CN112552794B - High-heat-resistance coating for battery case and preparation method thereof - Google Patents
High-heat-resistance coating for battery case 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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- 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
- C09D5/18—Fireproof paints including high temperature resistant 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
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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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- 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
- C09D7/63—Additives non-macromolecular organic
Abstract
The invention discloses a high heat-resistant coating for a storage battery shell and a preparation method thereof, wherein the high heat-resistant coating comprises the following raw materials in parts by weight: 50-60 parts of epoxy resin E44, 10-15 parts of reinforcing filler, 3-5 parts of graphene, 3-5 parts of talcum powder, 20-30 parts of ethanol, 20-30 parts of ethylene glycol ethyl ether, 3-5 parts of film-forming assistant, 1-3 parts of defoaming agent and 8-10 parts of diethylenetriamine; this reinforcing filler contains quartzy, simultaneously with the cooperation of other inorganic fillers make high heat-resisting coating's shock resistance further promote, and this reinforcing filler surface contains a large amount of oxazine ring structures and conjugated double bond structure, can promote the heat resistance of coating greatly, the surface contains a large amount of imide structures simultaneously, make the reinforcing filler on contain a large amount of ether linkages, further promote coating toughness, make the battery case when receiving the collision, it can not appear damaged to film, and then the protection of filming to the battery case of assurance, the life of storage battery has been increased.
Description
Technical Field
The invention relates to the technical field of coating preparation, in particular to a high-heat-resistance coating for a storage battery shell and a preparation method thereof.
Background
Coatings have been widely used in various areas of daily life, including their functions of decoration, protection, and other specific purposes. The coating material is generally composed of a film-forming resin, a filler, and the like. Acrylic resins are a widely used class of coating film-forming resins. The coating properties such as strength, hardness, scratch resistance, aging resistance and the like can be improved by the crosslinking treatment. During crosslinking, the functional groups of the film-forming resin chemically react to form a crosslinked network of polymers. For example, the polymer network is formed by chemical reactions between epoxy groups, isocyanate groups, amine groups, carboxyl groups, and vinyl groups.
The material of storage battery shell is mostly plastics, and plastics are easy to appear ageing at long-time use, consequently can paint coating on storage battery shell surface, and current coating heat resistance is general, under the higher environment of temperature, film can appear the fracture bubble, leads to droing and then unable protection storage battery shell even, and removes the in-process at the storage battery and easily receives to collide with, collides with and makes to film the damage, leads to filming unable protection storage battery shell.
Disclosure of Invention
The invention aims to provide a high-heat-resistance coating for a storage battery shell and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the material of storage battery shell is mostly plastics, and plastics are easy to appear ageing at long-time use, consequently can paint coating on storage battery shell surface, and current coating heat resistance is general, under the higher environment of temperature, film can appear the fracture bubble, leads to droing and then unable protection storage battery shell even, and removes the in-process at the storage battery and easily receives to collide with, collides with and makes to film the damage, leads to filming unable protection storage battery shell.
The purpose of the invention can be realized by the following technical scheme:
a high heat-resistant coating for a storage battery shell comprises the following raw materials in parts by weight: 50-60 parts of epoxy resin E44, 10-15 parts of reinforcing filler, 3-5 parts of graphene, 3-5 parts of talcum powder, 20-30 parts of ethanol, 20-30 parts of ethylene glycol ethyl ether, 3-5 parts of film-forming assistant, 1-3 parts of defoaming agent and 8-10 parts of diethylenetriamine;
the high heat-resistant coating is prepared by the following steps:
step S1: adding ethanol, ethylene glycol ethyl ether and a film-forming additive into a stirring kettle, stirring for 20-30min under the condition that the rotation speed is 300-500r/min, adding epoxy resin E44, and continuously stirring for 1-1.5h to prepare a first mixture;
step S2: adding the first mixture prepared in the step S1 and a defoaming agent into a stirring kettle, and stirring for 1-1.5h under the condition that the rotating speed is 800-;
step S3: and (4) adding the second mixture prepared in the step (S2), the reinforcing filler, the talcum powder, the graphene and the diethylenetriamine into a stirring kettle, and carrying out ultrasonic treatment for 30-50min under the condition that the frequency is 8-10MHz to prepare the high-heat-resistance coating.
Furthermore, the fineness of the reinforcing filler, the graphene and the talcum powder is 200-300 meshes, the film-forming assistant is one or two of propylene glycol butyl ether and propylene glycol methyl ether acetate which are mixed in any proportion, and the defoaming agent is one or more of polydimethylsiloxane, tributyl phosphate and polyoxyethylene polyoxypropylene pentaerythritol ether which are mixed in any proportion.
