CN112457735A - Graphene-containing automobile paint and preparation method thereof - Google Patents
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses an automobile paint containing graphene. The invention discloses a preparation method of the graphene-containing automobile paint, which comprises the following steps: continuously stirring propylene glycol butyl ether and tert-carbonic acid glycidyl ester, and heating to 130-140 ℃ under the protection of nitrogen in the stirring process to obtain premix a; adding nano graphene oxide into an ethanol aqueous solution, performing ultrasonic dispersion, performing spray drying, adding nano cellulose, and grinding to obtain pretreated nano graphene oxide; uniformly mixing methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, m-methylstyrene, p-methylstyrene and the pretreated nano graphene oxide, then dropwise adding the mixture into the premix a, adjusting the temperature to 140 ℃ and 150 ℃, and then sequentially adding the initiator, acrylic acid and dodecyl mercaptan and uniformly stirring to obtain a premix b; and cooling the premix b to 80-88 ℃, adding a neutralizer, stirring at a high speed, cooling to 50-60 ℃, and adding water for emulsification to obtain the graphene-containing automobile paint.
Description
Technical Field
The invention relates to the technical field of automotive coatings, in particular to an automobile paint containing graphene and a preparation method thereof.
Background
At present, the huge automobile production and sale market must drive the rapid development of the automobile coating, the huge automobile holding capacity is provided, a wide development space is provided for the automobile coating, the automobile coating dosage is increased rapidly, the automobile coating is mainly solvent-based, and the solvent-based coating occupies a large share in the automobile coating market due to the good construction effect and excellent film coating performance of the solvent-based coating. However, the solvent-based coating has high VOC, the volatile organic solvent seriously affects the health of people, and the water-based automobile coating does not accord with the national environmental protection policy, and the water-based automobile coating is increasingly concerned by the market. However, the existing water-based automobile coating generally has the technical problems of poor waterproof performance and easy delamination after long-time placement.
In recent years, with the continuous development of nanotechnology, the preparation technology of nanomaterials is mature, and inorganic nanoparticles can generate special properties such as small-size effect, surface effect and quantum effect due to the characteristics of small particle size, large specific surface area and the like, so that the nanocomposite has more excellent performance than conventional materials. The nano technology is utilized to modify the automobile coating, the physical and mechanical properties of the nano material are fully utilized, and besides better conventional properties can be given to the automobile coating, how to enhance the waterproof property and the placing stability of the automobile water-based coating becomes a technical problem to be solved urgently at present.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides graphene-containing automobile paint and a preparation method thereof.
A preparation method of graphene-containing automobile paint comprises the following steps:
s1, continuously stirring propylene glycol butyl ether and tert-carbonic acid glycidyl ester, and heating to 130-140 ℃ under the protection of nitrogen in the stirring process to obtain premix a;
s2, adding the nano graphene oxide into an ethanol aqueous solution, performing ultrasonic dispersion for 1-2h, performing ultrasonic power of 400-500W, performing spray drying, adding nano cellulose for grinding, wherein the grinding time is 10-12h, the grinding speed is 1200-1400r/min, and the grinding pressure is 1.2-1.6MPa, so as to obtain the pretreated nano graphene oxide;
s3, uniformly mixing methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, m-methylstyrene, p-methylstyrene and the pretreated nano graphene oxide, then dropwise adding the mixture into the premix a, adjusting the temperature to 140 ℃ and 150 ℃, and then sequentially adding the initiator, acrylic acid and dodecyl mercaptan and uniformly stirring to obtain a premix b;
s4, cooling the premix b to 80-88 ℃, adding a neutralizer, stirring at a high speed for 10-15min, cooling to 50-60 ℃, adding water, and emulsifying to obtain the graphene-containing automobile paint.
Preferably, in S1, the mass ratio of the propylene glycol butyl ether to the glycidyl versatate is 2-8: 1-5.
Preferably, in S2, the mass fraction of the ethanol aqueous solution is 40-60%, and the mass ratio of the nano graphene oxide to the ethanol aqueous solution to the nano cellulose is 2-8: 50-100: 1-2.
Preferably, in S2, the length-diameter ratio of the nano-cellulose is 500-1000, and the diameter of the nano-cellulose is 10-20 nm.
