CN112341907A - Environment-friendly conductive powder coating and preparation method thereof - Google Patents
Environment-friendly conductive powder coating and preparation method thereof Download PDFInfo
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- CN112341907A CN112341907A CN202011364333.4A CN202011364333A CN112341907A CN 112341907 A CN112341907 A CN 112341907A CN 202011364333 A CN202011364333 A CN 202011364333A CN 112341907 A CN112341907 A CN 112341907A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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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
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- 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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Abstract
The invention discloses an environment-friendly conductive powder coating which is characterized by being prepared from the following components in parts by weight: based on 2-3 parts of ferrocenyl alkynyl aniline Schiff base, 5-10 parts of graphene-coated nano aluminum powder, 55-65 parts of epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate, 20-30 parts of filler, 0.5-1.5 parts of phosphorus pentoxide, 4-8 parts of 2, 5-diaminobenzene sulfonic acid, 0.1-0.3 part of 1, 4-naphthoquinone, 2-5 parts of dispersant and 1-3 parts of flatting agent. The invention also discloses a preparation method of the environment-friendly conductive powder coating. The environment-friendly conductive powder coating disclosed by the invention has the advantages of good comprehensive performance, good conductivity, weather resistance and performance stability, high mechanical strength and coating adhesion, and safety and environment friendliness in use.
Description
Technical Field
The invention relates to the technical field of powder coatings, in particular to an environment-friendly conductive powder coating and a preparation method thereof.
Background
Electrically conductive coatings are functional coatings with the ability to conduct electrical current and dissipate accumulated static charge, and have important applications in a wide variety of fields. Can prevent the electronic component from being broken down due to electrostatic discharge in the antistatic field; the coating can be coated on the walls of a petroleum storage tank and a pipeline to release accumulated static charges so as to prevent explosion accidents; aiming at the electromagnetic interference in daily life, the conductive coating can play a role in absorbing electromagnetic waves; the conductive paint generates heat when electrified and can be used on the surface of some substrates needing heat as heating paint. With the rapid development of modern science and technology, the conductive coating also shows more and more superiority, and is widely applied to various military and civil industrial fields such as electronics, electric appliances, aviation, chemical engineering, printing and the like.
The conductive coating materials are mainly classified into an intrinsic type and an additive type, and among them, research on the additive type is more. The additive static conductive coating mainly fills conductive carbon series, metals, metal oxides, high molecular ions and the like, and the conductive coatings have the biggest problems of poor dispersibility and compatibility, direct influence on the adhesive force of the coating, easy oxidation of the metals, volatilization of harmful substances during preparation and use, environmental pollution, damage to human health, poor wear resistance and chemical resistance, thin construction film and low drying speed. In addition, most of the conductive coatings on the market adopt organic solvents as dispersion media, so that environmental pollution is easily caused, and the cost is increased due to the use of the organic solvents; although the water-based paint can better avoid environmental pollution and reduce cost, the water-based paint is slow to dry because water is used as a dispersion medium.
The powder coating is a novel solvent-free 100% solid powder coating, and has the characteristics of no solvent, no pollution, recoverability, environmental protection, energy and resource saving, labor intensity reduction, high mechanical strength of film coating and the like. The conductive powder coating has the advantages of low price, environmental protection, simple construction process and wide application prospect in the fields of corrosion prevention, electromagnetic shielding, static resistance and the like. However, the conductive powder coating in the prior art has poor mechanical strength and coating adhesion, the surface is easy to crack, and the corrosion resistance, the conductivity, the performance stability and the weather resistance are also required to be further improved.
The Chinese patent with application number 201710469206.2 discloses a new formula of a conductive powder coating, which comprises the following compounds in parts by weight: 56-60% of polyester resin, 2.7-4.6% of curing agent, 0.2-1.0% of sand streak agent, 0.1-0.8% of flatting agent, 0.3-0.8% of benzoin, 0.1-0.8% of wear-resistant wax powder, 0.5-10% of conductive carbon black, 10-20% of steel powder, 10-20% of electromagnetic shielding reinforcing agent and 0.1-2% of auxiliary agent, wherein the sum of the proportions of the components is 100%. The invention also discloses a preparation method of the novel formula of the conductive powder coating. By adding the electromagnetic shielding reinforcing agent, the produced coating has extremely low resistivity, good conductivity and excellent chemical properties. However, the steel powder added in the conductive filler has low connection strength, and can generate particle migration phenomenon under the conditions of direct current electric field and moisture, thereby reducing the conductive performance and influencing the service life of the conductive filler.
