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CN114015342A - Antistatic scratch-resistant automobile paint and preparation method thereof - Google Patents

Antistatic scratch-resistant automobile paint and preparation method thereof Download PDF

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Publication number
CN114015342A
CN114015342A CN202111478853.2A CN202111478853A CN114015342A CN 114015342 A CN114015342 A CN 114015342A CN 202111478853 A CN202111478853 A CN 202111478853A CN 114015342 A CN114015342 A CN 114015342A
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mass
stirring
hydroxyl
rpm
self
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黄超财
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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/833—Chemically modified polymers by nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses an antistatic scratch-resistant automobile paint and a preparation method thereof, and relates to the technical field of automobile paints. The invention firstly utilizes the cyano piperazine, hydroxyl phenylacetaldehyde and bromochlorochalcone modified polyurethane to enable the car paint to self-repair scratches under ultraviolet light and improve the heat resistance of the car paint; and then, the self-made filler is treated by the ultrasonic waves, and finally, the self-made filler is stirred and mixed with the modified polyurethane and the auxiliary agent to form a conductive network, so that the antistatic property of the vehicle paint is improved. The antistatic scratch-resistant automobile paint prepared by the invention has the effects of antistatic property, scratch resistance and high temperature resistance.

Description

Antistatic scratch-resistant automobile paint and preparation method thereof
Technical Field
The invention relates to the technical field of automobile coatings, in particular to an antistatic scratch-resistant automobile paint and a preparation method thereof.
Background
The automobile paint is sprayed on an automobile, and not only can play a role in protection, but also can play a role in decoration. The outer layer of modern vehicle paint is also called a transparent paint layer, is only 0.05mm thick, has beautiful luster, and can form a protective layer on the surface of a vehicle body, so that the vehicle paint layer is not easy to corrode and scrape, and the service life of the vehicle body can be prolonged. Since automobiles are exposed to wind and rain all the year round, extremely high requirements are put on the performance of automobile paint films as automobile paint protective films, and the automobile paint protective films not only need to have good mechanical properties, good fullness and high gloss, but also put higher requirements on heat resistance and scratch resistance. In the prior art, nano powder is often added, and car paint is obtained by using a mechanical physical dispersion method, but the nano powder cannot be uniformly dispersed in a resin matrix by the method, and is easy to agglomerate, so that the scratch resistance is not strong; in addition, after the automobile paint is scraped, the automobile paint is usually filled or replaced by a nursing agent, which often increases the burden of an automobile owner.
In addition, cold and dry in the north in winter, car owners often can be hit by static electricity accumulated on the car when opening the car door and the car, especially when filling in a gas station, accident can be caused, and moreover, the static electricity often adsorbs a large amount of dust to influence the car beautifulness, so herein we have invented an antistatic self-repairing scratch car paint to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide an antistatic scratch-resistant automobile paint and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the antistatic scratch-resistant automobile paint is characterized by mainly comprising, by weight, 60-80 parts of modified polyurethane, 10-20 parts of self-made filler, 1-4 parts of wetting agent, 0.1-0.5 part of defoaming agent, 3-6 parts of thickening agent and 40-50 parts of deionized water.
Further, the modified polyurethane is prepared from polyurethane, cyano piperazine, hydroxyl phenylacetaldehyde and bromochlorochalcone.
Furthermore, the self-made filler is prepared by depositing silver on the carbon nano tube by utilizing radio frequency glow discharge, ultrasonic waves and electrostatic field to assist electron beams.
Further, the wetting agent is one or a mixture of a plurality of polysorbate, polyoxyethylene octylphenol ether, sulfonated oil or alkyl naphthalene sulfonic acid sodium salt.
Further, the defoaming agent is one or a mixture of tributyl phosphate, polydimethylsiloxane, glycerol polyether or polyoxyethylene ether.
Further, the thickening agent is one or more of distearate, polyurethane, stearyl alcohol or cetyl alcohol.
Further, the preparation method of the antistatic scratch-resistant automobile paint is characterized by mainly comprising the following preparation steps:
(1) dissolving hydroxyl propiophenonal in absolute ethyl alcohol which is 5-6 times of the mass of the hydroxyl propiophenonal, heating to 80-85 ℃, dropwise adding a potassium hydroxide/ethanol solution which is 3-4 times of the mass of the hydroxyl propiophenonal at a speed of 2-4 mL/min, wherein the mass ratio of potassium hydroxide to absolute ethyl alcohol in the potassium hydroxide/ethanol solution is 1:4.70, adding bromochlorochalcone which is 2-3 times of the mass of the hydroxyl propiophenonal, reacting for 3-5 hours, carrying out rotary evaporation at 200-300 rpm and 80 ℃ for 1-2 hours, adding a sodium hydroxide solution which is 10.5-11 times of the mass of the hydroxyl propiophenonal and has a mass fraction of 20%, carrying out suction filtration, and washing for 5-7 times by using the absolute ethyl alcohol to obtain a bromophenylacetone compound;
(2) mixing cyano piperazine, a bromoacetone compound and acetonitrile according to a mass ratio of 1: 0.6-1.5: 33.5-34, stirring and dissolving, adding potassium carbonate with the mass 1.5-2 times that of the cyanopiperazine, heating to 85-90 ℃, reacting for 5-7 h, filtering, carrying out rotary evaporation at 300-400 rpm and 82 ℃ for 2-3 h, adding absolute ethyl alcohol with the mass 7.5-8 times of that of the cyanopiperazine, placing in an ice-water bath at the temperature of 0-5 ℃, adding sodium borohydride with the mass of 0.2-0.3 times that of the cyanopiperazine at the speed of 0.12-0.2 g/min, reacting for 0.5-1 h at 100-200 rpm, distilling at 0.06-0.1 MPa and 55 ℃ for 70-90 min, adding ethyl acetate with the mass of 9-10 times that of the cyanopiperazine, stirring and dissolving, washing with distilled water for 3-5 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 4-6 h, filtering, and concentrating at 200-300 rpm and 105 ℃ for 40-50 min to obtain a hydroxyl compound;
(3) adding a hydroxyl compound, triethylamine and dichloromethane into a reaction bottle according to the mass ratio of 1: 1-1.5: 10.5-11, stirring at 50-100 rpm at the temperature of 0 ℃, adding methanesulfonyl chloride mixed liquid with the mass being 3.5-4 times that of the hydroxyl compound at the speed of 1-2 mL/min, wherein the mass ratio of methanesulfonyl chloride to dichloromethane in the methanesulfonyl chloride mixed liquid is 1:2.09, reacting for 60-70 min, heating to 40 ℃, reacting for 150-165 min, adding saturated sodium thiosulfate with the mass being 5-5.5 times that of the hydroxyl compound, separating liquid, and taking a water layer; adding dichloromethane with 2.5-3 times of the mass of the hydroxyl compound into a water layer, extracting for 3-5 times, sequentially washing for 3-5 times by using deionized water and saturated salt solution, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 6-7 hours, and concentrating for 2-3 hours at 60 ℃ under 0.05-0.1 MPa to obtain a sulfonic acid compound;
(4) adding a sulfonic acid compound, ethanol and sodium hydrosulfide into a reaction bottle according to the mass ratio of 1: 2.4-3: 0.38-0.44, stirring and reacting at the temperature of 80 ℃ and the rpm of 100-200 for 2-3 h, cooling to room temperature, distilling at the temperature of 200-300 rpm and the temperature of 75 ℃ for 50-65 min, adding sodium iodide accounting for 0.002-0.003 times of the mass of the sulfonic acid compound and ethyl acetate accounting for 3.4-4.1 times of the mass of the sulfonic acid compound, adding 30% hydrogen peroxide accounting for 0.15-0.2 times of the mass of the sulfonic acid compound while stirring at the speed of 50-100 rpm, and reacting at the temperature of 30 ℃, stirring for 30-45 min at the same speed, adding saturated sodium thiosulfate with the mass 32-32.5 times of that of the sulfonic acid compound, stirring uniformly, adding ethyl acetate with the mass 17.2-17.7 times of that of the sulfonic acid compound, extracting for 2-4 times, washing for 3-5 times with saturated salt solution, adding anhydrous sodium sulfate until no agglomeration appears, drying for 3-5 h, and carrying out rotary evaporation at 200-300 rpm and 65 ℃ for 55-70 min to obtain a disulfide;
(5) mixing disulfide, absolute ethyl alcohol and absolute nickel dichloride according to the mass ratio of 1: 9.6-10.2: 0.5-1, adding sodium borohydride with the mass of 1.4 to 2 times of that of disulfide into the mixture at the speed of 0.9 to 1.3g/min, stirring the mixture for 3 to 4 hours at the temperature of between 40 and 50 ℃ and at the rpm of between 50 and 100, cooling to room temperature, adding hydrochloric acid with the mass fraction of 60% and the mass of 9.6-10.2 times of that of the disulfide, stirring at the same speed for 65-75 min, distilling at 55 ℃ under 0.1-0.2 MPa for 130-145 min, adding 28% ammonia water until the pH of the solution is 7-8, adding diethyl ether with the mass 3-4 times of that of disulfide, extracting for 3-4 times, washing for 4-6 times with saturated salt solution, filtering, concentrating at 80 ℃ at 200-300 rpm for 70-80 min, adding polyurethane with the mass of 1.6-2.2 times of that of disulfide at 40 ℃, and stirring at 200-300 rpm for 20-24 hours to obtain modified polyurethane;
(6) placing the carbon nano tube in a ball milling tank for ball milling for 20-30 min, wherein the ball material ratio is 5:1, placing the carbon nano tube in a glass slide, focusing laser on the carbon nano tube, and irradiating for 10-25 s to obtain a pretreated carbon nano tube;
(7) placing the pretreated carbon nano tube on a glass slide of a substrate of an electron beam evaporation machine, placing an electrostatic plate 10-15 cm away from the glass slide, and vacuumizing to 5 multiplied by 10-4～7×10-4Pa, the evaporation time is 15-20 min, and the filler is obtained;
(8) placing the self-made filler into an ultrasonic crusher, treating the self-made filler for 10-15 min with the power of the ultrasonic crusher being 500-600W and the frequency being 40-50 kHz to obtain the self-made filler for ultrasonic treatment;
(9) mixing the self-made filler subjected to ultrasonic treatment and the modified polyurethane according to the mass ratio of 1: 4-6, stirring at 1000-1500 rpm for 30-40 min, adding a wetting agent, a defoaming agent, a thickening agent and deionized water according to the mass ratio of 1: 0.1-0.2: 2-4: 12.5-40, and stirring at the same speed for 40-50 min to obtain the antistatic scratch-resistant automobile paint.