Preferably, in S3, the mass ratio of methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, m-methylstyrene, p-methylstyrene, pretreated nano graphene oxide, premix a, initiator, acrylic acid, and dodecyl mercaptan is 20-40: 15-30: 10-20: 5-12: 4-10: 4-10: 5-15: 1-2: 20-30: 1-2.
Preferably, in S3, the initiator includes tert-butyl peroxide and di-tert-amyl peroxide, and the mass ratio of tert-butyl peroxide to di-tert-amyl peroxide is 10: 2-6.
Preferably, in S3, the specific operation of adding the initiator is as follows: adding tert-butyl peroxide during stirring, keeping the temperature for 20-40min, adding acrylic acid and dodecyl mercaptan, stirring uniformly, keeping the temperature for 10-20min, adding di-tert-amyl peroxide, stirring uniformly, and keeping the temperature for 2-6min to obtain premix b.
Preferably, in S4, the mass ratio of the premix b to the neutralizing agent is 50-70: 4-8.
Preferably, the neutralizing agent is at least one of triethylamine, dimethylethanolamine, N-ethylmorpholine, 2-amino-2-methyl-1-propanol.
The graphene-containing automobile paint is prepared by adopting the preparation method of the graphene-containing automobile paint.
The technical effects of the invention are as follows:
according to the requirement of the current automobile water-based paint on waterproof performance, the nano graphene oxide is introduced, has high specific surface energy and mechanical performance and high surface activity, can be combined with methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, m-methylstyrene and p-methylstyrene to form a high-efficiency waterproof layer in the paint, and has excellent waterproof performance;
however, the nano graphene oxide is easy to agglomerate, so that the nano graphene oxide is pretreated, ultrasonic dispersion is matched with spray drying in an ethanol solution, the lamellar structure of the nano graphene oxide can be pre-opened, so that the primary intercalation of nano cellulose is facilitated, the structural intercalation of the nano graphene oxide by the nano cellulose can be promoted by controlling the diameter of the nano cellulose and matching with a grinding process, the nano graphene oxide can be stably dispersed in a multi-layer form, the intercalated nano cellulose can be stably combined among the structures of the nano graphene oxide, the pretreated nano graphene oxide has good dispersion performance, is not easy to agglomerate, is convenient to combine with methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, m-methyl styrene and p-methyl styrene, and realizes no layering phenomenon during long-term storage of the waterproof coating, so that the waterproof coating has good storage performance under the condition of meeting the national standard requirements; the pretreated nano graphene oxide can effectively reduce acting force and intermolecular winding among macromolecular polymers, effectively reduce system viscosity, further improve the dispersion effect of the nano graphene oxide in a system, ensure more uniform dispersion, promote the coating to have higher wettability, and be applied to the field of automobiles.
The VOC content of the water-based automobile coating is lower than 15%, the water-based automobile coating completely meets the strictest environmental protection requirement, the water-based automobile coating is extremely friendly to the environment, the use and dependence on organic solvents are greatly reduced, the energy is effectively saved, and the water-based automobile coating is compact in paint film, good in waterproof performance and excellent in comprehensive performance.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of graphene-containing automobile paint comprises the following steps:
s1, adding 2kg of propylene glycol butyl ether and 5kg of tert-carbonic acid glycidyl ester into a stirrer, heating to 130 ℃ under the protection of nitrogen in the stirring process, and stirring at the speed of 120r/min to obtain premix a;
s2, adding 2kg of nano graphene oxide into 100kg of 40% ethanol aqueous solution, performing ultrasonic dispersion for 2h, wherein the ultrasonic power is 400W, after spray drying, adding 2kg of nano cellulose with the diameter of 10-20nm and the length-diameter ratio of 513, and feeding the nano graphene oxide into a grinding machine to grind for 12h, wherein the grinding speed is 1200r/min, and the grinding pressure is 1.6MPa, so as to obtain pretreated nano graphene oxide;
s3, adding 20kg of methyl methacrylate, 30kg of ethyl acrylate, 10kg of hydroxyethyl acrylate, 12kg of m-methylstyrene, 4kg of p-methylstyrene and 10kg of pretreated nano graphene oxide into a stirrer, uniformly mixing, then dropwise adding into 5kg of premix a, adjusting the temperature to 150 ℃, adding 0.625kg of tert-butyl peroxide in the stirring process, preserving heat for 40min, then adding 20kg of acrylic acid and 2kg of dodecyl mercaptan, uniformly stirring, continuously preserving heat for 10min, then adding 0.375kg of di-tert-amyl peroxide, uniformly stirring, and preserving heat for 2min to obtain premix b;
s4, cooling 70kg of premix b to 80 ℃, adding 8kg of triethylamine for neutralization, stirring at a high speed for 10min at the stirring speed of 400r/min, cooling to 50 ℃, adding water for emulsification, stirring at the speed of 1200r/min for 10min, and pausing for 2S every 30S of stirring to obtain the graphene-containing automotive paint.