Therefore, the environment-friendly conductive powder coating which has good comprehensive performance, good conductivity, weather resistance and performance stability, high mechanical strength and high film adhesion, is safe and environment-friendly to use, meets the market demand, has wide market value and application prospect, and plays an important role in promoting the development of the functional coating industry.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides an environment-friendly conductive powder coating which is characterized by being prepared from the following components in parts by weight: based on 2-3 parts of ferrocenyl alkynyl aniline Schiff base, 5-10 parts of graphene-coated nano aluminum powder, 55-65 parts of epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate, 20-30 parts of filler, 0.5-1.5 parts of phosphorus pentoxide, 4-8 parts of 2, 5-diaminobenzene sulfonic acid, 0.1-0.3 part of 1, 4-naphthoquinone, 2-5 parts of dispersant and 1-3 parts of flatting agent.
Preferably, the leveling agent is one or more of a polyacrylate leveling agent, a cellulose acetate butyrate leveling agent and a polyvinyl butyral leveling agent.
Preferably, the dispersant is at least one of EFKA4046, sodium hexametaphosphate and sodium polycarboxylate.
Preferably, the filler is at least one of calcium hydrogen peroxide, titanium dioxide and talcum powder; the grain diameter of the filler is 800-1000 meshes.
Preferably, the preparation method of the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate comprises the following steps:
step D1, adding 2,3,5, 6-tetrafluoroterephthalic acid, 2, 4-diamino-6-diethylamino-1, 3, 5-triazine into a high boiling point solvent, reacting for 2-3 hours at 185-195 ℃ under normal pressure, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, heating to 210-230 ℃, carrying out primary polycondensation for 5-7 hours, transferring the reaction solution into a reaction kettle, vacuumizing to 500Pa, heating to 235-255 ℃, carrying out polycondensation for 6-8 hours, cooling to room temperature after the reaction is finished, adjusting to normal pressure, precipitating in water, carrying out suction filtration, washing the crude product for 4-8 times by ethanol, placing in a vacuum drying oven at 85-95 ℃ and drying to constant weight, obtaining 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate;
and D2, adding the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate prepared in the step D1 and epoxy chloropropane into dimethyl sulfoxide, stirring and reacting for 4-6 hours at 40-60 ℃, precipitating in ethanol, and drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate.
Preferably, the molar ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 2, 4-diamino-6-diethylamino-1, 3, 5-triazine, the high boiling point solvent, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine in the step D1 is 1:1 (8-15) to 0.8-1.2: 0.5.
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the mass ratio of the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate, epichlorohydrin and dimethyl sulfoxide in the step D2 is (3-5): (0.4-0.7): (15-25).
Preferably, the preparation method of the ferrocenyl alkynyl aniline based Schiff base comprises the following steps: adding ferrocenyl formaldehyde and m-aminophenylacetylene into an organic solvent, stirring and reacting for 3-5 hours at 80-90 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation to obtain the ferrocenyl alkynyl aniline Schiff base.
Preferably, the molar ratio of the ferrocenecarboxaldehyde to the m-aminophenylacetylene to the organic solvent is 1:1 (6-10).
Preferably, the organic solvent is any one of ethanol, isopropanol, toluene and tetrahydrofuran.
Another objective of the present invention is to provide a method for preparing the environment-friendly conductive powder coating, which is characterized by comprising the following steps: putting the components in parts by weight into a high-speed mixer, mixing for 5-8min to obtain a mixture, then feeding the mixture into a double-screw extruder for melt extrusion, tabletting the obtained molten material by a tabletting machine, controlling the thickness to be 3-6mm, crushing and feeding the obtained molten material into a grinding mill for crushing and grading, separating fine powder, impurities and the like by a cyclone separator, screening the product by a powder screen to obtain a product, sieving the powder to 200-300 meshes, and curing for 3-4 days to obtain the finished product of the environment-friendly conductive powder coating.
Preferably, the melt extrusion temperature is 115-135 ℃.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the environment-friendly conductive powder coating provided by the invention is simple and feasible, has high preparation effect and yield, is convenient to operate and control, is suitable for continuous large-scale production, and has higher economic value, social value and ecological value.