Further, in the step (6), the laser wavelength is 620-635 nm, and the power is 10-20 mW.
Further, the target material of the electron beam evaporation machine in the step (7) is a silver target, the temperature of the substrate frame is 300-350 ℃, and the beam current is 150-190 mA; the output voltage of the electrostatic plate is 2000-2100A, and the current is 0.2-0.6 mA.
Further, placing a radio frequency coil in the electron beam evaporation machine in the step (7) at a distance of 40-50 cm from the target material, wherein the power is 90-120W; an ultrasonic generator is arranged 20-30 cm away from the radio frequency coil, the frequency of ultrasonic waves is 40-60 kHz, and the power is 300-400W.
Compared with the prior art, the invention has the following beneficial effects:
the automobile paint is prepared through the steps of polyurethane modification, self-made filler preparation and the like in sequence, so that the effects of static resistance, scratch resistance and heat resistance are realized.
Firstly, modified polyurethane is prepared from polyurethane, cyano piperazine, hydroxyl phenylacetaldehyde and bromochlorochalcone; after the hydroxyl of hydroxyl phenylacetaldehyde and the chloride ion of bromochlorochalcone react, the imino of the cyanopiperazine and the bromide ion of the bromochlorochalcone react to form a multi-component compound, and the multi-component compound, the hydroxyl of the hydroxyl phenylacetaldehyde and the bromide ion of the bromochlorochalcone are in a straight-chain structure, so that the hard segment of the modified polyurethane is concentrated, and the heat resistance and the hardness of the vehicle paint are improved; reducing carbonyl of a multi-component compound into hydroxyl, sulfonylating the hydroxyl to generate a sulfydryl compound, and condensing the sulfydryl compound and the sulfydryl compound to form a photosensitive group disulfide bond, so that the car paint can self-repair scratches under ultraviolet light; the conjugation of hydroxyl benzaldehyde and disulfide bonds reduces the bond energy of the disulfide bonds, cracking easily occurs, the photoresponse degree is improved, the self-repairing efficiency is improved, and the scratch-resistant effect is enhanced; and finally, reducing the cyano group of the cyanopiperazine into amino group, reacting with a polyurethane active group to generate a polyurethane paint containing a plurality of rigid benzene rings, and further improving the heat resistance and hardness of the vehicle paint, wherein the molecular cohesive energy is large.
Secondly, the self-made filler is prepared from metal silver and carbon nano tubes; firstly, the carbon nano tubes are pre-treated by laser burning, the gaps of the carbon nano tubes are enlarged, and the electron scattering at the contact part of the silver and the carbon nano tubes is increased, so that the silver is favorably deposited on the surfaces of the carbon nano tubes; then, preparing silver/carbon nanotubes by using radio frequency glow discharge, ultrasonic waves and electrostatic field to assist electron beam deposition; forming silver vapor through an electron beam, and ionizing the silver vapor to generate plasma by utilizing radio frequency glow discharge; due to the cavitation effect of the ultrasonic wave, the plasma is hollow, and the inner wall of the cavity is charged; under the action of an electrostatic field, leading the plasma to be vertically deposited at the gaps of the carbon nanotubes and grow outwards in a tree shape, and improving the conductivity of the carbon nanotubes so that the car paint has a better antistatic effect; the electrostatic field accelerates the electron motion of the plasma, accelerates the deposition speed, and also accelerates the collision with the carbon nano tube, so that the silver is deeply inserted into the carbon nano tube to form better embedded connection, and the long-acting antistatic performance of the vehicle paint is improved; finally, the silver/carbon nano tube is treated by ultrasonic again, so that the surface hydroxyl is changed into free radicals, and the free radicals and the aryl of the modified polyurethane are subjected to addition reaction to form a cross-linked network structure, form a conductive path and improve the antistatic property of the vehicle paint.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to illustrate the method of the present invention more clearly, the following examples are given, and the method for testing the indexes of the anti-static scratch-resistant automobile manufactured in the following examples is as follows:
antistatic property: the same mass of the examples and comparative examples was sprayed on a steel plate, and an antistatic effect test was performed to measure the surface resistivity using a megohmmeter.
Scratch resistance: spraying the embodiment and the comparative example with the same quality on a steel plate, performing scratch resistance test, scratching a scratch with the length of 1cm by using a surgical blade, irradiating for 10min under an ultraviolet lamp, measuring the length of the scratch, and calculating the repair efficiency; repair efficiency (scratch length before repair-scratch length after repair)/scratch length before repair.
High temperature resistance: and (3) spraying the same mass of the embodiment and the comparative example on a steel plate, carrying out a high temperature resistance test, placing the steel plate in a 700 ℃ oven, carrying out heat preservation for 15min, and checking the surface condition of the vehicle paint.
Example 1
The antistatic scratch-resistant automobile paint mainly comprises the following components in parts by weight: 60 parts of modified polyurethane, 10 parts of self-made filler, 1 part of polysorbate, 0.1 part of tributyl phosphate, 3 parts of distearate and 40 parts of deionized water.