Further, the reinforcing filler is prepared by the following steps:
step A1: drying the quartz powder for 40-50min at the temperature of 160-180 ℃, soaking the quartz powder in an ammonia solution at the rotation speed of 300-500r/min at the temperature of 60-80 ℃ for 1.5-3h to prepare active quartz powder;
step A2: adding dimethyl diethoxy silane, methyl triethoxysilane and xylene into a reaction kettle, stirring for 10-15min under the conditions of the rotation speed of 150-200r/min and the temperature of 65-70 ℃, dropwise adding a hydrochloric acid solution for 40-60min, adding the active quartz prepared in the step A1 after dropwise adding, reacting for 3-5h under the condition of the temperature of 75-80 ℃, filtering to remove filtrate, drying a filter cake for 15-20min under the conditions of the vacuum degree of 0.08-0.1MPa and the temperature of 95-100 ℃, heating to the temperature of 120-130 ℃, and continuing to dry for 30-40min to prepare a modified carrier;
step A3: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions of conversion to 150-plus-one (200 r/min) and temperature of 10-15 ℃, reacting for 1-1.5h under the condition of temperature of 40-45 ℃ to obtain an intermediate 1, adding the intermediate 1, iron powder and ethanol into the reaction kettle, performing reflux reaction for 3-5h under the condition of temperature of 80-85 ℃, adding a hydrochloric acid solution for 20min, continuously reacting for 5-8h, adjusting the pH value of a reaction solution to 7-8 to obtain an intermediate 2, mixing the intermediate 2 with deionized water, and performing reflux for 10-15min under the condition of temperature of 110-plus-one (120 ℃) to obtain an intermediate 3;
the reaction process is as follows:
step A4: adding the intermediate 3, paraformaldehyde, N-dimethylacetamide and xylene into a reaction kettle, stirring for 20-30min at the rotation speed of 150-;
the reaction process is as follows:
step A5: adding the intermediate 6, hydroxylamine hydrochloride and ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of a rotation speed of 150-35 ℃ and a temperature of 30-35 ℃, reacting for 3-5h, heating to a temperature of 70-80 ℃, refluxing for 5-8min, adding hydrochloric acid solution, stirring for 5-10min to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3-5h under the conditions of a rotation speed of 200-300r/min and a temperature of 40-50 ℃, cooling to a temperature of 0 ℃, adding ammonia water and sodium hydroxide solution, reacting for 30-50min under the condition of a temperature of 25-30 ℃ to obtain an intermediate 8, dispersing the modified carrier prepared in the step A2 in deionized water, adding oxalic acid and concentrated sulfuric acid, refluxing for 2-3h at the temperature of 110-120 ℃, adding the intermediate 8 and 1-hydroxybenzotriazole, reacting for 4-5h at the temperature of 50-60 ℃, filtering to remove filtrate, and drying a filter cake to obtain the reinforcing filler.
The reaction process is as follows:
further, the ammonia water solution in the step A1 is ammonia water with the mass fraction of 30% and deionized water which are mixed according to the volume ratio of 1: 3.
Further, the dosage ratio of the dimethyldiethoxysilane, the methyltriethoxysilane, the xylene, the hydrochloric acid solution and the active quartz in the step A2 is 12g to 9g to 20mL to 8mL to 3g, and the mass fraction of the hydrochloric acid solution is 0.8-1%.
Further, in the step A3, the dosage ratio of aluminum trichloride, carbon tetrachloride and nitrobenzene is 13g:22g:7.8g, the dosage ratio of the intermediate 1, iron powder, ethanol and hydrochloric acid solution is 3.2g:5g:80mL:10mL, the volume fraction of ethanol is 90%, the hydrochloric acid solution is formed by mixing concentrated hydrochloric acid with the mass fraction of 36% and ethanol with the volume fraction of 95% in a volume ratio of 1:9, and the dosage ratio of the intermediate 2 and deionized water is 3g:20 mL.
Further, the amount ratio of the intermediate 3, paraformaldehyde, N-dimethylacetamide, xylene, and p-aminophenol described in step A4 is 0.01mol:0.02mol:10mL:10mL:0.02mol, the amount ratio of the intermediate 4, phthalic anhydride, and acetone is 10g:9.5g:70mL, and the amount ratio of the intermediate 5, p-toluenesulfonic acid, and tetrahydrofuran is 15g:1.35g:20 mL.
