamine, aminoacetonitrile and p-aminobenzonitrile.
The invention relates to a preparation method of functionalized graphene for a modified cathode electrophoretic coating, which comprises the following specific operation steps:
ultrasonically dispersing graphene oxide in a solvent, pumping the solvent and an activating agent into a mixer for premixing, pumping the solvent and the activating agent into a microchannel reactor for amination reaction after the premixing is finished, setting the working temperature of the microreactor to be-10-200 ℃, controlling the flow of an outlet of the microreactor by a quantitative pressure control valve, and setting the working pressure of a pipeline to be 0.2-2Mpa.
The organic acids used in the present invention are: formic acid, sulfamic acid, lactic acid, nitric acid and the like.
A use method of functionalized graphene for a modified cathode electrophoretic coating comprises the following steps:
uniformly premixing the functionalized graphene and cathode electrophoretic paint color paste according to the formula amount, wherein the stirring speed is 300-3000rmp, and the premixing time is 0.5-2h, so as to obtain the functionalized graphene cathode electrophoretic paint premixed slurry. Adding the premixed slurry of the functionalized graphene cathode electrophoretic coating into a homogenizer for homogenization treatment, wherein the homogenization pressure is 50-200bar, the homogenization flow is 20-500g/min, and the homogenization times are 1-5 times, so as to obtain the functionalized graphene modified cathode electrophoretic coating color paste.
Preparing the functional graphene modified cathode electrophoretic paint color paste, epoxy resin and deionized water into cathode electrophoretic paint liquid according to the formula amount, stirring and curing for 24-48 h, and performing electrophoretic coating. Under the condition of continuous stirring, controlling the temperature of a cathode electrophoretic coating working solution to be 30 +/-1 ℃, soaking a piece of antirust steel material into the cathode electrophoretic coating working solution, connecting a power supply anode to be used as an anode for electrophoretic coating, soaking a piece of cold-rolled plate subjected to phosphating treatment into the cathode electrophoretic coating working solution to be used as a cathode, connecting a power supply cathode, introducing direct current, performing electrophoresis for 1-5min under the electrophoresis voltage of 60-200V, after the electrophoresis is finished, washing floating paint on a coating film by using deionized water, drying water stain of the coating film by using cold air, and then putting the coating film into an oven to be dried for 20min at the temperature of 105 ℃. And (3) curing reaction, namely transferring the dried paint film to a 170 ℃ oven for baking and curing for 25min, taking out the paint film, and adjusting the paint film at the normal temperature of a drying oven for 24h to obtain the functionalized graphene modified epoxy resin cathode electrophoresis paint film.
The preparation and use method of the functional graphene modified cathode electrophoretic paint color paste according to claim 1, which is characterized by comprising the following steps: the thickness of a paint film is 18-22 mu m, the pencil hardness is 5H, and the time of resisting neutral salt spray reaches 1500H.
Drawings
FIG. 1 is a functional graphene modified cathode electrophoretic coating co-deposition diagram
Compared with other technologies, the invention has the following remarkable advantages
(1) The reaction is uniform, and no by-product is generated;
(2) The operation is simplified, and the safety is high;
(3) Successful co-deposition of graphene and cathodic electrocoat onto a substrate
Detailed Description
The present invention is further described with reference to the following specific examples, but the scope of the present invention is not limited to the examples, and any technical solutions falling within the spirit of the present invention should fall within the scope of the present invention. It should also be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention.