The preparation method of the antistatic scratch-resistant automobile paint mainly comprises the following preparation steps:
(1) dissolving hydroxyl propiophenonal in absolute ethyl alcohol which is 5 times of the mass of the hydroxyl propiophenonal, heating to 80 ℃, dropwise adding a potassium hydroxide/ethanol solution which is 3 times of the mass of the hydroxyl propiophenonal at a speed of 2mL/min, wherein the mass ratio of potassium hydroxide to absolute ethyl alcohol in the potassium hydroxide/ethanol solution is 1:4.70, adding bromochlorochalcone which is 2 times of the mass of the hydroxyl propiophenonal, reacting for 3 hours, carrying out rotary evaporation at 200rpm and 80 ℃ for 2 hours, adding a sodium hydroxide solution which is 10.5 times of the mass of the hydroxyl phenylacetylaldehyde and has a mass fraction of 20%, carrying out suction filtration, and washing for 5 times by using absolute ethyl alcohol to obtain a bromoacetonide;
(2) mixing cyanopiperazine, bromoacetone compound and acetonitrile according to the mass ratio of 1:0.6:33.5, stirring and dissolving, adding potassium carbonate with the mass of 1.5 times of that of the cyanopiperazine, heating to 85 ℃, reacting for 5 hours, filtering, carrying out rotary evaporation at 300rpm and 82 ℃ for 3 hours, adding absolute ethyl alcohol with the mass of 7.5 times of that of the cyanopiperazine, placing in an ice-water bath at 5 ℃, adding sodium borohydride with the mass of 0.2 time of that of the cyanopiperazine at the speed of 0.12g/min, reacting for 1 hour at 100rpm, distilling for 90 minutes at 0.1MPa and 55 ℃, adding ethyl acetate with the mass of 9 times of the cyanopiperazine, stirring and dissolving, washing for 3 times with distilled water, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 4 hours, filtering, and concentrating for 50 minutes at 200rpm and 105 ℃ to obtain a hydroxyl compound;
(3) adding a hydroxyl compound, triethylamine and dichloromethane into a reaction bottle according to the mass ratio of 1:1:10.5, stirring at 50rpm at the temperature of 0 ℃, adding methanesulfonyl chloride mixed liquid with the mass being 3.5 times that of the hydroxyl compound at the speed of 1mL/min, wherein the mass ratio of methanesulfonyl chloride to dichloromethane in the methanesulfonyl chloride mixed liquid is 1:2.09, reacting for 60min, heating to 40 ℃, reacting for 150min, adding saturated sodium thiosulfate with the mass being 5 times that of the hydroxyl compound, separating liquid, and taking a water layer; adding dichloromethane with 2.5 times of hydroxyl compound mass into water layer, extracting for 3 times, sequentially washing with deionized water and saturated saline solution for 3 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 6h, and concentrating at 60 deg.C under 0.05MPa for 2h to obtain sulfonic acid compound;
(4) adding a sulfonic acid compound, ethanol and sodium hydrosulfide into a reaction bottle according to the mass ratio of 1:2.4:0.38, stirring and reacting at 80 ℃ and 100rpm for 3h, cooling to room temperature, distilling at 200rpm and 75 ℃ for 65min, adding sodium iodide and ethyl acetate, the mass fraction of which is 0.002 times that of the sulfonic acid compound and is 3.4 times that of the sulfonic acid compound, stirring at 50rpm while adding 30% hydrogen peroxide, the mass fraction of which is 0.15 times that of the sulfonic acid compound, stirring at 30 ℃ and the same speed for 45min, adding saturated sodium thiosulfate, the mass fraction of which is 32 times that of the sulfonic acid compound, stirring uniformly, adding ethyl acetate, the mass of which is 17.2 times that of the sulfonic acid compound, extracting for 2 times, washing for 3 times with saturated saline water, adding anhydrous sodium sulfate until no agglomeration appears, drying for 3h, and carrying out rotary evaporation at 200rpm and 65 ℃ for 70min to obtain a disulfide;
(5) mixing disulfide, absolute ethyl alcohol and anhydrous nickel dichloride according to the mass ratio of 1:9.6:0.5, adding sodium borohydride with the mass of 1.4 times that of the disulfide at the speed of 0.9g/min, stirring at 40 ℃ and 50rpm for 4h, cooling to room temperature, adding hydrochloric acid with the mass fraction of 60% and the mass fraction of 9.6 times that of the disulfide, stirring at the same speed for 75min, distilling at 0.1MPa and 55 ℃ for 130min, adding ammonia water with the mass fraction of 28% until the pH of the solution is 7, adding diethyl ether with the mass fraction of 3 times that of the disulfide, extracting for 3 times, washing for 4 times with saturated saline solution, filtering, concentrating at 200rpm and 80 ℃ for 80min, adding polyurethane with the mass fraction of 1.6 times that of the disulfide at 40 ℃, and stirring at 200rpm for 24h to obtain modified polyurethane;
(6) placing the carbon nano tube in a ball milling tank for ball milling for 20min, wherein the ball material ratio is 5:1, placing the carbon nano tube in a glass slide, focusing laser on the carbon nano tube, and irradiating for 10s to obtain a pretreated carbon nano tube;
(7) placing the pretreated carbon nanotube on a glass slide of a substrate of an electron beam evaporation machine, placing an electrostatic plate 10cm away from the glass slide, and vacuumizing to 7 x 10-4Pa, evaporation time of 15min and self-made filler;
(8) placing the self-made filler in an ultrasonic crusher, wherein the power of the ultrasonic crusher is 500W, the frequency is 40kHz, and treating for 10min to obtain the self-made filler subjected to ultrasonic treatment;
(9) mixing the self-made filler subjected to ultrasonic treatment and the modified polyurethane according to the mass ratio of 1:6, stirring for 40min at 1000rpm, adding polysorbate, tributyl phosphate, distearate and deionized water according to the mass ratio of 1:0.1:3:40, and stirring for 50min at the same speed to obtain the antistatic scratch-resistant automobile paint.
Further, the laser wavelength in the step (6) is 620nm, and the power is 10 mW.
Further, the target material of the electron beam evaporation machine in the step (7) is a silver target, the temperature of the substrate holder is 300 ℃, and the beam current is 150 mA; the output voltage of the electrostatic plate is 2000A, and the current is 0.2 mA.
Further, a radio frequency coil is arranged in the electron beam evaporation machine in the step (7) at a distance of 40cm from the target material, and the power is 90W; an ultrasonic generator was placed 20cm from the radio frequency coil, the ultrasonic frequency was 40kHz, and the power was 300W.
Example 2
The antistatic scratch-resistant automobile paint mainly comprises the following components in parts by weight: 80 parts of modified polyurethane, 20 parts of self-made filler, 4 parts of polysorbate, 0.5 part of tributyl phosphate, 6 parts of distearate and 50 parts of deionized water.
The preparation method of the antistatic scratch-resistant automobile paint mainly comprises the following preparation steps:
(1) dissolving hydroxyl propiophenonal in absolute ethyl alcohol with the mass 6 times of that of the hydroxyl propiophenonal, heating to 85 ℃, dropwise adding a potassium hydroxide/ethanol solution with the mass 4 times of that of the hydroxyl propiophenonal at a speed of 4mL/min, wherein the mass ratio of potassium hydroxide to absolute ethyl alcohol in the potassium hydroxide/ethanol solution is 1:4.70, adding bromochlorochalcone with the mass 3 times of that of the hydroxyl phenylacetaldehyde, reacting for 5 hours, carrying out rotary evaporation at 300rpm and 80 ℃ for 1 hour, adding a sodium hydroxide solution with the mass fraction of 20% 11 times of that of the hydroxyl phenylacetaldehyde, carrying out suction filtration, and washing for 7 times by using absolute ethyl alcohol to obtain a bromoacetone compound;
(2) mixing cyanopiperazine, bromoacetone compound and acetonitrile according to a mass ratio of 1:1.5:34, stirring and dissolving, adding potassium carbonate with 2 times of the mass of the cyanopiperazine, heating to 90 ℃, reacting for 7h, filtering, carrying out rotary evaporation at 400rpm and 82 ℃ for 2h, adding absolute ethyl alcohol with 8 times of the mass of the cyanopiperazine, placing in a 0 ℃ ice water bath, adding sodium borohydride with 0.3 times of the mass of the cyanopiperazine at a speed of 0.2g/min, reacting for 0.5h at 200rpm, distilling at 0.06MPa and 55 ℃ for 70min, adding ethyl acetate with 10 times of the mass of the cyanopiperazine, stirring and dissolving, washing with distilled water for 5 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 6h, filtering, and concentrating at 300rpm and 105 ℃ for 40min to obtain a hydroxyl compound;
(3) adding a hydroxyl compound, triethylamine and dichloromethane into a reaction bottle according to the mass ratio of 1:1.5:11, stirring at 100rpm at the temperature of 0 ℃, adding methanesulfonyl chloride mixed liquid with the mass 4 times that of the hydroxyl compound at the speed of 2mL/min, wherein the mass ratio of methanesulfonyl chloride to dichloromethane in the methanesulfonyl chloride mixed liquid is 1:2.09, reacting for 70min, heating to 40 ℃, reacting for 165min, adding saturated sodium thiosulfate with the mass 5.5 times that of the hydroxyl compound, separating liquid, and taking a water layer; adding dichloromethane with the mass 3 times of that of the hydroxyl compound into the water layer, extracting for 5 times, sequentially washing for 5 times by using deionized water and saturated saline, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 7 hours, and concentrating for 3 hours at the temperature of 60 ℃ under the pressure of 0.1MPa to obtain a sulfonic acid compound;
(4) adding a sulfonic acid compound, ethanol and sodium hydrosulfide into a reaction bottle according to the mass ratio of 1:3:0.44, stirring at 200rpm for 2 hours at 80 ℃, cooling to room temperature, distilling at 300rpm and 75 ℃ for 50 minutes, adding sodium iodide accounting for 0.003 time of the mass of the sulfonic acid compound and ethyl acetate accounting for 4.1 times of the mass of the sulfonic acid compound, stirring at 100rpm while adding 30% hydrogen peroxide accounting for 0.2 time of the mass of the sulfonic acid compound, stirring at 30 ℃ for 30 minutes at the same speed, adding saturated sodium thiosulfate accounting for 32.5 times of the mass of the sulfonic acid compound, stirring uniformly, adding ethyl acetate accounting for 17.7 times of the mass of the sulfonic acid compound, extracting for 4 times, washing with saturated saline solution for 5 times, adding anhydrous sodium sulfate till no agglomeration appears, drying for 5 hours, and carrying out rotary evaporation at 300rpm and 65 ℃ for 55 minutes to obtain a disulfide;
(5) mixing disulfide, absolute ethyl alcohol and anhydrous nickel dichloride according to a mass ratio of 1:10.2:1, adding sodium borohydride with 2 times of the mass of the disulfide at a speed of 1.3g/min, stirring at 50 ℃ and 100rpm for 3h, cooling to room temperature, adding hydrochloric acid with a mass fraction of 60% which is 10.2 times of the mass of the disulfide, stirring at the same speed for 65min, distilling at 0.2MPa and 55 ℃ for 145min, adding ammonia water with a mass fraction of 28% until the pH of the solution is 8, adding diethyl ether with 4 times of the mass of the disulfide, extracting for 4 times, washing for 6 times with saturated salt water, filtering, concentrating at 300rpm and 80 ℃ for 70min, adding polyurethane with 2.2 times of the mass of the disulfide at 40 ℃, and stirring at 300rpm for 20h to obtain modified polyurethane;
(6) placing the carbon nano tube in a ball milling tank for ball milling for 30min, wherein the ball material ratio is 5:1, placing the carbon nano tube in a glass slide, focusing laser on the carbon nano tube, and irradiating for 25s to obtain a pretreated carbon nano tube;
(7) placing the pretreated carbon nanotube on a glass slide of a substrate of an electron beam evaporation machine, placing an electrostatic plate 15cm away from the glass slide, and vacuumizing to 5 x 10-4Pa, the evaporation time is 20min and the filler is prepared;
(8) placing the self-made filler in an ultrasonic crusher, wherein the power of the ultrasonic crusher is 600W, the frequency is 50kHz, and treating for 15min to obtain the self-made filler subjected to ultrasonic treatment;
(9) mixing the self-made filler subjected to ultrasonic treatment and the modified polyurethane according to the mass ratio of 1:4, stirring for 30min at 1500rpm, adding polysorbate, tributyl phosphate, distearate and deionized water according to the mass ratio of 1:0.125:1.5:12.5, and stirring for 40min at the same speed to obtain the antistatic scratch-resistant automobile paint.