(2) The environment-friendly conductive powder coating provided by the invention overcomes the defects that the conductive powder coating in the prior art is poor in mechanical strength and coating adhesion, easy to crack on the surface, and further needs to be improved in corrosion resistance, conductivity, performance stability and weather resistance, and has the advantages of good comprehensive performance, good conductivity, weather resistance and performance stability, high mechanical strength and coating adhesion, safety in use and environment friendliness through the synergistic effect of the components.
(3) According to the environment-friendly conductive powder coating provided by the invention, the ferrocenyl alkynyl aniline Schiff base is added, so that the conductivity is effectively improved under the dual effects of an electronic effect and a conjugate effect; the graphene coated nano aluminum powder has a synergistic effect with the graphene coated nano aluminum powder, so that the conductive, antistatic and electromagnetic shielding functions are better; the aluminum powder can be effectively protected by coating the graphene, and the defects that the aluminum powder is corroded, the connection strength is low, and the conductivity is reduced and the service life is influenced due to the fact that the particle migration phenomenon is generated under the conditions of a direct current electric field and moisture are effectively overcome; the advantages of various conductive fillers are combined, so that the conductivity and the performance stability are better.
(4) The environment-friendly conductive powder coating provided by the invention takes epoxy group 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate as a film forming substance, the film forming substance has good film forming performance, triazine, amide and fluorobenzene structures are introduced on a molecular chain, the coating has better weather resistance, aging resistance, water resistance and mechanical property under the synergistic action, and reaction sites can be provided for the subsequent coating crosslinking and curing through the introduction of the epoxy group; the introduction of quaternary ammonium salt cationic groups can play roles in resisting bacteria and static electricity and improving the adhesion between the coating and the base material.
(5) According to the environment-friendly conductive powder coating provided by the invention, 2, 5-diaminobenzene sulfonic acid is added, under the catalytic action of phosphorus pentoxide, the sulfonic group on the coating is easy to be connected with a benzene ring on the basis of ferrocenyl alkynyl aniline Schiff base through chemical reaction, and meanwhile, the sulfonic group can be connected with quaternary ammonium salt on a film-forming polymer molecular chain through ion exchange in an ionic bond; the amino groups on the film-forming polymer can generate crosslinking curing reaction with epoxy groups on the molecular chain of the film-forming polymer, so that the components form a three-dimensional network structure in the form of chemical bonds, and the comprehensive performance and the performance stability of the film-forming polymer are effectively improved; the addition of the 1, 4-naphthoquinone can effectively improve the stability of the ferrocenyl alkynyl aniline Schiff base, so that the conductive stability is improved. The coating takes air as a dispersion medium, so that the coating has better environmental protection performance and faster drying and curing.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention; the preparation method of the graphene coated nano aluminum powder involved in the embodiment of the invention is disclosed in the embodiment 1 of the Chinese patent with the application number of 201510319344.3; other raw materials were all purchased commercially.
Example 1
The environment-friendly conductive powder coating is characterized by being prepared from the following components in parts by weight: based on 2 parts of ferrocenyl alkynyl aniline Schiff base, 5 parts of graphene-coated nano aluminum powder, 55 parts of epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate, 20 parts of filler, 0.5 part of phosphorus pentoxide, 4 parts of 2, 5-diaminobenzene sulfonic acid, 0.1 part of 1, 4-naphthoquinone, 2 parts of dispersant and 1 part of flatting agent.
The flatting agent is a polyacrylate flatting agent; the dispersing agent is EFKA 4046; the filler is double flying powder; the particle size of the filler is 800 meshes.
The preparation method of the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate comprises the following steps:
step D1, mixing 2,3,5, 6-tetrafluoroterephthalic acid, 2, 4-diamino-6-diethylamino-1, 3,5-
Adding triazine into high boiling point solvent, reacting at 185 deg.C under normal pressure for 2 hr, adding 1-ethyl
Heating- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine to 210 ℃, carrying out primary polycondensation for 5 hours, then transferring the reaction liquid into a reaction kettle, vacuumizing to 500Pa, heating to 235 ℃, carrying out polycondensation for 6 hours, cooling to room temperature after the reaction is finished, adjusting to normal pressure, precipitating in water, carrying out suction filtration, washing the crude product for 4 times by using ethanol, and then placing in a vacuum drying box at 85 ℃ for drying to constant weight to obtain a 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate;
and D2, adding the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate prepared in the step D1 and epoxy chloropropane into dimethyl sulfoxide, stirring and reacting for 4 hours at 40 ℃, precipitating in ethanol, and drying in a vacuum drying oven at 80 ℃ to constant weight to obtain the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate.