A preparation and use method of functionalized graphene for a modified cathode electrophoretic coating comprises the following steps:
(1) Preparing aminated graphene: and mixing the graphene oxide dispersion liquid and an amination reagent, pumping the mixture into a microchannel reactor for amination reaction to obtain the aminated graphene. The method specifically comprises the steps of ultrasonically dispersing graphene oxide in a solvent, pumping a graphene dispersion liquid and an activating agent into a mixer according to a formula ratio for pre-activation, pumping an activated graphene mixture and an amination agent into a microchannel reactor for amination after the pre-activation is completed, setting the working temperature of a microreactor to be-10-200 ℃, controlling the flow of an outlet of the microreactor by a quantitative pressure control valve, and setting the working pressure of a pipeline to be 0.2-2Mpa, thereby finally obtaining the aminated graphene. The graphene oxide is one or a mixture of more of hydroxylated graphene, carboxylated graphene and epoxidized graphene. The amination reagent is an activating agent and an amination agent, wherein the activating agent comprises one or more mixed compounds such as n-propyl phosphoric anhydride, phosphonium hexafluorophosphate, nitrobenzene sulfonyl chloride, carbodiimide hydrochloride, stannic chloride, diphenyl phosphoryl chloride, concentrated sulfuric acid, boron trifluoride diethyl etherate and the like; preferred are phosphonium hexafluorophosphates, tin tetrachloride, nitrobenzenesulfonyl chlorides, boron trifluoride etherate. The aminating agent comprises one or more mixed compounds such as dimethyl phenylenediamine, o-amino azotoluene, diaminodiphenyl ether, triamino triphenylamine, aminoacetonitrile, p-aminobenzonitrile and the like; preferred are dimethyl phenylenediamine, o-aminoazotoluene, diaminodiphenyl ether, p-aminobenzonitrile.
(2) Preparing a functionalized graphene dispersion liquid: mixing aminated graphene and organic acid, performing ultrasonic treatment, filtering, and washing for multiple times until the dispersion liquid is weakly acidic to obtain the functionalized graphene dispersion liquid. The organic acid is: formic acid, sulfamic acid, lactic acid, nitric acid and the like.
(3) Preparing graphene modified cathode electrophoretic coating color paste: and homogenizing the functionalized graphene and the cathode electrophoretic paint color paste by a homogenizer to obtain the graphene modified cathode electrophoretic paint color paste. The method comprises the following specific steps: and uniformly premixing the functionalized graphene and the cathode electrophoretic paint color paste according to the formula amount at the stirring speed of 300-3000rmp for 0.5-2h to obtain the functionalized graphene cathode electrophoretic paint premixed slurry. Pouring the premixed slurry of the functionalized graphene cathode electrophoretic coating after premixing into a homogenizer for homogenization treatment, wherein the homogenization pressure is 50-200bar, the homogenization flow is 20-500g/min, and the homogenization times are 1-5 times, thus finally obtaining the functionalized graphene modified cathode electrophoretic coating color paste.
(4) Preparation of functionalized graphene modified cathode electrophoretic coating
Mixing the cathode electrophoretic coating emulsion, the functionalized graphene modified electrophoretic color paste and deionized water in proportion to obtain a functionalized graphene modified cathode electrophoretic coating working solution, carrying out electrophoretic coating and filming by using the working solution, and baking and curing at high temperature to obtain a functionalized graphene modified epoxy resin cathode electrophoretic paint film. The method specifically comprises the following steps: preparing the functional graphene modified cathode electrophoretic paint color paste, epoxy resin and deionized water into cathode electrophoretic paint liquid according to the formula amount, stirring and curing for 24-48 h, and performing electrophoretic coating. Under the condition of continuous stirring, controlling the temperature of a cathode electrophoretic coating working solution to be 30 +/-1 ℃, soaking a piece of antirust steel material into the cathode electrophoretic coating working solution, connecting a power supply anode to be used as an anode for electrophoretic coating, soaking a piece of cold-rolled plate subjected to phosphating treatment into the cathode electrophoretic coating working solution to be used as a cathode, connecting a power supply cathode, introducing direct current, performing electrophoresis for 1-5min under the electrophoresis voltage of 60-200V, after the electrophoresis is finished, washing floating paint on a coating film by using deionized water, drying water stain of the coating film by using cold air, and then putting the coating film into an oven to be dried for 20min at the temperature of 105 ℃. And (3) curing, namely transferring the dried paint film to an oven at 170 ℃, baking and curing for 25min, taking out the paint film, and adjusting the paint film at normal temperature for 24h in a drying oven to obtain the functionalized graphene modified epoxy resin cathode electrophoresis paint film. The method is characterized in that: the thickness of a paint film is 18-20 mu m, the hardness reaches 5H, and the neutral salt spray time reaches 1500H.