Further, in the step (6), the laser wavelength is 635nm, and the power is 20 mW.
Further, the target material of the electron beam evaporation machine in the step (7) is a silver target, the temperature of the substrate holder is 350 ℃, and the beam current is 190 mA; the electrostatic plate output voltage was 2100A and the current was 0.6 mA.
Further, placing a radio frequency coil in the electron beam evaporation machine in the step (7) at a power of 120W, wherein the distance between the radio frequency coil and the target is 50 cm; an ultrasonic generator is arranged at a distance of 30cm from the radio frequency coil, the frequency of the ultrasonic wave is 60kHz, and the power is 400W.
Comparative example 1
The antistatic scratch-resistant automobile paint mainly comprises the following components in parts by weight: 72 parts of polyurethane, 14 parts of self-made filler, 2 parts of polysorbate, 0.3 part of tributyl phosphate, 5 parts of distearate and 46 parts of deionized water.
The preparation method of the antistatic scratch-resistant automobile paint mainly comprises the following preparation steps:
(1) placing the carbon nano tube in a ball milling tank for ball milling for 25min, wherein the ball material ratio is 5:1, placing the carbon nano tube in a glass slide, focusing laser on the carbon nano tube, and irradiating for 22s to obtain a pretreated carbon nano tube;
(2) placing the pretreated carbon nanotube on a glass slide of an electron beam evaporator substrate, placing an electrostatic plate 13cm away from the glass slide, and vacuumizing to 6 x 10-4Pa, evaporation time of 17min and self-made filler;
(3) placing the self-made filler into an ultrasonic crusher, wherein the power of the ultrasonic crusher is 550W, the frequency is 46kHz, and treating for 12min to obtain the self-made filler subjected to ultrasonic treatment;
(4) mixing the self-made filler subjected to ultrasonic treatment with polyurethane according to the mass ratio of 1:5.1, stirring at 1420rpm for 36min, adding polysorbate, tributyl phosphate, distearate and deionized water according to the mass ratio of 1:0.15:2.5:23, and stirring at the same speed for 43min to obtain the antistatic scratch-resistant automobile paint.
Further, the laser wavelength in the step (1) is 630nm, and the power is 15 mW.
Further, the target material of the electron beam evaporation machine in the step (2) is a silver target, the temperature of the substrate holder is 330 ℃, and the beam current is 170 mA; the output voltage of the electrostatic plate is 2050A, and the current is 0.4 mA.
Further, a radio frequency coil is arranged in the electron beam evaporation machine in the step (2) and is 42cm away from the target, and the power is 100W; an ultrasonic generator was placed 24cm from the radio frequency coil, with an ultrasonic frequency of 50kHz and power of 350W.
Comparative example 2
The antistatic scratch-resistant automobile paint mainly comprises the following components in parts by weight: 72 parts of modified polyurethane, 14 parts of self-made filler, 2 parts of polysorbate, 0.3 part of tributyl phosphate, 5 parts of distearate and 46 parts of deionized water.
The preparation method of the antistatic scratch-resistant automobile paint mainly comprises the following preparation steps:
(1) dissolving hydroxyl propiophenonal in absolute ethyl alcohol which is 5.34 times of the mass of the hydroxyl propiophenonal, heating to 81 ℃, dropwise adding a potassium hydroxide/ethanol solution which is 3.56 times of the mass of the hydroxyl propiophenonal at a speed of 3mL/min, wherein the mass ratio of potassium hydroxide to absolute ethyl alcohol in the potassium hydroxide/ethanol solution is 1:4.70, adding bromochlorochalcone which is 2.73 times of the mass of the hydroxyl propiophenonal, reacting for 4 hours, carrying out rotary evaporation at 260rpm and 80 ℃ for 1.5 hours, adding a sodium hydroxide solution which is 10.71 times of the mass of the hydroxyl phenylacetaldehyde and has a mass fraction of 20%, carrying out suction filtration, and washing for 6 times by using absolute ethyl alcohol to obtain a bromophenylacetone compound;
(2) mixing cyanopiperazine, bromoacetone compound and acetonitrile according to a mass ratio of 1:1.19:33.77, stirring and dissolving, adding potassium carbonate with the mass of 1.69 times that of the cyanopiperazine, heating to 88 ℃, reacting for 6.5h, filtering, carrying out rotary evaporation at 350rpm and 82 ℃ for 2.5h, adding absolute ethyl alcohol with the mass of 7.81 times that of the cyanopiperazine, placing in an ice-water bath at 2 ℃, adding sodium borohydride with the mass of 0.26 time that of the cyanopiperazine at the speed of 0.18g/min, reacting for 0.8h at 145rpm, distilling for 82min at 0.09MPa and 55 ℃, adding ethyl acetate with the mass of the cyanopiperazine of 9.15 times, stirring and dissolving, washing for 4 times with distilled water, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 4.5h, filtering, and concentrating for 430min at 255rpm and 105 ℃ to obtain a hydroxyl compound;
(3) adding a hydroxyl compound, triethylamine and dichloromethane into a reaction bottle according to the mass ratio of 1:1.37:10.82, stirring at 80rpm at the temperature of 0 ℃, adding methanesulfonyl chloride mixed liquid with the mass being 3.77 times that of the hydroxyl compound at the speed of 1.5mL/min, wherein the mass ratio of methanesulfonyl chloride to dichloromethane in the methanesulfonyl chloride mixed liquid is 1:2.09, heating to 40 ℃ after reacting for 66min, reacting for 160min, adding saturated sodium thiosulfate with the mass being 5.33 times that of the hydroxyl compound, separating liquid, and taking a water layer; adding dichloromethane with 2.60 times of hydroxyl compound mass into water layer, extracting for 4 times, sequentially washing with deionized water and saturated saline solution for 4 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 6.5h, and concentrating at 60 deg.C under 0.08MPa for 2.5h to obtain sulfonic acid compound;
(4) adding a sulfonic acid compound, ethanol and sodium hydrosulfide into a reaction bottle according to the mass ratio of 1:2.83:0.42, stirring and reacting at the temperature of 80 ℃ and the speed of 160rpm for 2.5h, cooling to the room temperature, distilling at the speed of 270rpm and the temperature of 75 ℃ for 61min, adding sodium iodide and ethyl acetate which are 0.0021 times of the mass of the sulfonic acid compound and 4.03 times of the mass of the sulfonic acid compound, stirring at the speed of 66rpm while adding 30% hydrogen peroxide which is 0.17 times of the mass of the sulfonic acid compound, stirring at the temperature of 30 ℃ for 39min, adding saturated sodium thiosulfate which is 32.39 times of the mass of the sulfonic acid compound, stirring uniformly, adding ethyl acetate which is 17.41 times of the mass of the sulfonic acid compound, extracting for 3 times, washing for 4 times with saturated salt water, adding anhydrous sodium sulfate until no caking appears, drying for 4h, and then carrying out rotary evaporation at the temperature of 260rpm and 65 ℃ for 68min to obtain a disulfide;
(5) mixing disulfide, absolute ethyl alcohol and anhydrous nickel dichloride according to the mass ratio of 1:9.95:0.73, adding sodium borohydride with the mass of 1.73 times that of the disulfide at the speed of 1.1g/min, stirring at 47 ℃ and 80rpm for 3.5h, cooling to room temperature, adding hydrochloric acid with the mass fraction of 60% and the mass of 10.03 times that of the disulfide, stirring at the same speed for 71min, distilling at 0.14MPa and 55 ℃ for 138min, adding ammonia water with the mass fraction of 28% until the pH of the solution is 7.5, adding ether with the mass of 3.33 times that of the disulfide, extracting for 4 times, washing for 5 times with saturated saline solution, filtering, concentrating at 270rpm and 80 ℃ for 74min, adding polyurethane with the mass of 1.72 times that of the disulfide at the temperature of 40 ℃, and stirring at 220rpm for 22h to obtain modified polyurethane;
(6) placing the carbon nano tube in a ball milling tank for ball milling for 25min, wherein the ball material ratio is 5:1, placing the carbon nano tube in a glass slide, focusing laser on the carbon nano tube, and irradiating for 22s to obtain a pretreated carbon nano tube;
(7) placing the pretreated carbon nanotube on a glass slide of an electron beam evaporator substrate, placing an electrostatic plate 13cm away from the glass slide, and vacuumizing to 6 x 10-4Pa, evaporation time of 17min and self-made filler;
(8) placing the self-made filler into an ultrasonic crusher, wherein the power of the ultrasonic crusher is 550W, the frequency is 46kHz, and treating for 12min to obtain the self-made filler subjected to ultrasonic treatment;
(9) mixing the self-made filler subjected to ultrasonic treatment and the modified polyurethane according to the mass ratio of 1:5.1, stirring at 1420rpm for 36min, adding polysorbate, tributyl phosphate, distearate and deionized water according to the mass ratio of 1:0.15:2.5:23, and stirring at the same speed for 43min to obtain the antistatic scratch-resistant automobile paint.