Example 2
A preparation method of graphene-containing automobile paint comprises the following steps:
s1, adding 8kg of propylene glycol butyl ether and 1kg of tert-carbonic acid glycidyl ester into a stirrer, heating to 140 ℃ under the protection of nitrogen in the stirring process, and stirring at the speed of 50r/min to obtain premix a;
s2, adding 8kg of nano graphene oxide into 50kg of ethanol aqueous solution with the mass fraction of 60%, ultrasonically dispersing for 1h, wherein the ultrasonic power is 500W, after spray drying, adding 1kg of nano cellulose with the diameter of 10-20nm and the length-diameter ratio of 988, and sending the nano graphene oxide into a grinding machine for grinding for 10h, wherein the grinding speed is 1400r/min, and the grinding pressure is 1.2MPa, so as to obtain the pretreated nano graphene oxide;
s3, adding 40kg of methyl methacrylate, 15kg of ethyl acrylate, 20kg of hydroxyethyl acrylate, 5kg of m-methylstyrene, 10kg of p-methylstyrene and 4kg of pretreated nano graphene oxide into a stirrer, uniformly mixing, then dropwise adding into 15kg of premix a, adjusting the temperature to 140 ℃, adding 1.65kg of tert-butyl peroxide in the stirring process, preserving heat for 20min, then adding 30kg of acrylic acid and 1kg of dodecyl mercaptan, uniformly stirring, continuously preserving heat for 20min, then adding 0.34kg of di-tert-amyl peroxide, uniformly stirring, and preserving heat for 6min to obtain premix b;
s4, cooling 50kg of premix b to 88 ℃, adding 4kg of dimethylethanolamine for neutralization, stirring at a high speed of 200r/min for 15min, cooling to 60 ℃, adding water for emulsification, stirring at a speed of 1000r/min for 20min, and pausing for 4S every 20S of stirring to obtain the graphene-containing automotive paint.
Example 3
A preparation method of graphene-containing automobile paint comprises the following steps:
s1, adding 4kg of propylene glycol butyl ether and 4kg of glycidyl versatate into a stirrer, heating to 133 ℃ under the protection of nitrogen in the stirring process, and stirring at the speed of 100r/min to obtain premix a;
s2, adding 4kg of nano graphene oxide into 80kg of 45% ethanol aqueous solution, performing ultrasonic dispersion for 1.7h, performing spray drying, adding 1.7kg of nano cellulose with the diameter of 10-20nm and the length-diameter ratio of 626, and feeding the nano cellulose into a grinding machine for grinding for 11.5h, wherein the grinding speed is 1250r/min, and the grinding pressure is 1.5MPa, so as to obtain pretreated nano graphene oxide;
s3, adding 25kg of methyl methacrylate, 26kg of ethyl acrylate, 12kg of hydroxyethyl acrylate, 11kg of m-methylstyrene, 6kg of p-methylstyrene and 8kg of pretreated nano graphene oxide into a stirrer, uniformly mixing, then dropwise adding into 8kg of premix a, adjusting the temperature to 148 ℃, adding 0.74kg of tert-butyl peroxide in the stirring process, keeping the temperature for 35min, then adding 22kg of acrylic acid and 1.7kg of dodecyl mercaptan, uniformly stirring, continuously keeping the temperature for 13min, then adding 0.37kg of di-tert-amyl peroxide, uniformly stirring, and keeping the temperature for 3min to obtain premix b;
s4, cooling 65kg of premix b to 82 ℃, adding 7kg of N-ethylmorpholine for neutralization, stirring at a high speed of 340r/min for 12min, cooling to 52 ℃, adding water for emulsification, stirring at a speed of 1150r/min for 13min, wherein the stirring is suspended for 2.5S every 28S, and thus the graphene-containing automobile paint is obtained.