Example 1
Taking 100g of carboxylated graphene, ultrasonically dispersing the carboxylated graphene in dimethylacetamide, pumping the carboxylated graphene and phosphonium hexafluorophosphate into a mixer, wherein the optimized feeding mass ratio of the carboxylated graphene to the phosphonium hexafluorophosphate is 1.2, pumping the mixed solution and diaminodiphenyl ether into a micro-channel reactor according to the flow volume ratio of 1. And washing and filtering the product for multiple times by using ethanol and deionized water to obtain the aminated graphene. Adding the aminated graphene into formic acid for ultrasonic dispersion, washing the aminated graphene to be neutral by using deionized water for multiple times, filtering, and re-dispersing a filter cake into formic acid solution with the pH =5-6.5 to obtain the functionalized graphene dispersion liquid.
And uniformly premixing the functionalized graphene and the cathode electrophoretic paint color paste, stirring at the speed of 3000rmp, and premixing for 1h to obtain the functionalized graphene cathode electrophoretic paint premixed paste. And adding the premixed slurry of the functionalized graphene cathode electrophoretic coating into a homogenizer for homogenization treatment, wherein the homogenization pressure is 100bar, the homogenization flow is 400g/min, and the homogenization times are 3 times, so as to obtain the functionalized graphene modified cathode electrophoretic coating color paste.
And finally, mixing the cathode electrophoretic coating emulsion, the functionalized graphene modified electrophoretic color paste and deionized water according to a ratio of 5.
Example 2
Dispersing 100g of hydroxylated graphene in dimethylformamide, pumping the mixture and boron trifluoride diethyl etherate into a mixer, wherein the optimized charging mass ratio of the hydroxylated graphene to tin tetrachloride is 1.5, pumping the mixed solution and the p-aminobenzonitrile into a microchannel reactor according to a flow volume ratio of 1:2.1, wherein the temperature of a pipeline is 80 ℃, and the working pressure of the pipeline is 1.1Mpa for carrying out an amination reaction. And washing the product with diethyl ether and deionized water for multiple times, and filtering to obtain the aminated graphene. And adding sulfamic acid into the aminated graphene for ultrasonic dispersion, washing the aminated graphene for multiple times by using deionized water until the aminated graphene is neutral, filtering the aminated graphene, and re-dispersing a filter cake into a sulfamic acid solution with the pH =5-6.5 to obtain the functionalized graphene dispersion liquid.
And uniformly premixing the functionalized graphene and the cathode electrophoretic paint color paste at a stirring speed of 3000rmp for 1h to obtain the functionalized graphene cathode electrophoretic paint premixed slurry. And adding the premixed slurry of the functionalized graphene cathode electrophoretic coating into a homogenizer for homogenization treatment, wherein the homogenization pressure is 70bar, the homogenization flow is 150g/min, and the homogenization times are 2 times, so as to obtain the functionalized graphene modified cathode electrophoretic coating color paste.
And finally, mixing the cathode electrophoretic coating emulsion, the functionalized graphene modified electrophoretic color paste and deionized water according to a ratio of 5.2 to 8.3 to obtain a functionalized graphene modified cathode electrophoretic coating working solution, carrying out electrophoretic coating and film coating by using the working solution, solidifying, drying and standing for 24 hours, and then carrying out film coating performance detection.
