CN112375461A - Conductive graphene composite coating for automobile and preparation method thereof - Google Patents
Conductive graphene composite coating for automobile and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/001—Conductive additives
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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
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- C08K2201/011—Nanostructured additives
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- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a conductive graphene composite coating for an automobile. The invention discloses a preparation method of the conductive graphene composite coating for the automobile, which comprises the following steps: adding sodium dodecyl benzene sulfonate into water, uniformly mixing, sequentially adding graphene oxide and nano titanium dioxide in a stirring state, and performing ultrasonic treatment after complete addition to obtain a prefabricated material a; adding a sodium hydroxide solution into the prefabricated material a, uniformly stirring, adding N-hydroxysuccinimide under a stirring state, adding linear polyethyleneimine, performing ultrasonic treatment, performing suction filtration and drying, and performing airflow crushing under the protection of nitrogen to obtain a prefabricated material b; dispersing the prefabricated material b in deionized water again, dropwise adding hydrazine hydrate for reduction, centrifuging, washing, and performing low-temperature ball milling to obtain a premix c; and (3) sequentially adding a stabilizer, a defoaming agent and a softening agent into the premix c, uniformly mixing, sequentially adding a water-based epoxy resin emulsion and a dispersing agent, uniformly mixing, ultrasonically oscillating, and filtering to obtain the conductive graphene composite coating for the automobile.
Description
Technical Field
The invention relates to the technical field of automobile coatings, in particular to an automobile conductive graphene composite coating and a preparation method thereof.
Background
The conductive coating is a special functional coating which is rapidly developed along with modern science and technology, the conductive coating is coated on a non-conductive substrate material by a spraying method, a brushing method or a coating process, so that the non-conductive substrate material has the functions of conducting current and eliminating accumulated static charges, the conductivity of the coating formed by the coating is generally more than 10S/m, and the conductive coating is applied to various military and civil industrial fields such as electronics, electrical appliances, aviation, chemical engineering, printing and the like at present.
The coating of plastic surfaces is rapidly changing from manual spraying to continuous electrostatic spraying by robots (arms). Compared with the traditional manual air spray gun spraying, the electrostatic spraying can improve the utilization rate of the coating by more than 20 percent, thereby effectively reducing the consumption of the coating, reducing the production cost, simultaneously reducing the single-vehicle emission of volatile organic matters and reducing the harm of the coating production to the environment and constructors. However, in the spraying process of automobiles, most plastic parts are insulators and have no conductivity, so that static charges generated by continuous electrostatic spraying cannot be timely conducted out, and the coating of a layer of conductive primer on the plastic parts becomes the mainstream of the coating process of the plastic surface.
The conductive primer is generally composed of film-forming resin, conductive filler and an auxiliary agent, wherein graphene with a two-dimensional ultrathin sheet layer structure in the conductive filler is a carbon material with a two-dimensional sheet structure, and has the characteristics of high temperature resistance, corrosion resistance, small expansion coefficient and the like, and the conductive primer is high in strength and good in conductivity, but the amount of the electronic paste filler is more, especially the amount of the graphene is more, so that the cost is high, the dispersibility is poor, the conductive effect of the coating is influenced, and meanwhile, the light transmittance is poor, so that the problem is urgently solved.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a conductive graphene composite coating for an automobile and a preparation method thereof.
The conductive graphene composite coating for the automobile comprises the following raw materials in parts by weight: 100 parts of water-based epoxy resin emulsion, 3-6 parts of graphene oxide, 20-40 parts of hydrazine hydrate, 1-3 parts of nano titanium dioxide, 1-3 parts of sodium dodecyl benzene sulfonate, 0.1-0.5 part of N-hydroxysuccinimide, 2-4 parts of linear polyethyleneimine, 4-10 parts of sodium hydroxide solution with the concentration of 1.5-2mol/L, 1-2 parts of stabilizer, 1-2 parts of defoaming agent, 1-2 parts of dispersant and 1-2 parts of softener.
Preferably, the nano titanium dioxide has a diameter of 50 to 200nm, a length of 1 to 2 μm, and a volume resistivity of 5.0 to 20.0. omega. cm.
Preferably, the stabilizer is any one of tetrapropylene sodium benzene sulfonate, diisooctyl succinate sodium sulfonate, dibutyl naphthalene sodium sulfonate, dodecyl benzene sodium sulfonate and dodecyl naphthalene sodium sulfonate.