Example 4
A preparation method of graphene-containing automobile paint comprises the following steps:
s1, adding 6kg of propylene glycol butyl ether and 2kg of glycidyl versatate into a stirrer, heating to 137 ℃ under the protection of nitrogen in the stirring process, and stirring at the speed of 60r/min to obtain premix a;
s2, adding 6kg of nano graphene oxide into 60kg of 55% ethanol aqueous solution by mass, ultrasonically dispersing for 1.3h with the ultrasonic power of 470W, after spray drying, adding 1.3kg of nano cellulose with the diameter of 10-20nm and the length-diameter ratio of 753, and sending the nano graphene oxide into a grinder to grind for 10.5h at the grinding speed of 1350r/min and the grinding pressure of 1.3MPa to obtain pretreated nano graphene oxide;
s3, adding 35kg of methyl methacrylate, 20kg of ethyl acrylate, 18kg of hydroxyethyl acrylate, 7kg of m-methylstyrene, 8kg of p-methylstyrene and 6kg of pretreated nano graphene oxide into a stirrer, uniformly mixing, then dropwise adding into 12kg of premix a, adjusting the temperature to 142 ℃, adding 1.23kg of tert-butyl peroxide in the stirring process, keeping the temperature for 25min, then adding 28kg of acrylic acid and 1.3kg of dodecyl mercaptan, uniformly stirring, continuously keeping the temperature for 17min, then adding 0.35kg of di-tert-amyl peroxide, uniformly stirring, and keeping the temperature for 5min to obtain premix b;
s4, cooling 55kg of premix b to 86 ℃, adding 5kg of 2-amino-2-methyl-1-propanol for neutralization, stirring at a high speed of 260r/min for 14min, cooling to 58 ℃, adding water for emulsification, stirring at a speed of 1050r/min for 17min, wherein the stirring is suspended for 3.5S every 22S, and obtaining the graphene-containing automobile paint.
Example 5
A preparation method of graphene-containing automobile paint comprises the following steps:
s1, adding 5kg of propylene glycol butyl ether and 3kg of glycidyl versatate into a stirrer, heating to 135 ℃ under the protection of nitrogen in the stirring process, and stirring at the speed of 80r/min to obtain premix a;
s2, adding 5kg of nano graphene oxide into 70kg of ethanol water solution with the mass fraction of 50%, ultrasonically dispersing for 1.5h, wherein the ultrasonic power is 450W, after spray drying, adding 1.5kg of nano cellulose with the diameter of 10-20nm and the length-diameter ratio of 703, sending the nano cellulose into a grinding machine, and grinding for 11h at the grinding speed of 1300r/min and the grinding pressure of 1.4MPa to obtain pretreated nano graphene oxide;
s3, adding 30kg of methyl methacrylate, 23kg of ethyl acrylate, 15kg of hydroxyethyl acrylate, 9kg of m-methylstyrene, 7kg of p-methylstyrene and 7kg of pretreated nano graphene oxide into a stirrer, uniformly mixing, then dropwise adding into 10kg of premix a, adjusting the temperature to 145 ℃, adding 0.98kg of tert-butyl peroxide in the stirring process, keeping the temperature for 30min, then adding 25kg of acrylic acid and 1.5kg of dodecyl mercaptan, uniformly stirring, continuously keeping the temperature for 15min, then adding 0.36kg of di-tert-amyl peroxide, uniformly stirring, and keeping the temperature for 4min to obtain premix b;
s4, cooling 60kg of premix b to 84 ℃, adding 6kg of 2-amino-2-methyl-1-propanol for neutralization, stirring at a high speed of 300r/min for 13min, cooling to 55 ℃, adding water for emulsification, stirring at a speed of 1100r/min for 15min, wherein stirring is suspended for 3S every 25S, and thus the graphene-containing automobile paint is obtained.
Comparative example 1
A commercially available water-based acrylic paint for vehicles was used.