Example 3
100g of hydroxylated graphene is dispersed in dimethylformamide and pumped into a mixer together with boron trifluoride diethyl etherate, the optimized feeding mass ratio of the hydroxylated graphene to tin tetrachloride is 1.5, the mixed solution and aminoacetonitrile are pumped into a microchannel reactor according to the flow volume ratio of 1 to 2.5, the temperature of a pipeline is 90 ℃, and the working pressure of the pipeline is 1.05Mpa for carrying out amination reaction. And washing the product with diethyl ether and deionized water for multiple times, and filtering to obtain the aminated graphene. Adding sulfamic acid into aminated graphene for ultrasonic dispersion, washing the aminated graphene to be neutral by using deionized water for multiple times, filtering, and re-dispersing a filter cake into a sulfamic acid solution with the pH =5-6.5 to obtain a functionalized graphene dispersion solution.
And uniformly premixing the functionalized graphene and the cathode electrophoretic paint color paste at a stirring speed of 3000rmp for 1h to obtain the functionalized graphene cathode electrophoretic paint premixed slurry. And adding the premixed slurry of the functionalized graphene cathode electrophoretic coating into a homogenizer for homogenization treatment, wherein the homogenization pressure is 70bar, the homogenization flow is 150g/min, and the homogenization times are 2 times, so as to obtain the functionalized graphene modified cathode electrophoretic coating color paste.
And finally, mixing the cathode electrophoretic coating emulsion, the functionalized graphene modified electrophoretic color paste and deionized water according to a ratio of 5.2 to 8.3 to obtain a functionalized graphene modified cathode electrophoretic coating working solution, carrying out electrophoretic coating and film coating by using the working solution, solidifying, drying and standing for 24 hours, and then carrying out film coating performance detection.
Example 4
Dispersing 100g of epoxidized graphene in ethylene glycol monobutyl ether, pumping the epoxidized graphene and boron trifluoride diethyl etherate into a mixer, wherein the optimized feeding mass ratio of the epoxidized graphene to the boron trifluoride diethyl etherate is 1.2, and mixing the mixed solution with dimethyl phenylenediamine according to the flow volume ratio of 1:1.2 pumping into a micro-channel reactor, carrying out amination reaction at the pipeline temperature of 100 ℃ and the pipeline working pressure of 1.15 Mpa. And washing the product with diethyl ether and deionized water for multiple times, and filtering to obtain the aminated graphene. Adding the aminated graphene into lactic acid for ultrasonic dispersion, washing the aminated graphene to be neutral by using deionized water for multiple times, filtering, and re-dispersing a filter cake into a lactic acid solution with the pH =5-6.5 to obtain a functionalized graphene dispersion liquid.
And uniformly premixing the functionalized graphene and the cathode electrophoretic paint color paste, stirring at the speed of 3000rmp, and premixing for 1h to obtain the functionalized graphene cathode electrophoretic paint premixed paste. And adding the premixed slurry of the functionalized graphene cathode electrophoretic coating into a homogenizer for homogenization treatment, wherein the homogenization pressure is 80bar, the homogenization flow is 300g/min, and the homogenization times are 2 times, so as to obtain the functionalized graphene modified cathode electrophoretic coating color paste.
And finally, mixing the cathode electrophoretic coating emulsion, the functionalized graphene modified electrophoretic color paste and deionized water according to a ratio of 5.5.
Example 5
Taking 100g of a mixture of hydroxylated graphene and epoxidized graphene, mixing and dispersing the mixture in dimethylformamide according to a ratio of 5: 1.2 pumping into a micro-channel reactor, carrying out amination reaction at the pipeline temperature of 120 ℃ and the pipeline working pressure of 1.15 Mpa. Washing the product with diethyl ether and deionized water for multiple times, and filtering to obtain the aminated graphene. Adding lactic acid into aminated graphene for ultrasonic dispersion, washing the aminated graphene for multiple times by using deionized water until the aminated graphene is neutral, filtering the mixture, and re-dispersing a filter cake into a lactic acid solution with the pH =5-6.5 to obtain a functionalized graphene dispersion liquid.