Further, the laser wavelength in the step (6) is 630nm, and the power is 15 mW.
Further, the target material of the electron beam evaporation machine in the step (7) is a silver target, the temperature of the substrate holder is 330 ℃, and the beam current is 170 mA; the output voltage of the electrostatic plate is 2050A, and the current is 0.4 mA.
Further, an ultrasonic generator is arranged in the electron beam evaporation machine in the step (7) at a distance of 24cm from the radio frequency coil, the frequency of the ultrasonic wave is 50kHz, and the power is 350W.
Comparative example 3
The antistatic scratch-resistant automobile paint mainly comprises the following components in parts by weight: 72 parts of modified polyurethane, 14 parts of self-made filler, 2 parts of polysorbate, 0.3 part of tributyl phosphate, 5 parts of distearate and 46 parts of deionized water.
The preparation method of the antistatic scratch-resistant automobile paint mainly comprises the following preparation steps:
(1) dissolving hydroxyl propiophenonal in absolute ethyl alcohol which is 5.34 times of the mass of the hydroxyl propiophenonal, heating to 81 ℃, dropwise adding a potassium hydroxide/ethanol solution which is 3.56 times of the mass of the hydroxyl propiophenonal at a speed of 3mL/min, wherein the mass ratio of potassium hydroxide to absolute ethyl alcohol in the potassium hydroxide/ethanol solution is 1:4.70, adding bromochlorochalcone which is 2.73 times of the mass of the hydroxyl propiophenonal, reacting for 4 hours, carrying out rotary evaporation at 260rpm and 80 ℃ for 1.5 hours, adding a sodium hydroxide solution which is 10.71 times of the mass of the hydroxyl phenylacetaldehyde and has a mass fraction of 20%, carrying out suction filtration, and washing for 6 times by using absolute ethyl alcohol to obtain a bromophenylacetone compound;
(2) mixing cyanopiperazine, bromoacetone compound and acetonitrile according to a mass ratio of 1:1.19:33.77, stirring and dissolving, adding potassium carbonate with the mass of 1.69 times that of the cyanopiperazine, heating to 88 ℃, reacting for 6.5h, filtering, carrying out rotary evaporation at 350rpm and 82 ℃ for 2.5h, adding absolute ethyl alcohol with the mass of 7.81 times that of the cyanopiperazine, placing in an ice-water bath at 2 ℃, adding sodium borohydride with the mass of 0.26 time that of the cyanopiperazine at the speed of 0.18g/min, reacting for 0.8h at 145rpm, distilling for 82min at 0.09MPa and 55 ℃, adding ethyl acetate with the mass of the cyanopiperazine of 9.15 times, stirring and dissolving, washing for 4 times with distilled water, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 4.5h, filtering, and concentrating for 430min at 255rpm and 105 ℃ to obtain a hydroxyl compound;
(3) adding a hydroxyl compound, triethylamine and dichloromethane into a reaction bottle according to the mass ratio of 1:1.37:10.82, stirring at 80rpm at the temperature of 0 ℃, adding methanesulfonyl chloride mixed liquid with the mass being 3.77 times that of the hydroxyl compound at the speed of 1.5mL/min, wherein the mass ratio of methanesulfonyl chloride to dichloromethane in the methanesulfonyl chloride mixed liquid is 1:2.09, heating to 40 ℃ after reacting for 66min, reacting for 160min, adding saturated sodium thiosulfate with the mass being 5.33 times that of the hydroxyl compound, separating liquid, and taking a water layer; adding dichloromethane with 2.60 times of hydroxyl compound mass into water layer, extracting for 4 times, sequentially washing with deionized water and saturated saline solution for 4 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 6.5h, and concentrating at 60 deg.C under 0.08MPa for 2.5h to obtain sulfonic acid compound;
(4) adding a sulfonic acid compound, ethanol and sodium hydrosulfide into a reaction bottle according to the mass ratio of 1:2.83:0.42, stirring and reacting at the temperature of 80 ℃ and the speed of 160rpm for 2.5h, cooling to the room temperature, distilling at the speed of 270rpm and the temperature of 75 ℃ for 61min, adding sodium iodide and ethyl acetate which are 0.0021 times of the mass of the sulfonic acid compound and 4.03 times of the mass of the sulfonic acid compound, stirring at the speed of 66rpm while adding 30% hydrogen peroxide which is 0.17 times of the mass of the sulfonic acid compound, stirring at the temperature of 30 ℃ for 39min, adding saturated sodium thiosulfate which is 32.39 times of the mass of the sulfonic acid compound, stirring uniformly, adding ethyl acetate which is 17.41 times of the mass of the sulfonic acid compound, extracting for 3 times, washing for 4 times with saturated salt water, adding anhydrous sodium sulfate until no caking appears, drying for 4h, and then carrying out rotary evaporation at the temperature of 260rpm and 65 ℃ for 68min to obtain a disulfide;
(5) mixing disulfide, absolute ethyl alcohol and anhydrous nickel dichloride according to the mass ratio of 1:9.95:0.73, adding sodium borohydride with the mass of 1.73 times that of the disulfide at the speed of 1.1g/min, stirring at 47 ℃ and 80rpm for 3.5h, cooling to room temperature, adding hydrochloric acid with the mass fraction of 60% and the mass of 10.03 times that of the disulfide, stirring at the same speed for 71min, distilling at 0.14MPa and 55 ℃ for 138min, adding ammonia water with the mass fraction of 28% until the pH of the solution is 7.5, adding ether with the mass of 3.33 times that of the disulfide, extracting for 4 times, washing for 5 times with saturated saline solution, filtering, concentrating at 270rpm and 80 ℃ for 74min, adding polyurethane with the mass of 1.72 times that of the disulfide at the temperature of 40 ℃, and stirring at 220rpm for 22h to obtain modified polyurethane;
(6) placing the carbon nano tube in a ball milling tank for ball milling for 25min, wherein the ball material ratio is 5:1, placing the carbon nano tube in a glass slide, focusing laser on the carbon nano tube, and irradiating for 22s to obtain a pretreated carbon nano tube;
(7) placing the pretreated carbon nanotube on a glass slide of an electron beam evaporator substrate, placing an electrostatic plate 13cm away from the glass slide, and vacuumizing to 6 x 10-4Pa, evaporation time of 17min and self-made filler;
(8) placing the self-made filler into an ultrasonic crusher, wherein the power of the ultrasonic crusher is 550W, the frequency is 46kHz, and treating for 12min to obtain the self-made filler subjected to ultrasonic treatment;
(9) mixing the self-made filler subjected to ultrasonic treatment and the modified polyurethane according to the mass ratio of 1:5.1, stirring at 1420rpm for 36min, adding polysorbate, tributyl phosphate, distearate and deionized water according to the mass ratio of 1:0.15:2.5:23, and stirring at the same speed for 43min to obtain the antistatic scratch-resistant automobile paint.
Further, the laser wavelength in the step (6) is 630nm, and the power is 15 mW.
Further, the target material of the electron beam evaporation machine in the step (7) is a silver target, the temperature of the substrate holder is 330 ℃, and the beam current is 170 mA; the output voltage of the electrostatic plate is 2050A, and the current is 0.4 mA.