Comparative example 2
A preparation method of graphene-containing automobile paint comprises the following steps:
s1, adding 5kg of propylene glycol butyl ether and 3kg of glycidyl versatate into a stirrer, heating to 135 ℃ under the protection of nitrogen in the stirring process, and stirring at the speed of 80r/min to obtain premix a;
s2, adding 30kg of methyl methacrylate, 23kg of ethyl acrylate, 15kg of hydroxyethyl acrylate, 9kg of m-methylstyrene, 7kg of p-methylstyrene and 7kg of nano graphene oxide into a stirrer, uniformly mixing, then dropwise adding into 10kg of premix a, adjusting the temperature to 145 ℃, adding 0.98kg of tert-butyl peroxide in the stirring process, preserving heat for 30min, then adding 25kg of acrylic acid and 1.5kg of dodecyl mercaptan, uniformly stirring, continuously preserving heat for 15min, then adding 0.36kg of di-tert-amyl peroxide, uniformly stirring, and preserving heat for 4min to obtain premix b;
s3, cooling 60kg of premix b to 84 ℃, adding 6kg of 2-amino-2-methyl-1-propanol for neutralization, stirring at a high speed of 300r/min for 13min, cooling to 55 ℃, adding water for emulsification, stirring at a speed of 1100r/min for 15min, wherein stirring is suspended for 3S every 25S, and thus the graphene-containing automobile paint is obtained.
The graphene-containing automotive paints obtained in example 5 and comparative example 2 and the waterborne acrylic coating for vehicles used in comparative example 1 were subjected to a standing test at an ambient temperature of 25 ± 2 ℃, an ambient humidity of 50 ± 5% RH, and a test time of 90d, and it was found that: the automotive water-based acrylic paint used in comparative example 1 was delaminated in 73.3 days, the graphene-containing automotive paint obtained in comparative example 2 was delaminated in 84.7 days, and the graphene-containing automotive paint obtained in example 5 was not delaminated during the test.
Then, the automobile paint containing graphene obtained in example 5 and comparative example 2 and the automobile water-based acrylic paint used in comparative example 1 are sprayed on the surface of high-strength interstitial free steel (IF-HSS) HC220YD + Z, paint films with the thickness of 5mm are obtained after drying, water and corrosion resistance tests are carried out on each group of paint films, namely, each group of paint films are respectively soaked in water for 3 months, and each group of paint films are respectively soaked in 5 mass percent hydrochloric acid, 10 mass percent sodium hydroxide solution and 3 mass percent sodium chloride solution for 168 hours, and the results are as follows:
| example 5 | Comparative example 2 | Comparative example 1 | |
| Water (W) | Without change | Delamination and cracking | Delamination and cracking |
| Hydrochloric acid with mass fraction of 5% | Without change | Delamination of | Delamination and discoloration |
| 10 percent of sodium hydroxide solution | Without change | Delamination and discoloration | Delamination of |
| Sodium chloride solution with mass fraction of 3% | Without change | Delamination of | Delamination and cracking |
Then, the mechanical property test is carried out on the paint films of the groups, and the results are as follows:
| example 5 | Comparative example 2 | Comparative example 1 | |
| Adhesion (cross-hatch method), grade | 1 | 1 | 2 |
| Impact strength, kg cm | 63 | 51 | 38 |
| Tensile strength, Mpa | 37 | 29 | 21 |
From the above table, it can be seen that: the graphene-containing automobile paint has good storage performance, realizes no layering phenomenon of the waterproof paint after long-term storage, has excellent mechanical performance and good waterproof performance, and is environment-friendly.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The preparation method of the graphene-containing automobile paint is characterized by comprising the following steps:
s1, continuously stirring propylene glycol butyl ether and tert-carbonic acid glycidyl ester, and heating to 130-140 ℃ under the protection of nitrogen in the stirring process to obtain premix a;
s2, adding the nano graphene oxide into an ethanol aqueous solution, performing ultrasonic dispersion for 1-2h, performing ultrasonic power of 400-500W, performing spray drying, adding nano cellulose for grinding, wherein the grinding time is 10-12h, the grinding speed is 1200-1400r/min, and the grinding pressure is 1.2-1.6MPa, so as to obtain the pretreated nano graphene oxide;
s3, uniformly mixing methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, m-methylstyrene, p-methylstyrene and the pretreated nano graphene oxide, then dropwise adding the mixture into the premix a, adjusting the temperature to 140 ℃ and 150 ℃, and then sequentially adding the initiator, acrylic acid and dodecyl mercaptan and uniformly stirring to obtain a premix b;
s4, cooling the premix b to 80-88 ℃, adding a neutralizer, stirring at a high speed for 10-15min, cooling to 50-60 ℃, adding water, and emulsifying to obtain the graphene-containing automobile paint.