The molar ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 2, 4-diamino-6-diethylamino-1, 3, 5-triazine, the high-boiling solvent, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine in the step D1 is 1:1:8:0.8: 0.5; the high boiling point solvent is dimethyl sulfoxide.
In the step D2, the mass ratio of the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate to epichlorohydrin to dimethyl sulfoxide is 3:0.4: 15.
The preparation method of the ferrocenyl alkynyl aniline Schiff base comprises the following steps: adding ferrocenyl formaldehyde and m-aminophenylacetylene into an organic solvent, stirring and reacting for 3 hours at 80 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation to obtain ferrocenyl alkynyl aniline Schiff base; the molar ratio of the ferrocene formaldehyde to the m-aminophenylacetylene to the organic solvent is 1:1: 6; the organic solvent is ethanol.
The preparation method of the environment-friendly conductive powder coating is characterized by comprising the following steps of: putting the components in parts by weight into a high-speed mixer, mixing for 5min to obtain a mixture, then feeding the mixture into a double-screw extruder for melt extrusion, tabletting the obtained molten material by a tablet machine, controlling the thickness to be 3mm, crushing and feeding the obtained molten material into a pulverizer for crushing and grading, separating fine powder, impurities and the like by a cyclone separator, screening the product by a powder screen, sieving the powder to 200 meshes, and curing for 3 days to obtain a finished product of the environment-friendly conductive powder coating; the melt extrusion temperature was 115 ℃.
Example 2
The environment-friendly conductive powder coating is characterized by being prepared from the following components in parts by weight: based on 2.3 parts of ferrocenyl alkynyl aniline Schiff base, 6 parts of graphene-coated nano aluminum powder, 57 parts of epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate, 23 parts of filler, 0.7 part of phosphorus pentoxide, 6 parts of 2, 5-diaminobenzene sulfonic acid, 0.15 part of 1, 4-naphthoquinone, 3 parts of dispersant and 1.5 parts of flatting agent.
The leveling agent is cellulose acetate butyrate leveling agent; the dispersant is sodium hexametaphosphate; the filler is titanium dioxide; the particle size of the filler is 850 meshes.
The preparation method of the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate comprises the following steps:
step D1, adding 2,3,5, 6-tetrafluoroterephthalic acid, 2, 4-diamino-6-diethylamino-1, 3, 5-triazine into a high boiling point solvent, reacting for 2.3 hours at 188 ℃ under normal pressure, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, heating to 215 ℃ for primary polycondensation for 5.5 hours, transferring the reaction solution into a reaction kettle, vacuumizing to 500Pa, heating to 240 ℃, performing polycondensation for 6.5 hours, cooling to room temperature after the reaction is finished, adjusting to normal pressure, precipitating in water, performing suction filtration, washing the crude product for 5 times by using ethanol, drying to constant weight at 86 ℃ in a vacuum drying box to obtain 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensates;
and D2, adding the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate prepared in the step D1 and epoxy chloropropane into dimethyl sulfoxide, stirring and reacting for 4.5 hours at 45 ℃, precipitating in ethanol, and drying in a vacuum drying oven at 83 ℃ to constant weight to obtain the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate.
The molar ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 2, 4-diamino-6-diethylamino-1, 3, 5-triazine, the high-boiling solvent, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine in the step D1 is 1:1:9:0.9: 0.5; the high boiling point solvent is N, N-dimethylformamide.
In the step D2, the mass ratio of the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate to epichlorohydrin to dimethyl sulfoxide is 3.5:0.5: 17.
The preparation method of the ferrocenyl alkynyl aniline Schiff base comprises the following steps: adding ferrocenyl formaldehyde and m-aminophenylacetylene into an organic solvent, stirring and reacting for 3.5 hours at 83 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation to obtain ferrocenyl alkynyl aniline Schiff base; the molar ratio of the ferrocene formaldehyde to the m-aminophenylacetylene to the organic solvent is 1:1: 7; the organic solvent is isopropanol.