Further, a radio frequency coil is arranged in the electron beam evaporation machine in the step (7) at a distance of 42cm from the target, and the power is 100W.
Comparative example 4
The antistatic scratch-resistant automobile paint mainly comprises the following components in parts by weight: 72 parts of modified polyurethane, 14 parts of self-made filler, 2 parts of polysorbate, 0.3 part of tributyl phosphate, 5 parts of distearate and 46 parts of deionized water.
The preparation method of the antistatic scratch-resistant automobile paint mainly comprises the following preparation steps:
(1) dissolving hydroxyl propiophenonal in absolute ethyl alcohol which is 5.34 times of the mass of the hydroxyl propiophenonal, heating to 81 ℃, dropwise adding a potassium hydroxide/ethanol solution which is 3.56 times of the mass of the hydroxyl propiophenonal at a speed of 3mL/min, wherein the mass ratio of potassium hydroxide to absolute ethyl alcohol in the potassium hydroxide/ethanol solution is 1:4.70, adding bromochlorochalcone which is 2.73 times of the mass of the hydroxyl propiophenonal, reacting for 4 hours, carrying out rotary evaporation at 260rpm and 80 ℃ for 1.5 hours, adding a sodium hydroxide solution which is 10.71 times of the mass of the hydroxyl phenylacetaldehyde and has a mass fraction of 20%, carrying out suction filtration, and washing for 6 times by using absolute ethyl alcohol to obtain a bromophenylacetone compound;
(2) mixing cyanopiperazine, bromoacetone compound and acetonitrile according to a mass ratio of 1:1.19:33.77, stirring and dissolving, adding potassium carbonate with the mass of 1.69 times that of the cyanopiperazine, heating to 88 ℃, reacting for 6.5h, filtering, carrying out rotary evaporation at 350rpm and 82 ℃ for 2.5h, adding absolute ethyl alcohol with the mass of 7.81 times that of the cyanopiperazine, placing in an ice-water bath at 2 ℃, adding sodium borohydride with the mass of 0.26 time that of the cyanopiperazine at the speed of 0.18g/min, reacting for 0.8h at 145rpm, distilling for 82min at 0.09MPa and 55 ℃, adding ethyl acetate with the mass of the cyanopiperazine of 9.15 times, stirring and dissolving, washing for 4 times with distilled water, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 4.5h, filtering, and concentrating for 430min at 255rpm and 105 ℃ to obtain a hydroxyl compound;
(3) adding a hydroxyl compound, triethylamine and dichloromethane into a reaction bottle according to the mass ratio of 1:1.37:10.82, stirring at 80rpm at the temperature of 0 ℃, adding methanesulfonyl chloride mixed liquid with the mass being 3.77 times that of the hydroxyl compound at the speed of 1.5mL/min, wherein the mass ratio of methanesulfonyl chloride to dichloromethane in the methanesulfonyl chloride mixed liquid is 1:2.09, heating to 40 ℃ after reacting for 66min, reacting for 160min, adding saturated sodium thiosulfate with the mass being 5.33 times that of the hydroxyl compound, separating liquid, and taking a water layer; adding dichloromethane with 2.60 times of hydroxyl compound mass into water layer, extracting for 4 times, sequentially washing with deionized water and saturated saline solution for 4 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 6.5h, and concentrating at 60 deg.C under 0.08MPa for 2.5h to obtain sulfonic acid compound;
(4) adding a sulfonic acid compound, ethanol and sodium hydrosulfide into a reaction bottle according to the mass ratio of 1:2.83:0.42, stirring and reacting at the temperature of 80 ℃ and the speed of 160rpm for 2.5h, cooling to the room temperature, distilling at the speed of 270rpm and the temperature of 75 ℃ for 61min, adding sodium iodide and ethyl acetate which are 0.0021 times of the mass of the sulfonic acid compound and 4.03 times of the mass of the sulfonic acid compound, stirring at the speed of 66rpm while adding 30% hydrogen peroxide which is 0.17 times of the mass of the sulfonic acid compound, stirring at the temperature of 30 ℃ for 39min, adding saturated sodium thiosulfate which is 32.39 times of the mass of the sulfonic acid compound, stirring uniformly, adding ethyl acetate which is 17.41 times of the mass of the sulfonic acid compound, extracting for 3 times, washing for 4 times with saturated salt water, adding anhydrous sodium sulfate until no caking appears, drying for 4h, and then carrying out rotary evaporation at the temperature of 260rpm and 65 ℃ for 68min to obtain a disulfide;
(5) mixing disulfide, absolute ethyl alcohol and anhydrous nickel dichloride according to the mass ratio of 1:9.95:0.73, adding sodium borohydride with the mass of 1.73 times that of the disulfide at the speed of 1.1g/min, stirring at 47 ℃ and 80rpm for 3.5h, cooling to room temperature, adding hydrochloric acid with the mass fraction of 60% and the mass of 10.03 times that of the disulfide, stirring at the same speed for 71min, distilling at 0.14MPa and 55 ℃ for 138min, adding ammonia water with the mass fraction of 28% until the pH of the solution is 7.5, adding ether with the mass of 3.33 times that of the disulfide, extracting for 4 times, washing for 5 times with saturated saline solution, filtering, concentrating at 270rpm and 80 ℃ for 74min, adding polyurethane with the mass of 1.72 times that of the disulfide at the temperature of 40 ℃, and stirring at 220rpm for 22h to obtain modified polyurethane;
(6) placing the carbon nano tube in a ball milling tank for ball milling for 25min, wherein the ball material ratio is 5:1, placing the carbon nano tube in a glass slide, focusing laser on the carbon nano tube, and irradiating for 22s to obtain a pretreated carbon nano tube;
(7) placing the pretreated carbon nanotube on a glass slide of the substrate of an electron beam evaporation machine, and vacuumizing to 6 multiplied by 10-4Pa, evaporation time of 17min and self-made filler;
(8) placing the self-made filler into an ultrasonic crusher, wherein the power of the ultrasonic crusher is 550W, the frequency is 46kHz, and treating for 12min to obtain the self-made filler subjected to ultrasonic treatment;
(9) mixing the self-made filler subjected to ultrasonic treatment and the modified polyurethane according to the mass ratio of 1:5.1, stirring at 1420rpm for 36min, adding polysorbate, tributyl phosphate, distearate and deionized water according to the mass ratio of 1:0.15:2.5:23, and stirring at the same speed for 43min to obtain the antistatic scratch-resistant automobile paint.
Further, the laser wavelength in the step (6) is 630nm, and the power is 15 mW.
Further, the target material of the electron beam evaporation machine in the step (7) is a silver target, the temperature of the substrate holder is 330 ℃, and the beam current is 170 mA.
Further, a radio frequency coil is arranged in the electron beam evaporation machine in the step (7) at a distance of 42cm from the target, and the power is 100W; an ultrasonic generator was placed 24cm from the radio frequency coil, with an ultrasonic frequency of 50kHz and power of 350W.
Comparative example 5
The antistatic scratch-resistant automobile paint mainly comprises the following components in parts by weight: 72 parts of modified polyurethane, 14 parts of self-made filler, 2 parts of polysorbate, 0.3 part of tributyl phosphate, 5 parts of distearate and 46 parts of deionized water.