And uniformly premixing the functionalized graphene and the cathode electrophoretic paint color paste at a stirring speed of 3000rmp for 1h to obtain the functionalized graphene cathode electrophoretic paint premixed slurry. And adding the premixed slurry of the functionalized graphene cathode electrophoretic coating into a homogenizer for homogenization treatment, wherein the homogenization pressure is 80bar, the homogenization flow is 300g/min, and the homogenization times are 2 times, so as to obtain the functionalized graphene modified cathode electrophoretic coating color paste.
And finally, mixing the cathode electrophoretic coating emulsion, the functionalized graphene modified electrophoretic color paste and deionized water according to a ratio of 5.5.
Example 6
Taking 100g of a mixture of carboxylated graphene, hydroxylated graphene and epoxidized graphene, and mixing the mixture according to the weight ratio of 2:5, mixing and dispersing the mixture in dimethylformamide, pumping the mixture and boron trifluoride diethyl etherate into a mixer, optimally adding the mixed graphene and boron trifluoride diethyl etherate in a mass ratio of 1:1.2 pumping into a micro-channel reactor, carrying out amination reaction at the pipeline temperature of 120 ℃ and the pipeline working pressure of 1.15 Mpa. And washing the product with diethyl ether and deionized water for multiple times, and filtering to obtain the aminated graphene. Adding the aminated graphene into lactic acid for ultrasonic dispersion, washing the aminated graphene to be neutral by using deionized water for multiple times, filtering, and re-dispersing a filter cake into a lactic acid solution with the pH =5-6.5 to obtain a functionalized graphene dispersion liquid.
And uniformly premixing the functionalized graphene and the cathode electrophoretic paint color paste, stirring at the speed of 3000rmp, and premixing for 1h to obtain the functionalized graphene cathode electrophoretic paint premixed paste. And adding the premixed slurry of the functionalized graphene cathode electrophoretic coating into a homogenizer for homogenization treatment, wherein the homogenization pressure is 80bar, the homogenization flow is 300g/min, and the homogenization times are 2 times, so as to obtain the functionalized graphene modified cathode electrophoretic coating color paste.
And finally, mixing the cathode electrophoretic coating emulsion, the functionalized graphene modified electrophoretic color paste and deionized water according to a ratio of 5.5.
Comparative example 1
The preparation of the cathode electrophoretic coating which is not modified by adding the graphene
| Name of raw materials | Parts by weight |
| 1. Color paste | 500 |
| 2. Cathodic electrophoretic emulsion | 2750 |
| 3. Deionized water | 4500 |
* Minfu Metal coating technology Co., ltd, zhejiang
Sequentially adding 1, 2 and 3 according to the formula, stirring and curing for 24h, and then carrying out electrophoretic coating.
After the obtained cathode electrophoretic coating film is placed in a drying oven at normal temperature for 24 hours, the coating film is tested according to the GB/T13452.2-2008, GB/T5210-2006, GB/T31588.1-2015 and GB/T6739-2006 standards, and the test performance evaluation is compared as shown in the following table.
| Film thickness | Adhesion force | Resistance to salt fog | Hardness of | |
| Example 1 | 20 | 100/100 | 1400 | 4H |
| Example 2 | 20 | 100/100 | 1500 | 5H |
| Example 3 | 20 | 100/100 | 1200 | 3H |
| Example 4 | 20 | 100/100 | 1300 | 4H |
| Example 5 | 20 | 100/100 | 1100 | 3H |
| Example 6 | 20 | 100/100 | 1000 | 3H |
| Comparative example 1 | 20 | 100/100 | 800 | 2H |
From the performance evaluation and evaluation results of examples 1 to 6 and comparative example 1, the epoxy resin cathode electrophoretic coating is subjected to nano modification by the functionalized graphene, and the corrosion resistance and the mechanical strength of the coating are obviously improved by the excellent mechanical property of the graphene and the physical barrier property of the graphene to the coating.