Preferably, the defoaming agent is any one of polyether defoaming agent, polyether modified silicon defoaming agent and polysiloxane defoaming agent.
Preferably, the dispersant is at least one of octadecyl dimethyl hydroxyethyl ammonium nitrate, octadecyl dimethyl hydroxyethyl ammonium perchlorate, dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, triethyl methyl ammonium chloride, triethyl methyl ammonium bromide and dodecyl trimethyl ammonium chloride.
Preferably, the softening agent is at least one of polysiloxane microemulsion, amino polysiloxane emulsion, polyether modified polysiloxane emulsion, epoxy modified polysiloxane and carboxyl modified polysiloxane.
The preparation method of the conductive graphene composite coating for the automobile comprises the following steps:
s1, adding sodium dodecyl benzene sulfonate into water, uniformly mixing, sequentially adding graphene oxide and nano titanium dioxide under a stirring state, and performing ultrasonic treatment for 10-20min after complete addition, wherein the ultrasonic power is 500-600W, so as to obtain a prefabricated material a;
s2, adding a sodium hydroxide solution into the prefabricated material a, uniformly stirring, adjusting the temperature to 70-80 ℃, adding N-hydroxysuccinimide under the stirring state, adding linear polyethyleneimine, performing ultrasonic treatment for 10-30min at the ultrasonic power of 300-400W, performing suction filtration and drying, and performing airflow crushing under the protection of nitrogen to obtain a prefabricated material b;
s3, re-dispersing the prefabricated material b in deionized water, heating to 90-100 ℃, dropwise adding hydrazine hydrate, refluxing for 18-20h, centrifuging, washing, then adding deionized water, and carrying out low-temperature ball milling for 5-8min at 10-15 ℃ to obtain premix c;
s4, sequentially adding a stabilizer, a defoaming agent and a softening agent into the premix c, uniformly mixing, sequentially adding the aqueous epoxy resin emulsion and a dispersing agent, uniformly mixing, carrying out 400-500W ultrasonic oscillation for 15-25min at an ultrasonic frequency of 15-30kHz, maintaining the temperature at 10-15 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
Preferably, in S2, the drying temperature after suction filtration is 60-80 ℃.
Preferably, in S2, the particle size of the preform b is 300-500 nm.
The technical effects of the invention are as follows:
the method comprises the steps of uniformly dispersing sodium dodecyl benzene sulfonate in water, adopting nano titanium dioxide to adsorb the surface of graphene oxide by controlling the pH value of a system, adding N-hydroxysuccinimide to perform network bridging on particles in an aqueous dispersion, reacting the N-hydroxysuccinimide with active groups in the graphene oxide, wherein the N-hydroxysuccinimide reacts with the active groups to form an activated intermediate, so that the nano titanium dioxide is stably combined with the graphene oxide, then the activated intermediate reacts with linear polyethyleneimine, and the ultra-dispersed conductive graphene is formed by reduction of hydrazine hydrate, so that the dispersion performance is excellent, the processing performance is good, the ultra-dispersed conductive graphene is highly uniformly mixed with an aqueous epoxy resin emulsion, the aggregation of the graphene can be effectively prevented, the stability of the dispersion system is kept, and meanwhile, the linear polyethyleneimine is spread and arranged in the aqueous phase, the method is favorable for orderly arranging the graphene in the aqueous epoxy resin emulsion. The conductive graphene composite coating obtained by the invention has good dispersibility in an aqueous solution, no sedimentation after 48 hours, whiteness between 22 and 65 ℃, low economic cost, simple operation and stable operation.
According to the invention, graphene is taken as a conductive component, and the uniform system conductive coating is prepared through the processes of grinding, ultrasonic oscillation and membrane filtration in sequence, so that the dispersibility of the graphene is effectively improved, the conductive coating can stably exist for a long time, the phenomena of layering and sedimentation are not generated, the coating has extremely high transparency, and the coating is easy to popularize and produce on a large scale, and is especially suitable for the field of conductive spraying of automobile plastics.