The preparation method of the antistatic scratch-resistant automobile paint mainly comprises the following preparation steps:
(1) dissolving hydroxyl propiophenonal in absolute ethyl alcohol which is 5.34 times of the mass of the hydroxyl propiophenonal, heating to 81 ℃, dropwise adding a potassium hydroxide/ethanol solution which is 3.56 times of the mass of the hydroxyl propiophenonal at a speed of 3mL/min, wherein the mass ratio of potassium hydroxide to absolute ethyl alcohol in the potassium hydroxide/ethanol solution is 1:4.70, adding bromochlorochalcone which is 2.73 times of the mass of the hydroxyl propiophenonal, reacting for 4 hours, carrying out rotary evaporation at 260rpm and 80 ℃ for 1.5 hours, adding a sodium hydroxide solution which is 10.71 times of the mass of the hydroxyl phenylacetaldehyde and has a mass fraction of 20%, carrying out suction filtration, and washing for 6 times by using absolute ethyl alcohol to obtain a bromophenylacetone compound;
(2) mixing cyanopiperazine, bromoacetone compound and acetonitrile according to a mass ratio of 1:1.19:33.77, stirring and dissolving, adding potassium carbonate with the mass of 1.69 times that of the cyanopiperazine, heating to 88 ℃, reacting for 6.5h, filtering, carrying out rotary evaporation at 350rpm and 82 ℃ for 2.5h, adding absolute ethyl alcohol with the mass of 7.81 times that of the cyanopiperazine, placing in an ice-water bath at 2 ℃, adding sodium borohydride with the mass of 0.26 time that of the cyanopiperazine at the speed of 0.18g/min, reacting for 0.8h at 145rpm, distilling for 82min at 0.09MPa and 55 ℃, adding ethyl acetate with the mass of the cyanopiperazine of 9.15 times, stirring and dissolving, washing for 4 times with distilled water, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 4.5h, filtering, and concentrating for 430min at 255rpm and 105 ℃ to obtain a hydroxyl compound;
(3) adding a hydroxyl compound, triethylamine and dichloromethane into a reaction bottle according to the mass ratio of 1:1.37:10.82, stirring at 80rpm at the temperature of 0 ℃, adding methanesulfonyl chloride mixed liquid with the mass being 3.77 times that of the hydroxyl compound at the speed of 1.5mL/min, wherein the mass ratio of methanesulfonyl chloride to dichloromethane in the methanesulfonyl chloride mixed liquid is 1:2.09, heating to 40 ℃ after reacting for 66min, reacting for 160min, adding saturated sodium thiosulfate with the mass being 5.33 times that of the hydroxyl compound, separating liquid, and taking a water layer; adding dichloromethane with 2.60 times of hydroxyl compound mass into water layer, extracting for 4 times, sequentially washing with deionized water and saturated saline solution for 4 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 6.5h, and concentrating at 60 deg.C under 0.08MPa for 2.5h to obtain sulfonic acid compound;
(4) adding a sulfonic acid compound, ethanol and sodium hydrosulfide into a reaction bottle according to the mass ratio of 1:2.83:0.42, stirring and reacting at the temperature of 80 ℃ and the speed of 160rpm for 2.5h, cooling to the room temperature, distilling at the speed of 270rpm and the temperature of 75 ℃ for 61min, adding sodium iodide and ethyl acetate which are 0.0021 times of the mass of the sulfonic acid compound and 4.03 times of the mass of the sulfonic acid compound, stirring at the speed of 66rpm while adding 30% hydrogen peroxide which is 0.17 times of the mass of the sulfonic acid compound, stirring at the temperature of 30 ℃ for 39min, adding saturated sodium thiosulfate which is 32.39 times of the mass of the sulfonic acid compound, stirring uniformly, adding ethyl acetate which is 17.41 times of the mass of the sulfonic acid compound, extracting for 3 times, washing for 4 times with saturated salt water, adding anhydrous sodium sulfate until no caking appears, drying for 4h, and then carrying out rotary evaporation at the temperature of 260rpm and 65 ℃ for 68min to obtain a disulfide;
(5) mixing disulfide, absolute ethyl alcohol and anhydrous nickel dichloride according to the mass ratio of 1:9.95:0.73, adding sodium borohydride with the mass of 1.73 times that of the disulfide at the speed of 1.1g/min, stirring at 47 ℃ and 80rpm for 3.5h, cooling to room temperature, adding hydrochloric acid with the mass fraction of 60% and the mass of 10.03 times that of the disulfide, stirring at the same speed for 71min, distilling at 0.14MPa and 55 ℃ for 138min, adding ammonia water with the mass fraction of 28% until the pH of the solution is 7.5, adding ether with the mass of 3.33 times that of the disulfide, extracting for 4 times, washing for 5 times with saturated saline solution, filtering, concentrating at 270rpm and 80 ℃ for 74min, adding polyurethane with the mass of 1.72 times that of the disulfide at the temperature of 40 ℃, and stirring at 220rpm for 22h to obtain modified polyurethane;
(6) placing the carbon nano tube in a ball milling tank for ball milling for 25min, wherein the ball material ratio is 5:1, placing the carbon nano tube in a glass slide, focusing laser on the carbon nano tube, and irradiating for 22s to obtain a pretreated carbon nano tube;
(7) placing the pretreated carbon nanotube on a glass slide of an electron beam evaporator substrate, placing an electrostatic plate 13cm away from the glass slide, and vacuumizing to 6 x 10-4Pa, evaporation time of 17min and self-made filler;
(8) mixing the self-made filler and the modified polyurethane according to the mass ratio of 1:5.1, stirring at 1420rpm for 36min, adding polysorbate, tributyl phosphate, distearate and deionized water according to the mass ratio of 1:0.15:2.5:23, and stirring at the same speed for 43min to obtain the antistatic scratch-resistant automobile paint.
Further, the laser wavelength in the step (6) is 630nm, and the power is 15 mW.
Further, the target material of the electron beam evaporation machine in the step (7) is a silver target, the temperature of the substrate holder is 330 ℃, and the beam current is 170 mA; the output voltage of the electrostatic plate is 2050A, and the current is 0.4 mA.
Further, a radio frequency coil is arranged in the electron beam evaporation machine in the step (7) at a distance of 42cm from the target, and the power is 100W; an ultrasonic generator was placed 24cm from the radio frequency coil, with an ultrasonic frequency of 50kHz and power of 350W.
Comparative example 6
The antistatic scratch-resistant automobile paint mainly comprises the following components in parts by weight: 72 parts of polyurethane, 14 parts of carbon nano tube, 2 parts of polysorbate, 0.3 part of tributyl phosphate, 5 parts of distearate and 46 parts of deionized water.
The preparation method of the antistatic scratch-resistant automobile paint mainly comprises the following preparation steps: mixing the carbon nano tube and the polyurethane according to the mass ratio of 1:5.1, stirring at 1420rpm for 36min, adding polysorbate, tributyl phosphate, distearate and deionized water according to the mass ratio of 1:0.15:2.5:23, and stirring at the same speed for 43min to obtain the antistatic scratch-resistant automobile paint.
Examples of effects
The following table 1 shows the results of performance analysis of the antistatic scratch resistant automobile paints using examples 1 to 2 of the present invention and comparative examples 1 to 6.
TABLE 1
Figure BDA0003394668190000161
Figure BDA0003394668190000171
Compared with the experimental data of the comparative examples 1 and 6, the modified polyurethane is used in the product to generate the photosensitive group disulfide bond, so that the self-repairing scratch can be realized under ultraviolet light, and the scratch resistance of the automobile paint is facilitated; the self-made filler is used to improve the conductivity of the automobile paint, so that the automobile paint has antistatic performance, and forms a conductive network with the modified polyurethane to improve the antistatic capability of the automobile paint; from the comparison of the experimental data of the examples 1 and 2 and the comparative example 1, it can be found that if the polyurethane modified by the cyanopiperazine, the hydroxyphenylpyruvaldehyde and the bromochlorochalcone is not used, a disulfide bond cannot be introduced into a polyurethane molecular chain, so that the automotive paint cannot be self-repaired under ultraviolet illumination, and a direct-connection structure cannot be formed at the same time, thereby affecting the heat resistance of the automotive paint, and a plurality of rigid benzene rings cannot be introduced, so that the intramolecular cohesive energy is reduced, and further the heat resistance of the automotive paint is affected; from the comparison of the experimental data of the examples 1 and 2 and the comparative example 2, it can be found that if the self-made filler is prepared without using the radio frequency glow discharge auxiliary electron beam, the silver vapor can not be converted into the plasma, and the plasma can not be modified by using the ultrasonic waves and the electrostatic field, so that the silver can not be deposited at the gaps of the carbon nanotubes, and the antistatic effect of the vehicle paint is influenced; from the comparison of the experimental data of the examples 1 and 2 and the comparative example 3, it can be found that if the self-made filler is prepared without using the ultrasonic-assisted electron beam, the plasma cannot be made hollow and carry charges, so that silver randomly grows on the surface of the carbon nanotube, the surface of the carbon nanotube has uneven conductive effect, and the antistatic effect of the vehicle paint is further reduced; compared with the experimental data of the embodiment 1 and the embodiment 2 and the comparative example 4, the experimental data shows that if the self-made filler is prepared without using the electrostatic field to assist the electron beam, silver grows disorderly, and meanwhile, less silver is deposited on the surface of the carbon nano tube and can not form a dendritic shape, so that a conductive network is formed with the modified polyurethane, and the antistatic property of the vehicle paint is reduced; compared with the experimental data of the comparative examples 1 and 5, the experimental data show that if the self-made filler is not treated by ultrasonic waves, the dispersibility of the self-made filler is improved, the self-made filler is easy to agglomerate in the modified polyurethane, the antistatic effect of the automobile paint is influenced, and meanwhile, the hydroxyl on the surface of the self-made filler cannot be changed into free radicals, so that the self-made filler cannot be crosslinked with the modified polyurethane to form a conductive network, electrons cannot move freely, and the antistatic performance of the automobile paint is influenced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. The antistatic scratch-resistant automobile paint is characterized by mainly comprising, by weight, 60-80 parts of modified polyurethane, 10-20 parts of self-made filler, 1-4 parts of wetting agent, 0.1-0.5 part of defoaming agent, 3-6 parts of thickening agent and 40-50 parts of deionized water.
2. The antistatic scratch-resistant automobile paint as claimed in claim 1, wherein the modified polyurethane is prepared from polyurethane, cyanopiperazine, hydroxyphenylpyruvaldehyde and bromochlorochalcone.