The preparation method of the environment-friendly conductive powder coating is characterized by comprising the following steps of: putting the components in parts by weight into a high-speed mixer, mixing for 6min to obtain a mixture, then feeding the mixture into a double-screw extruder for melt extrusion, tabletting the obtained molten material by a tablet machine, controlling the thickness to be 4mm, crushing and feeding the obtained molten material into a pulverizer for crushing and grading, separating fine powder, impurities and the like by a cyclone separator, screening the product by a powder screen, wherein the powder screen is 220 meshes, and curing for 3.2 days to obtain a finished product of the environment-friendly conductive powder coating; the melt extrusion temperature was 120 ℃.
Example 3
The environment-friendly conductive powder coating is characterized by being prepared from the following components in parts by weight: based on 2.5 parts of ferrocenyl alkynyl aniline Schiff base, 7.5 parts of graphene-coated nano aluminum powder, 60 parts of epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate, 25 parts of filler, 1 part of phosphorus pentoxide, 6 parts of 2, 5-diaminobenzene sulfonic acid, 0.2 part of 1, 4-naphthoquinone, 3.5 parts of dispersant and 2 parts of flatting agent.
The flatting agent is a polyvinyl butyral flatting agent; the dispersant is sodium polycarboxylate; the filler is talcum powder; the particle size of the filler is 900 meshes.
The preparation method of the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate comprises the following steps:
step D1, adding 2,3,5, 6-tetrafluoroterephthalic acid, 2, 4-diamino-6-diethylamino-1, 3, 5-triazine into a high boiling point solvent, reacting for 2.5 hours at 190 ℃ under normal pressure, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, heating to 220 ℃ for primary polycondensation for 6 hours, transferring the reaction liquid into a reaction kettle, vacuumizing to 500Pa, heating to 245 ℃, performing polycondensation for 7 hours, cooling to room temperature after the reaction is finished, adjusting to normal pressure, precipitating in water, performing suction filtration, washing the crude product with ethanol for 6 times, drying in a vacuum drying oven at 90 ℃ to constant weight to obtain 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensates;
and D2, adding the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate prepared in the step D1 and epoxy chloropropane into dimethyl sulfoxide, stirring and reacting for 5 hours at 50 ℃, precipitating in ethanol, and drying in a vacuum drying oven at 85 ℃ to constant weight to obtain the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate.
The molar ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 2, 4-diamino-6-diethylamino-1, 3, 5-triazine, the high-boiling-point solvent, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine in the step D1 is 1:1:12:1: 0.5; the high boiling point solvent is N, N-dimethylacetamide.
In the step D2, the mass ratio of the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate to epichlorohydrin to dimethyl sulfoxide is 4:0.55: 20.
The preparation method of the ferrocenyl alkynyl aniline Schiff base comprises the following steps: adding ferrocenyl formaldehyde and m-aminophenylacetylene into an organic solvent, stirring and reacting for 4 hours at 85 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation to obtain ferrocenyl alkynyl aniline Schiff base; the molar ratio of the ferrocene formaldehyde to the m-aminophenylacetylene to the organic solvent is 1:1: 8; the organic solvent is toluene.
The preparation method of the environment-friendly conductive powder coating is characterized by comprising the following steps of: putting the components in parts by weight into a high-speed mixer, mixing for 6.5min to obtain a mixture, then feeding the mixture into a double-screw extruder for melt extrusion, tabletting the obtained molten material by a tabletting machine, controlling the thickness to be 4.5mm, crushing and feeding the obtained molten material into a grinding mill for crushing and grading, separating fine powder, impurities and the like by a cyclone separator, screening the product by a powder screen to obtain a product, and curing for 3.5 days to obtain a finished product of the environment-friendly conductive powder coating; the melt extrusion temperature was 125 ℃.
Example 4
The environment-friendly conductive powder coating is characterized by being prepared from the following components in parts by weight: based on 2.8 parts of ferrocenyl alkynyl aniline Schiff base, 9 parts of graphene-coated nano aluminum powder, 63 parts of epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate, 28 parts of filler, 1.3 parts of phosphorus pentoxide, 7.5 parts of 2, 5-diaminobenzene sulfonic acid, 0.25 part of 1, 4-naphthoquinone, 4.5 parts of dispersant and 2.5 parts of flatting agent.