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 conductive graphene composite coating for automobiles comprises the following steps:
s1, adding 1kg of sodium dodecyl benzene sulfonate into water, uniformly mixing, adding 6kg of graphene oxide under a stirring state, stirring at a speed of 1000r/min for 15min, adding 1kg of nano titanium dioxide with a length of 1-2 mu m, a diameter of 50-200nm and a volume resistivity of 19.3 omega cm under a stirring state, and performing ultrasonic treatment for 10min after complete addition, wherein the ultrasonic power is 600W to obtain a prefabricated material a;
s2, adding 4kg of 2mol/L sodium hydroxide solution into the prefabricated material a, uniformly stirring, adjusting the temperature to 70 ℃, adding 0.5kg of N-hydroxysuccinimide under a stirring state, adding 2kg of linear polyethyleneimine, carrying out ultrasonic treatment for 30min, carrying out suction filtration, drying at 80 ℃, and crushing by using a jet mill under the protection of nitrogen to obtain a prefabricated material b with the average particle size of 310 nm;
s3, re-dispersing the prefabricated material b in deionized water, heating to 100 ℃, dropwise adding 20kg of hydrazine hydrate, refluxing for 20h, centrifuging, washing, then adding deionized water, and carrying out low-temperature ball milling for 8min at 10 ℃ to obtain premix c;
s4, sequentially adding 1kg of tetrapropylene sodium benzenesulfonate, 2kg of polyether defoamer and 1kg of polysiloxane microemulsion into premix c, uniformly mixing, sequentially adding 100kg of aqueous epoxy resin emulsion and 2kg of triethylmethylammonium bromide, uniformly mixing, feeding into an ultrasonic oscillator, oscillating for 25min at 400W, wherein the ultrasonic frequency is 15kHz, the temperature is maintained at 15 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
Example 2
A preparation method of conductive graphene composite coating for automobiles comprises the following steps:
s1, adding 3kg of sodium dodecyl benzene sulfonate into water, uniformly mixing, adding 3kg of graphene oxide under a stirring state, stirring at a speed of 2000r/min for 5min, adding 3kg of nano titanium dioxide with the length of 1-2 mu m, the diameter of 50-200nm and the volume resistivity of 5.6 omega cm under a stirring state, and carrying out ultrasonic treatment for 20min after complete addition, wherein the ultrasonic power is 500W to obtain a prefabricated material a;
s2, adding 10kg of sodium hydroxide solution with the concentration of 1.5mol/L into the prefabricated material a, uniformly stirring, adjusting the temperature to 80 ℃, adding 0.1kg of N-hydroxysuccinimide under the stirring state, adding 4kg of linear polyethyleneimine, performing ultrasonic treatment for 10min, wherein the ultrasonic power is 400W, performing suction filtration, drying at 60 ℃, and crushing by using a jet mill under the protection of nitrogen to obtain a prefabricated material b with the average particle size of 480 nm;
s3, re-dispersing the prefabricated material b in deionized water, heating to 90 ℃, dropwise adding 40kg of hydrazine hydrate, refluxing for 18h, centrifuging, washing, then adding deionized water, and carrying out low-temperature ball milling for 5min at 15 ℃ to obtain premix c;
s4, sequentially adding 2kg of sodium diisooctyl succinate sulfonate, 1kg of polyether defoamer and 2kg of amino polysiloxane emulsion into the premix c, uniformly mixing, sequentially adding 100kg of aqueous epoxy resin emulsion and 1kg of octadecyl dimethyl hydroxyethyl ammonium perchlorate, uniformly mixing, sending into an ultrasonic oscillator, oscillating for 15min at 500W of power, wherein the ultrasonic frequency is 30kHz, the temperature is maintained at 10 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
Example 3
A preparation method of conductive graphene composite coating for automobiles comprises the following steps:
s1, adding 1.5kg of sodium dodecyl benzene sulfonate into water, uniformly mixing, adding 5kg of graphene oxide under a stirring state, stirring at a speed of 1200r/min for 12min, adding 1.5kg of nano titanium dioxide with a length of 1.2-1.8 mu m, a diameter of 80-100nm and a volume resistivity of 14.2 omega cm under a stirring state, carrying out ultrasonic treatment for 12min after complete addition, and obtaining a prefabricated material a with ultrasonic power of 570W;