Further, the intermediate 6, the hydroxylamine hydrochloride and the ethanol solution in the step A5 are used in a ratio of 5g to 3g to 15mL, the ethanol solution is 80% by mass, the hydrochloric acid solution is 10-13% by mass, the intermediate 7, the zinc powder, the concentrated hydrochloric acid, the ammonia water and the sodium hydroxide solution are used in a ratio of 0.02mol to 0.2mol to 0.4mol to 25mL to 60mL, the concentrated hydrochloric acid is 37% by mass, the ammonia water is 30% by mass, the sodium hydroxide solution is 20% by mass, the modified carrier, the oxalic acid, the concentrated sulfuric acid, the intermediate 8 and the 1-hydroxybenzotriazole are used in a ratio of 10g to 3g to 7mL to 5g to 2.3g, and the concentrated sulfuric acid is 95% by mass.
A preparation method of a high heat-resistant coating for a storage battery shell specifically comprises the following steps:
step S1: adding ethanol, ethylene glycol ethyl ether and a film-forming additive into a stirring kettle, stirring for 20-30min under the condition that the rotation speed is 300-500r/min, adding epoxy resin E44, and continuously stirring for 1-1.5h to prepare a first mixture;
step S2: adding the first mixture prepared in the step S1 and a defoaming agent into a stirring kettle, and stirring for 1-1.5h under the condition that the rotating speed is 800-;
step S3: and (4) adding the second mixture prepared in the step (S2), the reinforcing filler, the talcum powder and the graphene into a stirring kettle, and carrying out ultrasonic treatment for 30-50min under the condition that the frequency is 8-10MHz to prepare the high-heat-resistance coating.
The invention has the beneficial effects that: the invention prepares a reinforced filler in the process of preparing a high heat-resistant coating for a battery case, the reinforced filler takes quartz powder as a raw material and is activated by ammonia water, active hydroxyl groups are distributed on the surface of the quartz powder, then dimethyl diethoxy silane and methyl triethoxy silane are hydrolyzed and polymerized to form organic silicon oligomer, the active quartz powder is added, the hydroxyl group on one side of the molecular chain of the organic silicon oligomer and the hydroxyl group on the surface of the active quartz powder form hydrogen bonds, then a layer of organic silicon oligomer is covered on the surface of the active quartz powder to prepare a modified carrier, nitrobenzene and carbon tetrachloride are reacted to prepare an intermediate 1, the intermediate 1 is reduced by iron powder to convert nitro groups into amino groups to prepare an intermediate 2, the intermediate 2 and deionized water are refluxed to prepare an intermediate 3, the intermediate 3, paraformaldehyde and p-aminophenol are reacted to prepare an intermediate 4, reacting the intermediate 4 with phthalic anhydride to obtain an intermediate 5, treating the intermediate 5 with p-toluenesulfonic acid to obtain an intermediate 6, treating the intermediate 6 with hydroxylamine hydrochloride, sodium hydroxide and hydrochloric acid solution to obtain an intermediate 7, further treating the intermediate 7 to obtain an intermediate 8, performing esterification reaction on a modified carrier and oxalic acid under the action of concentrated sulfuric acid to ensure that one carboxyl of the oxalic acid is subjected to esterification reaction with hydroxyl on the modified carrier, adding the intermediate 8, performing dehydration condensation on amino on the intermediate 8 and the residual carboxyl of the oxalic acid under the action of 1-hydroxybenzotriazole to obtain a reinforcing filler, wherein the reinforcing filler contains quartz, is matched with other inorganic fillers to further improve the impact resistance of the high-heat-resistant coating, and contains a large number of oxazine ring structures and conjugated double bond structures on the surface of the reinforcing filler, the heat resistance of coating can be greatly improved, and the surface contains a large amount of imide structures simultaneously for contain a large amount of ether linkages on the reinforcing filler, further promoted coating toughness, make the storage battery shell when receiving the collision, the damage can not appear filming, and then the protection of filming to the storage battery shell of assurance, increased the life of storage battery.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
A high heat-resistant coating for a storage battery shell comprises the following raw materials in parts by weight: 50 parts of epoxy resin E44, 10 parts of reinforcing filler, 3 parts of graphene, 3 parts of talcum powder, 20 parts of ethanol, 20 parts of ethylene glycol ethyl ether, 3 parts of propylene glycol butyl ether, 1 part of polydimethylsiloxane and 8 parts of diethylenetriamine;
the high heat-resistant coating is prepared by the following steps:
step S1: adding ethanol, ethylene glycol ethyl ether and propylene glycol butyl ether into a stirring kettle, stirring for 20min at the rotation speed of 300r/min, adding epoxy resin E44, and continuously stirring for 1h to obtain a first mixture;
step S2: adding the first mixture prepared in the step S1 and polydimethylsiloxane into a stirring kettle, and stirring for 1h at the rotating speed of 800r/min to prepare a second mixture;
step S3: and (4) adding the second mixture prepared in the step (S2), the reinforcing filler, the talcum powder, the graphene and the diethylenetriamine into a stirring kettle, and carrying out ultrasonic treatment for 30min under the condition that the frequency is 8MHz to prepare the high-heat-resistance coating.