The flatting agent is formed by mixing a polyacrylate flatting agent, a cellulose acetate butyrate flatting agent and a polyvinyl butyral flatting agent according to the mass ratio of 1:2: 3; the dispersing agent is formed by mixing EFKA4046, sodium hexametaphosphate and sodium polycarboxylate according to the mass ratio of 2:1: 4; the filler is formed by mixing double flying powder, titanium dioxide and talcum powder according to the mass ratio of 2:2: 5; the particle size of the filler is 950 meshes.
The preparation method of the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate comprises the following steps:
step D1, adding 2,3,5, 6-tetrafluoroterephthalic acid, 2, 4-diamino-6-diethylamino-1, 3, 5-triazine into a high boiling point solvent, reacting for 2.8 hours at 193 ℃ under normal pressure, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, heating to 225 ℃, carrying out primary polycondensation for 6.5 hours, transferring the reaction solution into a reaction kettle, vacuumizing to 500Pa, heating to 253 ℃, carrying out polycondensation for 7.8 hours, cooling to room temperature after the reaction is finished, adjusting to normal pressure, precipitating in water, carrying out suction filtration, washing the crude product with ethanol for 7 times, placing in a vacuum drying oven for drying at 93 ℃ to constant weight to obtain 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensates;
and D2, adding the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate prepared in the step D1 and epoxy chloropropane into dimethyl sulfoxide, stirring and reacting for 5.7 hours at 55 ℃, precipitating in ethanol, and drying in a vacuum drying oven at 88 ℃ to constant weight to obtain the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate.
The molar ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 2, 4-diamino-6-diethylamino-1, 3, 5-triazine, the high-boiling solvent, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine in the step D1 is 1:1:14:1.1: 0.5; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 4:3:5: 1.
In the step D2, the mass ratio of the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate to epichlorohydrin to dimethyl sulfoxide is 4.8:0.65: 23.
The preparation method of the ferrocenyl alkynyl aniline Schiff base comprises the following steps: adding ferrocenyl formaldehyde and m-aminophenylacetylene into an organic solvent, stirring and reacting for 4.5 hours at 88 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation to obtain ferrocenyl alkynyl aniline Schiff base; the molar ratio of the ferrocene formaldehyde to the m-aminophenylacetylene to the organic solvent is 1:1: 9.5; the organic solvent is tetrahydrofuran.
The preparation method of the environment-friendly conductive powder coating is characterized by comprising the following steps of: putting the components in parts by weight into a high-speed mixer, mixing for 7.5min to obtain a mixture, then feeding the mixture into a double-screw extruder for melt extrusion, tabletting the obtained molten material by a tabletting machine, controlling the thickness to be 5mm, crushing and feeding the obtained molten material into a flour mill for crushing and grading, separating fine powder, impurities and the like by a cyclone separator, screening the product by a powder screen, wherein the powder screen is 280 meshes, and curing for 3.8 days to obtain a finished product of the environment-friendly conductive powder coating; the melt extrusion temperature was 130 ℃.
Example 5
The environment-friendly conductive powder coating is characterized by being prepared from the following components in parts by weight: based on 3 parts of ferrocenyl alkynyl aniline Schiff base, 10 parts of graphene-coated nano aluminum powder, 65 parts of epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate, 30 parts of filler, 1.5 parts of phosphorus pentoxide, 8 parts of 2, 5-diaminobenzene sulfonic acid, 0.3 part of 1, 4-naphthoquinone, 5 parts of dispersant and 3 parts of flatting agent.
The flatting agent is a polyacrylate flatting agent; the dispersant is sodium hexametaphosphate; the filler is talcum powder; the particle size of the filler is 1000 meshes.
The preparation method of the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate comprises the following steps:
step D1, adding 2,3,5, 6-tetrafluoroterephthalic acid, 2, 4-diamino-6-diethylamino-1, 3, 5-triazine into a high boiling point solvent, reacting for 3 hours at 195 ℃ under normal pressure, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, heating to 230 ℃, carrying out primary polycondensation for 7 hours, transferring the reaction solution into a reaction kettle, vacuumizing to 500Pa, heating to 255 ℃, carrying out polycondensation for 8 hours, cooling to room temperature after the reaction is finished, adjusting to normal pressure, precipitating in water, carrying out suction filtration, washing the crude product for 8 times by ethanol, drying in a vacuum drying oven at 95 ℃ to constant weight to obtain 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensates;
and D2, adding the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate prepared in the step D1 and epoxy chloropropane into dimethyl sulfoxide, stirring and reacting for 6 hours at 60 ℃, precipitating in ethanol, and drying in a vacuum drying oven at 90 ℃ to constant weight to obtain the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate.