Claims (5)
1. A preparation method and a use method of functionalized graphene for a modified cathode electrophoretic coating are characterized by comprising the following steps:
mixing the graphene oxide dispersion liquid with an amination reagent, pumping into a microreactor, and carrying out amination reaction to obtain aminated graphene;
mixing aminated graphene and organic acid, performing ultrasonic treatment, filtering, and washing for multiple times until the dispersion liquid is weakly acidic to obtain a functionalized graphene dispersion liquid;
and finally, homogenizing the functionalized graphene dispersion liquid and the cathode electrophoretic coating color paste by a homogenizer, mixing the cathode electrophoretic coating emulsion, the functionalized graphene modified electrophoretic color paste and deionized water in proportion to obtain a functionalized graphene modified cathode electrophoretic coating working solution, carrying out electrophoretic coating and filming by using the working solution, and baking and curing at high temperature to obtain a film with the thickness of 18-22 mu m, the hardness of 5H and the neutral salt spray time of 1500H.
2. The preparation method of the functionalized graphene for the modified cathode electrophoretic coating according to claim 1, comprising:
the graphene oxide is as follows: one or a mixture of more of hydroxylated graphene, carboxylated graphene and epoxidized graphene;
the amination reagent comprises an activating agent and an aminating agent;
the activating agent is: one or more mixtures of n-propyl phosphoric anhydride, phosphonium hexafluorophosphate, p-nitrobenzenesulfonyl chloride, tin tetrachloride, diphenylphosphoryl chloride, concentrated sulfuric acid, boron trifluoride diethyl etherate complex, and the like;
the aminating agent is as follows: one or more amine compounds such as dimethyl phenylenediamine, o-aminoazotoluene, diaminodiphenyl ether, triaminotriphenylamine, aminoacetonitrile, and p-aminobenzonitrile;
the organic acid is: formic acid, sulfamic acid, lactic acid, nitric acid and the like.
3. The use method of the functionalized graphene for the modified cathode electrophoretic coating according to claim 1, wherein the functionalized graphene and the cathode electrophoretic coating color paste are uniformly premixed according to the formula amount, the stirring speed is 300-3000rmp, and the premixing time is 0.5-2h to obtain the functionalized graphene cathode electrophoretic coating premixed slurry; adding the premixed slurry of the functionalized graphene cathode electrophoretic coating into a homogenizer for homogenization treatment, wherein the homogenization pressure is 50-200bar, the homogenization flow is 20-500g/min, and the homogenization times are 1-5 times, so as to obtain the functionalized graphene modified cathode electrophoretic coating color paste.
4. The use method of the functionalized graphene for the modified cathode electrophoretic paint according to claim 1, wherein the cathode electrophoretic paint is prepared by taking the color paste of the functionalized graphene modified cathode electrophoretic paint, epoxy resin and deionized water according to the formula amount, stirring and curing for 24-48 h, and then carrying out electrophoretic coating; under the condition of continuous stirring, controlling the temperature of a cathode electrophoretic coating working solution to be 30 +/-1 ℃, soaking a piece of antirust steel material into the cathode electrophoretic coating working solution, connecting a power supply anode to be used as an anode for electrophoretic coating, soaking a piece of cold-rolled plate subjected to phosphating treatment into the cathode electrophoretic coating working solution to be used as a cathode, connecting a power supply cathode, introducing direct current, carrying out electrophoresis for 1-5min under the electrophoresis voltage of 60-200V, washing floating paint on a coating film by using deionized water after electrophoresis is finished, drying water stains of the coating film by using cold air, and then putting the coating film into an oven to be dried for 20min at 105 ℃; and (3) curing reaction, namely transferring the dried paint film to a 170 ℃ oven for baking and curing for 25min, taking out the paint film, and adjusting the paint film at the normal temperature of a drying oven for 24h to obtain the functionalized graphene modified epoxy resin cathode electrophoresis paint film.
5. The preparation and use method of the functionalized graphene modified cathode electrophoretic coating color paste according to claim 1, is characterized by comprising the following steps: the thickness of a paint film is 18-22 mu m, the pencil hardness reaches 5H, and the neutral salt spray resistance time reaches 1500H.
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