The reinforcing filler is prepared by the following steps:
step A1: drying quartz powder at 160 ℃ for 40min, soaking the quartz powder in an ammonia water solution at a rotation speed of 300r/min and a temperature of 60 ℃ for 1.5h to obtain active quartz powder;
step A2: adding dimethyldiethoxysilane, methyltriethoxysilane and xylene into a reaction kettle, stirring for 10min at the rotation speed of 150r/min and the temperature of 65 ℃, dropwise adding a hydrochloric acid solution for 40min, adding the active quartz prepared in the step A1 after dropwise adding, reacting for 3h at the temperature of 75 ℃, filtering to remove filtrate, drying a filter cake for 15min at the vacuum degree of 0.08MPa and the temperature of 95 ℃, heating to 120 ℃, and continuing to dry for 30min to prepare a modified carrier;
step A3: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions of 150r/min and 10 ℃, reacting for 1h under the condition of 40 ℃ to obtain an intermediate 1, adding the intermediate 1, iron powder and ethanol into the reaction kettle, performing reflux reaction for 3h under the condition of 80 ℃, adding a hydrochloric acid solution, adding for 20min, continuing to react for 5h, adjusting the pH value of a reaction solution to 7 to obtain an intermediate 2, mixing the intermediate 2 with deionized water, and performing reflux for 10min under the condition of 110 ℃ to obtain an intermediate 3;
step A4: adding the intermediate 3, paraformaldehyde, N-dimethylacetamide and xylene into a reaction kettle, stirring for 20min at the rotation speed of 150r/min and the temperature of 20 ℃, adding p-aminophenol, reacting for 5h at the temperature of 120 ℃ to obtain an intermediate 4, adding the intermediate 4, phthalic anhydride and acetone into the reaction kettle, reacting for 1.5h at the rotation speed of 120r/min and the temperature of 0 ℃ to obtain an intermediate 5, adding the intermediate 5, p-toluenesulfonic acid and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 5h at the temperature of 110 ℃ to obtain an intermediate 6;
step A5: adding the intermediate 6, hydroxylamine hydrochloride and ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotation speed of 150r/min and the temperature of 30 ℃, reacting for 3 hours, heating to the temperature of 70 ℃, refluxing for 5 minutes, adding hydrochloric acid solution, stirring for 5 minutes to prepare an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3 hours under the conditions of the rotation speed of 200r/min and the temperature of 40 ℃, cooling to the temperature of 0 ℃, adding ammonia water and sodium hydroxide solution, reacting for 30 minutes under the temperature of 25 ℃ to prepare an intermediate 8, dispersing the modified carrier prepared in the step A2 in deionized water, adding oxalic acid and concentrated sulfuric acid, refluxing for 2 hours under the temperature of 110 ℃, adding the intermediate 8 and 1-hydroxybenzotriazole, reacting for 4 hours at the temperature of 50 ℃, filtering to remove filtrate, and drying a filter cake to obtain the reinforcing filler.
Example 2
A high heat-resistant coating for a storage battery shell comprises the following raw materials in parts by weight: 53 parts of epoxy resin E44, 12 parts of reinforcing filler, 4 parts of graphene, 4 parts of talcum powder, 23 parts of ethanol, 23 parts of ethylene glycol ethyl ether, 4 parts of propylene glycol butyl ether, 2 parts of polydimethylsiloxane and 9 parts of diethylenetriamine;
the high heat-resistant coating is prepared by the following steps:
step S1: adding ethanol, ethylene glycol ethyl ether and propylene glycol butyl ether into a stirring kettle, stirring for 30min at the rotation speed of 300r/min, adding epoxy resin E44, and continuously stirring for 1h to obtain a first mixture;
step S2: adding the first mixture prepared in the step S1 and polydimethylsiloxane into a stirring kettle, and stirring for 1h at the rotation speed of 1000r/min to prepare a second mixture;
step S3: and (4) adding the second mixture prepared in the step (S2), the reinforcing filler, the talcum powder, the graphene and the diethylenetriamine into a stirring kettle, and carrying out ultrasonic treatment for 30min under the condition that the frequency is 10MHz to prepare the high-heat-resistance coating.