The molar ratio of the 2,3,5, 6-tetrafluoroterephthalic acid, the 2, 4-diamino-6-diethylamino-1, 3, 5-triazine, the high-boiling solvent, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine in the step D1 is 1:1:15:1.2: 0.5; the high boiling point solvent is N-methyl pyrrolidone.
In the step D2, the mass ratio of the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate to epichlorohydrin to dimethyl sulfoxide is 5:0.7: 25.
The preparation method of the ferrocenyl alkynyl aniline Schiff base comprises the following steps: adding ferrocenyl formaldehyde and m-aminophenylacetylene into an organic solvent, stirring and reacting for 5 hours at 90 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation to obtain ferrocenyl alkynyl aniline Schiff base; the molar ratio of the ferrocene formaldehyde to the m-aminophenylacetylene to the organic solvent is 1:1: 10; the organic solvent is ethanol.
The preparation method of the environment-friendly conductive powder coating is characterized by comprising the following steps of: putting the components in parts by weight into a high-speed mixer, mixing for 8min to obtain a mixture, then feeding the mixture into a double-screw extruder for melt extrusion, tabletting the obtained molten material by a tablet machine, controlling the thickness to be 6mm, crushing and feeding the obtained molten material into a pulverizer for crushing and grading, separating fine powder, impurities and the like by a cyclone separator, screening the product by a powder screen, and aging for 4 days to obtain a finished product of the environment-friendly conductive powder coating, wherein the powder screen is 300 meshes; the melt extrusion temperature was 135 ℃.
Comparative example 1
This example provides an environmentally friendly conductive powder coating, which is formulated and prepared substantially the same as in example 1, except that no ferrocenyl alkynyl aniline based schiff base is added.
Comparative example 2
The present example provides an environment-friendly conductive powder coating, which has a formulation and a preparation method substantially the same as those of example 1, except that no graphene-coated nano aluminum powder is added.
Comparative example 3
The present example provides an environment-friendly conductive powder coating, the formulation and preparation method of which are substantially the same as those of example 1, except that graphene is used instead of graphene to coat nano aluminum powder.
Comparative example 4
This example provides an environmentally friendly conductive powder coating having substantially the same formulation and preparation as example 1, except that no 2, 5-diaminobenzenesulphonic acid is added.
The environmental-friendly conductive powder coatings obtained in the above examples 1 to 5 and comparative examples 1 to 4 were subjected to the relevant performance tests, and the test results and the test methods are shown in table 1.
TABLE 1 environmental protection conductive powder coating test Performance of examples and comparative examples
As can be seen from Table 1, the environment-friendly conductive powder coating disclosed by the embodiment of the invention has better conductive, water-resistant and impact-resistant properties and stronger adhesive force and thermal hardness compared with a comparative product, which are the results of synergistic action of the components.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The environment-friendly conductive powder coating is characterized by being prepared from the following components in parts by weight: based on 2-3 parts of ferrocenyl alkynyl aniline Schiff base, 5-10 parts of graphene-coated nano aluminum powder, 55-65 parts of epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate, 20-30 parts of filler, 0.5-1.5 parts of phosphorus pentoxide, 4-8 parts of 2, 5-diaminobenzene sulfonic acid, 0.1-0.3 part of 1, 4-naphthoquinone, 2-5 parts of dispersant and 1-3 parts of flatting agent.
2. The environment-friendly conductive powder coating as claimed in claim 1, wherein the leveling agent is one or more of a polyacrylate leveling agent, a cellulose acetate butyrate leveling agent and a polyvinyl butyral leveling agent; the dispersing agent is at least one of EFKA4046, sodium hexametaphosphate and sodium polycarboxylate.
3. The environment-friendly conductive powder coating as claimed in claim 1, wherein the filler is at least one of calcium carbonate, titanium dioxide and talcum powder; the grain diameter of the filler is 800-1000 meshes.