3. The antistatic scratch-resistant automobile paint as claimed in claim 2, wherein the self-made filler is prepared by depositing silver on carbon nanotubes by using radio frequency glow discharge, ultrasonic waves and electrostatic field assisted electron beams.
4. The antistatic scratch-resistant automobile paint as claimed in claim 3, wherein the wetting agent is one or more of polysorbate, polyoxyethylene octylphenol ether, sulfonated oil or sodium alkyl naphthalene sulfonate.
5. The antistatic scratch-resistant automobile paint as claimed in claim 4, wherein the defoaming agent is one or more of tributyl phosphate, polydimethylsiloxane, glycerol polyether or polyoxyethylene ether.
6. The antistatic scratch-resistant automotive paint as claimed in claim 5, wherein the thickener is one or more of distearate, polyurethane, stearyl alcohol or cetyl alcohol.
7. The preparation method of the antistatic scratch-resistant automobile paint is characterized by mainly comprising the following preparation steps of:
(1) dissolving hydroxyl propiophenonal in absolute ethyl alcohol which is 5-6 times of the mass of the hydroxyl propiophenonal, heating to 80-85 ℃, dropwise adding a potassium hydroxide/ethanol solution which is 3-4 times of the mass of the hydroxyl propiophenonal at a speed of 2-4 mL/min, wherein the mass ratio of potassium hydroxide to absolute ethyl alcohol in the potassium hydroxide/ethanol solution is 1:4.70, adding bromochlorochalcone which is 2-3 times of the mass of the hydroxyl propiophenonal, reacting for 3-5 hours, carrying out rotary evaporation at 200-300 rpm and 80 ℃ for 1-2 hours, adding a sodium hydroxide solution which is 10.5-11 times of the mass of the hydroxyl propiophenonal and has a mass fraction of 20%, carrying out suction filtration, and washing for 5-7 times by using the absolute ethyl alcohol to obtain a bromophenylacetone compound;
(2) mixing cyano piperazine, a bromoacetone compound and acetonitrile according to a mass ratio of 1: 0.6-1.5: 33.5-34, stirring and dissolving, adding potassium carbonate with the mass 1.5-2 times that of the cyanopiperazine, heating to 85-90 ℃, reacting for 5-7 h, filtering, carrying out rotary evaporation at 300-400 rpm and 82 ℃ for 2-3 h, adding absolute ethyl alcohol with the mass 7.5-8 times of that of the cyanopiperazine, placing in an ice-water bath at the temperature of 0-5 ℃, adding sodium borohydride with the mass of 0.2-0.3 times that of the cyanopiperazine at the speed of 0.12-0.2 g/min, reacting for 0.5-1 h at 100-200 rpm, distilling at 0.06-0.1 MPa and 55 ℃ for 70-90 min, adding ethyl acetate with the mass of 9-10 times that of the cyanopiperazine, stirring and dissolving, washing with distilled water for 3-5 times, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 4-6 h, filtering, and concentrating at 200-300 rpm and 105 ℃ for 40-50 min to obtain a hydroxyl compound;
(3) adding a hydroxyl compound, triethylamine and dichloromethane into a reaction bottle according to the mass ratio of 1: 1-1.5: 10.5-11, stirring at 50-100 rpm at the temperature of 0 ℃, adding methanesulfonyl chloride mixed liquid with the mass being 3.5-4 times that of the hydroxyl compound at the speed of 1-2 mL/min, wherein the mass ratio of methanesulfonyl chloride to dichloromethane in the methanesulfonyl chloride mixed liquid is 1:2.09, reacting for 60-70 min, heating to 40 ℃, reacting for 150-165 min, adding saturated sodium thiosulfate with the mass being 5-5.5 times that of the hydroxyl compound, separating liquid, and taking a water layer; adding dichloromethane with 2.5-3 times of the mass of the hydroxyl compound into a water layer, extracting for 3-5 times, sequentially washing for 3-5 times by using deionized water and saturated salt solution, adding anhydrous magnesium sulfate until no agglomeration appears, drying for 6-7 hours, and concentrating for 2-3 hours at 60 ℃ under 0.05-0.1 MPa to obtain a sulfonic acid compound;
(4) adding a sulfonic acid compound, ethanol and sodium hydrosulfide into a reaction bottle according to the mass ratio of 1: 2.4-3: 0.38-0.44, stirring and reacting at the temperature of 80 ℃ and the rpm of 100-200 for 2-3 h, cooling to room temperature, distilling at the temperature of 200-300 rpm and the temperature of 75 ℃ for 50-65 min, adding sodium iodide accounting for 0.002-0.003 times of the mass of the sulfonic acid compound and ethyl acetate accounting for 3.4-4.1 times of the mass of the sulfonic acid compound, adding 30% hydrogen peroxide accounting for 0.15-0.2 times of the mass of the sulfonic acid compound while stirring at the speed of 50-100 rpm, and reacting at the temperature of 30 ℃, stirring for 30-45 min at the same speed, adding saturated sodium thiosulfate with the mass 32-32.5 times of that of the sulfonic acid compound, stirring uniformly, adding ethyl acetate with the mass 17.2-17.7 times of that of the sulfonic acid compound, extracting for 2-4 times, washing for 3-5 times with saturated salt solution, adding anhydrous sodium sulfate until no agglomeration appears, drying for 3-5 h, and carrying out rotary evaporation at 200-300 rpm and 65 ℃ for 55-70 min to obtain a disulfide;
(5) mixing disulfide, absolute ethyl alcohol and absolute nickel dichloride according to the mass ratio of 1: 9.6-10.2: 0.5-1, adding sodium borohydride with the mass of 1.4 to 2 times of that of disulfide into the mixture at the speed of 0.9 to 1.3g/min, stirring the mixture for 3 to 4 hours at the temperature of between 40 and 50 ℃ and at the rpm of between 50 and 100, cooling to room temperature, adding hydrochloric acid with the mass fraction of 60% and the mass of 9.6-10.2 times of that of the disulfide, stirring at the same speed for 65-75 min, distilling at 55 ℃ under 0.1-0.2 MPa for 130-145 min, adding 28% ammonia water until the pH of the solution is 7-8, adding diethyl ether with the mass 3-4 times of that of disulfide, extracting for 3-4 times, washing for 4-6 times with saturated salt solution, filtering, concentrating at 80 ℃ at 200-300 rpm for 70-80 min, adding polyurethane with the mass of 1.6-2.2 times of that of disulfide at 40 ℃, and stirring at 200-300 rpm for 20-24 hours to obtain modified polyurethane;
(6) placing the carbon nano tube in a ball milling tank for ball milling for 20-30 min, wherein the ball material ratio is 5:1, placing the carbon nano tube in a glass slide, focusing laser on the carbon nano tube, and irradiating for 10-25 s to obtain a pretreated carbon nano tube;
(7) placing the pretreated carbon nano tube on a glass slide of a substrate of an electron beam evaporation machine, placing an electrostatic plate 10-15 cm away from the glass slide, and vacuumizing to 5 multiplied by 10-4～7×10-4Pa, the evaporation time is 15-20 min, and the filler is obtained;
(8) placing the self-made filler into an ultrasonic crusher, treating the self-made filler for 10-15 min with the power of the ultrasonic crusher being 500-600W and the frequency being 40-50 kHz to obtain the self-made filler for ultrasonic treatment;
(9) mixing the self-made filler subjected to ultrasonic treatment and the modified polyurethane according to the mass ratio of 1: 4-6, stirring at 1000-1500 rpm for 30-40 min, adding a wetting agent, a defoaming agent, a thickening agent and deionized water according to the mass ratio of 1: 0.1-0.2: 2-4: 12.5-40, and stirring at the same speed for 40-50 min to obtain the antistatic scratch-resistant automobile paint.
8. The preparation method of the antistatic scratch-resistant automobile paint as claimed in claim 7, wherein the laser wavelength in the step (6) is 620-635 nm, and the power is 10-20 mW.
9. The preparation method of the antistatic scratch-resistant automobile paint as claimed in claim 8, wherein the target material of the electron beam evaporation machine in the step (7) is a silver target, the temperature of a substrate holder is 300-350 ℃, and the beam current is 150-190 mA; the output voltage of the electrostatic plate is 2000-2100A, and the current is 0.2-0.6 mA.
10. The method for preparing the antistatic and scratch-resistant automobile paint as claimed in claim 9, wherein in the step (7), a radio frequency coil is placed in the electron beam evaporator at a distance of 40-50 cm from the target material, and the power is 90-120W; an ultrasonic generator is arranged 20-30 cm away from the radio frequency coil, the frequency of ultrasonic waves is 40-60 kHz, and the power is 300-400W.
CN202111478853.2A 2021-12-06 2021-12-06 Antistatic scratch-resistant automobile paint and preparation method thereof Pending CN114015342A (en)

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