2. The method for preparing the graphene-containing automotive paint according to claim 1, wherein in S1, the mass ratio of the butyl ether of propylene glycol to the glycidyl versatate is 2-8: 1-5.
3. The method for preparing the graphene-containing automotive paint according to claim 1, wherein in S2, the mass fraction of the ethanol aqueous solution is 40-60%, and the mass ratio of the nano graphene oxide to the ethanol aqueous solution to the nano cellulose is 2-8: 50-100: 1-2.
4. The method for preparing the graphene-containing automotive paint as claimed in claim 1, wherein in S2, the length-diameter ratio of the nanocellulose is 500-1000, and the diameter of the nanocellulose is 10-20 nm.
5. The method for preparing graphene-containing automotive paint according to claim 1, wherein in S3, the mass ratio of methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, m-methylstyrene, p-methylstyrene, pre-treated nano graphene oxide, premix a, initiator, acrylic acid and dodecyl mercaptan is 20-40: 15-30: 10-20: 5-12: 4-10: 4-10: 5-15: 1-2: 20-30: 1-2.
6. The method for preparing graphene-containing automotive paint according to claim 1, wherein in S3, the initiator comprises tert-butyl peroxide and di-tert-amyl peroxide, and the mass ratio of tert-butyl peroxide to di-tert-amyl peroxide is 10: 2-6.
7. The method for preparing the graphene-containing automotive paint according to claim 6, wherein the initiator is added in S3 by the following steps: adding tert-butyl peroxide during stirring, keeping the temperature for 20-40min, adding acrylic acid and dodecyl mercaptan, stirring uniformly, keeping the temperature for 10-20min, adding di-tert-amyl peroxide, stirring uniformly, and keeping the temperature for 2-6min to obtain premix b.
8. The method for preparing graphene-containing automotive paint according to claim 1, wherein in S4, the mass ratio of premix b to neutralizing agent is 50-70: 4-8.
9. The method for preparing an automotive paint containing graphene according to claim 1, wherein the neutralizing agent is at least one of triethylamine, dimethylethanolamine, N-ethylmorpholine, and 2-amino-2-methyl-1-propanol.
10. An automobile paint containing graphene, which is characterized by being prepared by the preparation method of the automobile paint containing graphene according to any one of claims 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977643A (en) * | 2017-03-24 | 2017-07-25 | 江阴恒兴涂料有限公司 | A kind of high salt fog resistance water soluble acrylic resin and preparation method thereof |
| CN107501467A (en) * | 2017-10-12 | 2017-12-22 | 清远市浩宇化工科技有限公司 | The preparation of a kind of stannic oxide/graphene nano modified acroleic acid ester aqueous dispersion and its applied to aqueous automobile paint |
| CN111019039A (en) * | 2019-12-24 | 2020-04-17 | 安徽优科新材料科技有限公司 | Acrylic acid aqueous dispersion and processing technology thereof |
| CN111574917A (en) * | 2020-06-09 | 2020-08-25 | 扬州工业职业技术学院 | Preparation method of composite material for polyurethane water-based paint |
-
2020
- 2020-10-30 CN CN202011184792.4A patent/CN112457735A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977643A (en) * | 2017-03-24 | 2017-07-25 | 江阴恒兴涂料有限公司 | A kind of high salt fog resistance water soluble acrylic resin and preparation method thereof |
| CN107501467A (en) * | 2017-10-12 | 2017-12-22 | 清远市浩宇化工科技有限公司 | The preparation of a kind of stannic oxide/graphene nano modified acroleic acid ester aqueous dispersion and its applied to aqueous automobile paint |
| CN111019039A (en) * | 2019-12-24 | 2020-04-17 | 安徽优科新材料科技有限公司 | Acrylic acid aqueous dispersion and processing technology thereof |
| CN111574917A (en) * | 2020-06-09 | 2020-08-25 | 扬州工业职业技术学院 | Preparation method of composite material for polyurethane water-based paint |
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Application publication date: 20210309 |