s2, adding 6kg of sodium hydroxide solution with the concentration of 1.8mol/L into the prefabricated material a, uniformly stirring, adjusting the temperature to 73 ℃, adding 0.4kg of N-hydroxysuccinimide under the stirring state, adding 2.5kg of linear polyethyleneimine, carrying out ultrasonic treatment for 25min, wherein the ultrasonic power is 330W, carrying out suction filtration, drying at 75 ℃, and crushing by adopting a jet mill under the protection of nitrogen to obtain a prefabricated material b with the average particle size of 330 nm;
s3, re-dispersing the prefabricated material b in deionized water, heating to 97 ℃, dropwise adding 25kg of hydrazine hydrate, refluxing for 19.5h, centrifuging, washing, then adding deionized water, and ball-milling at a low temperature of 12 ℃ for 7min to obtain a premix c;
s4, sequentially adding 1.3kg of sodium dibutylnaphthalenesulfonate, 1.8kg of polyether modified silicon defoamer and 1.4kg of epoxy modified polysiloxane into the premix c, uniformly mixing, sequentially adding 100kg of water-based epoxy resin emulsion and 1.7kg of triethylmethylammonium chloride, uniformly mixing, feeding into an ultrasonic oscillator, oscillating for 22min at the power of 420W, wherein the ultrasonic frequency is 20kHz, the temperature is maintained at 14 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
Example 4
A preparation method of conductive graphene composite coating for automobiles comprises the following steps:
s1, adding 2.5kg of sodium dodecyl benzene sulfonate into water, uniformly mixing, adding 4kg of graphene oxide under a stirring state, stirring at 1800r/min for 8min, adding 2.5kg of nano titanium dioxide with the length of 1.2-1.8 mu m, the diameter of 80-100nm and the volume resistivity of 9.7 omega cm under a stirring state, carrying out ultrasonic treatment for 18min after complete addition, wherein the ultrasonic power is 530W, and obtaining a prefabricated material a;
s2, adding 8kg of sodium hydroxide solution with the concentration of 1.6mol/L into the prefabricated material a, uniformly stirring, adjusting the temperature to 77 ℃, adding 0.2kg of N-hydroxysuccinimide under the stirring state, adding 3.5kg of linear polyethyleneimine, carrying out ultrasonic treatment for 15min, wherein the ultrasonic power is 370W, carrying out suction filtration, drying at 65 ℃, and crushing by adopting a jet mill under the protection of nitrogen to obtain a prefabricated material b with the average particle size of 440 nm;
s3, re-dispersing the prefabricated material b in deionized water, heating to 93 ℃, dropwise adding 35kg of hydrazine hydrate, refluxing for 18.5h, centrifuging, washing, then adding deionized water, and ball-milling at a low temperature of 14 ℃ for 6min to obtain a premix c;
s4, sequentially adding 1.7kg of sodium dodecyl naphthalene sulfonate, 1.2kg of polyether modified silicon defoamer and 1.6kg of polyether modified polysiloxane emulsion into premix c, uniformly mixing, sequentially adding 100kg of aqueous epoxy resin emulsion and 1.3kg of dioctadecyl dimethyl ammonium bromide, uniformly mixing, sending into an ultrasonic oscillator, oscillating for 18min at 480W power, wherein the ultrasonic frequency is 26kHz, the temperature is maintained at 12 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
Example 5
A preparation method of conductive graphene composite coating for automobiles comprises the following steps:
s1, adding 2kg of sodium dodecyl benzene sulfonate into water, uniformly mixing, adding 4.5kg of graphene oxide under a stirring state, stirring at a speed of 1500r/min for 10min, adding 2kg of nano titanium dioxide with the length of 1.2-1.8 mu m, the diameter of 80-100nm and the volume resistivity of 12.7 omega cm under a stirring state, carrying out ultrasonic treatment for 15min after complete addition, and obtaining a prefabricated material a with the ultrasonic power of 550W;
s2, adding 7kg of sodium hydroxide solution with the concentration of 1.7mol/L into the prefabricated material a, uniformly stirring, adjusting the temperature to 75 ℃, adding 0.3kg of N-hydroxysuccinimide under the stirring state, adding 3kg of linear polyethyleneimine, performing ultrasonic treatment for 20min, wherein the ultrasonic power is 350W, performing suction filtration, drying at 70 ℃, and crushing by using a jet mill under the protection of nitrogen to obtain a prefabricated material b with the average particle size of 390 nm;