4. The environmentally friendly conductive powder coating of claim 1, wherein the epoxy-based 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate is prepared by a method comprising the steps of:
step D1, adding 2,3,5, 6-tetrafluoroterephthalic acid, 2, 4-diamino-6-diethylamino-1, 3, 5-triazine into a high boiling point solvent, reacting for 2-3 hours at 185-195 ℃ under normal pressure, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, heating to 210-230 ℃, carrying out primary polycondensation for 5-7 hours, transferring the reaction solution into a reaction kettle, vacuumizing to 500Pa, heating to 235-255 ℃, carrying out polycondensation for 6-8 hours, cooling to room temperature after the reaction is finished, adjusting to normal pressure, precipitating in water, carrying out suction filtration, washing the crude product for 4-8 times by ethanol, placing in a vacuum drying oven at 85-95 ℃ and drying to constant weight, obtaining 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate;
and D2, adding the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate prepared in the step D1 and epoxy chloropropane into dimethyl sulfoxide, stirring and reacting for 4-6 hours at 40-60 ℃, precipitating in ethanol, and drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the epoxy 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate.
5. The environmentally friendly conductive powder coating of claim 4, wherein the molar ratio of 2,3,5, 6-tetrafluoroterephthalic acid, 2, 4-diamino-6-diethylamino-1, 3, 5-triazine, high boiling point solvent, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine in step D1 is 1:1 (8-15) to (0.8-1.2) to 0.5.
6. The environmentally friendly conductive powder coating of claim 4, wherein the high boiling point solvent is at least one of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
7. The environmentally friendly conductive powder coating of claim 4, wherein the mass ratio of the 2,3,5, 6-tetrafluoroterephthalic acid/2, 4-diamino-6-diethylamino-1, 3, 5-triazine polycondensate, epichlorohydrin and dimethylsulfoxide in step D2 is (3-5): (0.4-0.7): (15-25).
8. The environment-friendly conductive powder coating as claimed in claim 1, wherein the preparation method based on ferrocenyl alkynyl aniline Schiff base comprises the following steps: adding ferrocenyl formaldehyde and m-aminophenylacetylene into an organic solvent, stirring and reacting for 3-5 hours at 80-90 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation to obtain the ferrocenyl alkynyl aniline Schiff base.
9. The environment-friendly conductive powder coating as claimed in claim 8, wherein the molar ratio of the ferrocene carboxaldehyde to the m-aminophenylacetylene to the organic solvent is 1:1 (6-10); the organic solvent is any one of ethanol, isopropanol, toluene and tetrahydrofuran.
10. A method for preparing the environment-friendly conductive powder coating according to any one of claims 1 to 9, which comprises the following steps: putting the components in parts by weight into a high-speed mixer, mixing for 5-8min to obtain a mixture, then feeding the mixture into a double-screw extruder for melt extrusion, tabletting the obtained molten material by a tabletting machine, controlling the thickness to be 3-6mm, crushing and feeding the obtained molten material into a grinding mill for crushing and grading, separating fine powder, impurities and the like by a cyclone separator, screening the product by a powder screen to obtain a product, sieving the powder to 200-300 meshes, and curing for 3-4 days to obtain the finished product of the environment-friendly conductive powder coating.
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| CN114672241A (en) * | 2022-03-02 | 2022-06-28 | 宁波辰磁电子科技有限公司 | Coating for magnetic roller surface of magnetic separator |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102604533A (en) * | 2012-03-14 | 2012-07-25 | 哈尔滨工程大学 | Polyaniline-graphene composite based anticorrosive paint and preparation method thereof |
| US20130274376A1 (en) * | 2012-04-17 | 2013-10-17 | Xerox Corporation | Surface coating and fuser member |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102604533A (en) * | 2012-03-14 | 2012-07-25 | 哈尔滨工程大学 | Polyaniline-graphene composite based anticorrosive paint and preparation method thereof |
| US20130274376A1 (en) * | 2012-04-17 | 2013-10-17 | Xerox Corporation | Surface coating and fuser member |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672241A (en) * | 2022-03-02 | 2022-06-28 | 宁波辰磁电子科技有限公司 | Coating for magnetic roller surface of magnetic separator |
| CN114672241B (en) * | 2022-03-02 | 2022-10-04 | 宁波辰磁电子科技有限公司 | Coating for surface of magnetic roller of magnetic separator |
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