s3, re-dispersing the prefabricated material b in deionized water, heating to 95 ℃, dropwise adding 30kg of hydrazine hydrate, refluxing for 19 hours, centrifuging, washing, then adding deionized water, and carrying out low-temperature ball milling for 6.5min at 13 ℃ to obtain premix c;
s4, sequentially adding 1.5kg of sodium dodecyl benzene sulfonate, 1.5kg of polysiloxane defoaming agent and 1.5kg of carboxyl modified polysiloxane into premix c, uniformly mixing, sequentially adding 100kg of aqueous epoxy resin emulsion and 1.5kg of dodecyl trimethyl ammonium chloride, uniformly mixing, feeding into an ultrasonic oscillator, oscillating for 20min at the power of 450W, wherein the ultrasonic frequency is 23kHz, the temperature is maintained at 13 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
Comparative example 1
A preparation method of conductive graphene composite coating for automobiles comprises the following steps:
s1, adding 2kg of sodium dodecyl benzene sulfonate into water, uniformly mixing, adding 4.5kg of graphene oxide under a stirring state, stirring at a speed of 1500r/min for 10min, adding 2kg of nano titanium dioxide with the length of 1.2-1.8 mu m, the diameter of 80-100nm and the volume resistivity of 12.7 omega cm under a stirring state, carrying out ultrasonic treatment for 15min after complete addition, and obtaining a prefabricated material a with the ultrasonic power of 550W;
s2, re-dispersing the prefabricated material a in deionized water, heating to 95 ℃, dropwise adding 30kg of hydrazine hydrate, refluxing for 19 hours, centrifuging, washing, then adding deionized water, and carrying out low-temperature ball milling for 6.5min at 13 ℃ to obtain premix c;
s3, sequentially adding 1.5kg of sodium dodecyl benzene sulfonate, 1.5kg of polysiloxane defoaming agent and 1.5kg of carboxyl modified polysiloxane into premix c, uniformly mixing, sequentially adding 100kg of aqueous epoxy resin emulsion and 1.5kg of dodecyl trimethyl ammonium chloride, uniformly mixing, feeding into an ultrasonic oscillator, oscillating for 20min at the power of 450W, wherein the ultrasonic frequency is 23kHz, the temperature is maintained at 13 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
Comparative example 2
A preparation method of conductive graphene composite coating for automobiles comprises the following steps:
s1, adding 2kg of sodium dodecyl benzene sulfonate into water, uniformly mixing, adding 4.5kg of graphene oxide under a stirring state, stirring at a speed of 1500r/min for 10min, adding 2kg of nano titanium dioxide with the length of 1.2-1.8 mu m, the diameter of 80-100nm and the volume resistivity of 12.7 omega cm under a stirring state, carrying out ultrasonic treatment for 15min after complete addition, and obtaining a prefabricated material a with the ultrasonic power of 550W;
s2, adding 7kg of sodium hydroxide solution with the concentration of 1.7mol/L into the prefabricated material a, uniformly stirring, adjusting the temperature to 75 ℃, adding 0.3kg of N-hydroxysuccinimide under the stirring state, adding 3kg of linear polyethyleneimine, performing ultrasonic treatment for 20min, wherein the ultrasonic power is 350W, performing suction filtration, drying at 70 ℃, and crushing by using a jet mill under the protection of nitrogen to obtain a prefabricated material b with the average particle size of 390 nm;
s3, re-dispersing the prefabricated material b in deionized water, heating to 95 ℃, dropwise adding 30kg of hydrazine hydrate, refluxing for 19h, centrifuging, and washing to obtain a premix c;
s4, sequentially adding 1.5kg of sodium dodecyl benzene sulfonate, 1.5kg of polysiloxane defoaming agent and 1.5kg of carboxyl modified polysiloxane into premix c, uniformly mixing, sequentially adding 100kg of aqueous epoxy resin emulsion and 1.5kg of dodecyl trimethyl ammonium chloride, uniformly mixing, feeding into an ultrasonic oscillator, oscillating for 20min at the power of 450W, wherein the ultrasonic frequency is 23kHz, the temperature is maintained at 13 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
Comparative example 3
A preparation method of conductive graphene composite coating for automobiles comprises the following steps:
s1, adding 2kg of sodium dodecyl benzene sulfonate into water, uniformly mixing, adding 4.5kg of graphene oxide under a stirring state, stirring at 1500r/min, carrying out ultrasonic treatment for 15min after complete addition, wherein the ultrasonic power is 550W, and obtaining a prefabricated material a;
s2, adding 7kg of sodium hydroxide solution with the concentration of 1.7mol/L into the prefabricated material a, uniformly stirring, adjusting the temperature to 75 ℃, adding 0.3kg of N-hydroxysuccinimide under the stirring state, adding 3kg of linear polyethyleneimine, performing ultrasonic treatment for 20min, wherein the ultrasonic power is 350W, performing suction filtration, drying at 70 ℃, and crushing by using a jet mill under the protection of nitrogen to obtain a prefabricated material b with the average particle size of 390 nm;
s3, re-dispersing the prefabricated material b in deionized water, heating to 95 ℃, dropwise adding 30kg of hydrazine hydrate, refluxing for 19 hours, centrifuging, washing, then adding deionized water, and carrying out low-temperature ball milling for 6.5min at 13 ℃ to obtain premix c;
s4, sequentially adding 1.5kg of sodium dodecyl benzene sulfonate, 1.5kg of polysiloxane defoaming agent and 1.5kg of carboxyl modified polysiloxane into premix c, uniformly mixing, sequentially adding 100kg of aqueous epoxy resin emulsion and 1.5kg of dodecyl trimethyl ammonium chloride, uniformly mixing, feeding into an ultrasonic oscillator, oscillating for 20min at the power of 450W, wherein the ultrasonic frequency is 23kHz, the temperature is maintained at 13 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
Comparative example 4
A preparation method of conductive graphene composite coating for automobiles comprises the following steps:
s1, adding 2kg of sodium dodecyl benzene sulfonate into water, uniformly mixing, adding 4.5kg of graphene oxide under a stirring state, stirring at a speed of 1500r/min for 10min, adding 2kg of nano titanium dioxide with the length of 1.2-1.8 mu m, the diameter of 80-100nm and the volume resistivity of 12.7 omega cm under a stirring state, carrying out ultrasonic treatment for 15min after complete addition, and obtaining a prefabricated material a with the ultrasonic power of 550W;
s2, adding 7kg of sodium hydroxide solution with the concentration of 1.7mol/L into the prefabricated material a, uniformly stirring, adjusting the temperature to 75 ℃, adding 0.3kg of N-hydroxysuccinimide under the stirring state, adding 3kg of dendritic polyethyleneimine, carrying out ultrasonic treatment for 20min, wherein the ultrasonic power is 350W, carrying out suction filtration, drying at 70 ℃, and crushing by adopting a jet mill under the protection of nitrogen to obtain a prefabricated material b with the average particle size of 390 nm;
s3, re-dispersing the prefabricated material b in deionized water, heating to 95 ℃, dropwise adding 30kg of hydrazine hydrate, refluxing for 19 hours, centrifuging, washing, then adding deionized water, and carrying out low-temperature ball milling for 6.5min at 13 ℃ to obtain premix c;
s4, sequentially adding 1.5kg of sodium dodecyl benzene sulfonate, 1.5kg of polysiloxane defoaming agent and 1.5kg of carboxyl modified polysiloxane into premix c, uniformly mixing, sequentially adding 100kg of aqueous epoxy resin emulsion and 1.5kg of dodecyl trimethyl ammonium chloride, uniformly mixing, feeding into an ultrasonic oscillator, oscillating for 20min at the power of 450W, wherein the ultrasonic frequency is 23kHz, the temperature is maintained at 13 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
Conducting performance tests are carried out on the conductive graphene composite coating for the automobile obtained in the example 5 and the comparative examples 1 to 4, and the specific steps are as follows: coating each group of coatings on an ABS (acrylonitrile butadiene styrene) plate of 5cm multiplied by 10cm, drying for 15min at 80 ℃, measuring the surface resistance of any position of the paint film for 3 times by using a universal meter, wherein the thickness of the paint film is 200 mu m after the paint film is dried, and taking an average value; the smaller the measured resistance is, the better the conductivity of the composite coating is.
From the above table, it can be seen that: the conductive graphene composite coating for the automobile, which is obtained by the invention, has the lowest surface resistance and the best conductivity.
And (3) carrying out mechanical property test on the paint film, wherein the adhesion measurement is carried out according to GB/T1720, the impact strength measurement is carried out according to GB/T1732, the hardness measurement is carried out according to GB/T6739, the light transmittance is measured by a Nippon Shimadzu UV-3600 ultraviolet-visible spectrophotometer, and the results are as follows:
| example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Adhesion (cross-hatch method), grade | 0 | 1 | 0 | 1 | 0 |
| Impact strength, kg cm | 53 | 43 | 48 | 45 | 56 |
| Hardness of | 3H | H | 2H | H | 3H |
| Light transmittance% | 92 | 80 | 83 | 75 | 88 |
From the above, it can be seen that: the conductive graphene composite coating for the automobile has good mechanical property and high light transmittance, and is suitable for automobile plastic parts.
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 (9)
1. The conductive graphene composite coating for the automobile is characterized by comprising the following raw materials in parts by weight: 100 parts of water-based epoxy resin emulsion, 3-6 parts of graphene oxide, 20-40 parts of hydrazine hydrate, 1-3 parts of nano titanium dioxide, 1-3 parts of sodium dodecyl benzene sulfonate, 0.1-0.5 part of N-hydroxysuccinimide, 2-4 parts of linear polyethyleneimine, 4-10 parts of sodium hydroxide solution with the concentration of 1.5-2mol/L, 1-2 parts of stabilizer, 1-2 parts of defoaming agent, 1-2 parts of dispersant and 1-2 parts of softener.
2. The conductive graphene composite coating for the automobile according to claim 1, wherein the nano titanium dioxide has a diameter of 50-200nm, a length of 1-2 μm, and a volume resistivity of 5.0-20.0 Ω -cm.
3. The conductive graphene composite coating for the automobile according to claim 1, wherein the stabilizer is any one of tetrapropylene sodium benzene sulfonate, diisooctyl succinate sodium sulfonate, dibutyl naphthalene sodium sulfonate, sodium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate.
4. The conductive graphene composite coating for the automobile according to claim 1, wherein the defoaming agent is any one of a polyether defoaming agent, a polyether modified silicon defoaming agent and a polysiloxane defoaming agent.
5. The conductive graphene composite coating for the automobile according to claim 1, wherein the dispersant is at least one of octadecyl dimethyl hydroxyethyl ammonium nitrate, octadecyl dimethyl hydroxyethyl ammonium perchlorate, dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, triethyl methyl ammonium chloride, triethyl methyl ammonium bromide, and dodecyl trimethyl ammonium chloride.
6. The conductive graphene composite coating for the automobile according to claim 1, wherein the softening agent is at least one of polysiloxane microemulsion, amino polysiloxane emulsion, polyether modified polysiloxane emulsion, epoxy modified polysiloxane, and carboxyl modified polysiloxane.
7. The preparation method of the conductive graphene composite coating for the automobile as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
s1, adding sodium dodecyl benzene sulfonate into water, uniformly mixing, sequentially adding graphene oxide and nano titanium dioxide under a stirring state, and performing ultrasonic treatment for 10-20min after complete addition, wherein the ultrasonic power is 500-600W, so as to obtain a prefabricated material a;
s2, adding a sodium hydroxide solution into the prefabricated material a, uniformly stirring, adjusting the temperature to 70-80 ℃, adding N-hydroxysuccinimide under the stirring state, adding linear polyethyleneimine, performing ultrasonic treatment for 10-30min at the ultrasonic power of 300-400W, performing suction filtration and drying, and performing airflow crushing under the protection of nitrogen to obtain a prefabricated material b;
s3, re-dispersing the prefabricated material b in deionized water, heating to 90-100 ℃, dropwise adding hydrazine hydrate, refluxing for 18-20h, centrifuging, washing, then adding deionized water, and carrying out low-temperature ball milling for 5-8min at 10-15 ℃ to obtain premix c;
s4, sequentially adding a stabilizer, a defoaming agent and a softening agent into the premix c, uniformly mixing, sequentially adding the aqueous epoxy resin emulsion and a dispersing agent, uniformly mixing, carrying out 400-500W ultrasonic oscillation for 15-25min at an ultrasonic frequency of 15-30kHz, maintaining the temperature at 10-15 ℃ in the ultrasonic process, and filtering to obtain the conductive graphene composite coating for the automobile.
8. The preparation method of the conductive graphene composite coating for the automobile according to claim 7, wherein in S2, the drying temperature after suction filtration is 60-80 ℃.
9. The preparation method of the conductive graphene composite coating for the automobile as claimed in claim 7, wherein in S2, the particle size of the prefabricated material b is 300-500 nm.
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