The reinforcing filler is prepared by the following steps:
step A1: drying quartz powder at 180 ℃ for 40min, soaking the quartz powder in an ammonia water solution at a rotation speed of 500r/min and a temperature of 60 ℃ for 3h to prepare active quartz powder;
step A2: adding dimethyldiethoxysilane, methyltriethoxysilane and xylene into a reaction kettle, stirring for 10min at the rotation speed of 150r/min and the temperature of 70 ℃, dropwise adding a hydrochloric acid solution for 60min, adding the active quartz prepared in the step A1 after dropwise adding, reacting for 5h at the temperature of 75 ℃, filtering to remove filtrate, drying a filter cake for 15min at the vacuum degree of 0.08MPa and the temperature of 100 ℃, heating to the temperature of 130 ℃, and continuing to dry for 30min to prepare a modified carrier;
step A3: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions of 200r/min and 10 ℃, reacting for 1h under the condition of 45 ℃ to obtain an intermediate 1, adding the intermediate 1, iron powder and ethanol into the reaction kettle, performing reflux reaction for 3h under the condition of 85 ℃, adding a hydrochloric acid solution, adding for 20min, continuing to react for 8h, adjusting the pH value of a reaction solution to 7 to obtain an intermediate 2, mixing the intermediate 2 with deionized water, and performing reflux for 10min under the condition of 120 ℃ to obtain an intermediate 3;
step A4: adding the intermediate 3, paraformaldehyde, N-dimethylacetamide and xylene into a reaction kettle, stirring for 30min at the rotation speed of 200r/min and the temperature of 20 ℃, adding p-aminophenol, reacting for 7h at the temperature of 120 ℃ to obtain an intermediate 4, adding the intermediate 4, phthalic anhydride and acetone into the reaction kettle, reacting for 3h at the rotation speed of 120r/min and the temperature of 0 ℃ to obtain an intermediate 5, adding the intermediate 5, p-toluenesulfonic acid and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 8h at the temperature of 110 ℃ to obtain an intermediate 6;
step A5: adding the intermediate 6, hydroxylamine hydrochloride and an ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotating speed of 150r/min and the temperature of 35 ℃, reacting for 3 hours, heating to the temperature of 80 ℃, refluxing for 5 minutes, adding the hydrochloric acid solution, stirring for 10 minutes to prepare an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3 hours under the conditions of the rotating speed of 200r/min and the temperature of 50 ℃, cooling to the temperature of 0 ℃, adding ammonia water and a sodium hydroxide solution, reacting for 30 minutes under the temperature of 30 ℃ to prepare an intermediate 8, dispersing the modified carrier prepared in the step A2 in deionized water, adding oxalic acid and concentrated sulfuric acid, refluxing for 2 hours under the temperature of 120 ℃, adding the intermediate 8 and 1-hydroxybenzotriazole, reacting for 4 hours at the temperature of 60 ℃, filtering to remove filtrate, and drying a filter cake to obtain the reinforcing filler.
Example 3
A high heat-resistant coating for a storage battery shell comprises the following raw materials in parts by weight: 58 parts of epoxy resin E44, 14 parts of reinforcing filler, 4 parts of graphene, 4 parts of talcum powder, 28 parts of ethanol, 25 parts of ethylene glycol ethyl ether, 4 parts of propylene glycol butyl ether, 2 parts of polydimethylsiloxane and 9 parts of diethylenetriamine;
the high heat-resistant coating is prepared by the following steps:
step S1: adding ethanol, ethylene glycol ethyl ether and propylene glycol butyl ether into a stirring kettle, stirring for 20min at the rotation speed of 500r/min, adding epoxy resin E44, and continuously stirring for 1.5h to obtain a first mixture;
step S2: adding the first mixture prepared in the step S1 and polydimethylsiloxane into a stirring kettle, and stirring for 1.5 hours at the rotation speed of 800r/min to prepare a second mixture;
step S3: and (4) adding the second mixture prepared in the step (S2), the reinforcing filler, the talcum powder, the graphene and the diethylenetriamine into a stirring kettle, and carrying out ultrasonic treatment for 50min under the condition that the frequency is 8MHz to prepare the high-heat-resistance coating.
The reinforcing filler is prepared by the following steps:
step A1: drying quartz powder at 160 ℃ for 50min, soaking the quartz powder in an ammonia water solution at a rotation speed of 300r/min and a temperature of 80 ℃ for 1.5h to obtain active quartz powder;
step A2: adding dimethyldiethoxysilane, methyltriethoxysilane and xylene into a reaction kettle, stirring for 15min at the rotation speed of 200r/min and the temperature of 65 ℃, dropwise adding a hydrochloric acid solution for 40min, adding the active quartz prepared in the step A1 after dropwise adding, reacting for 3h at the temperature of 80 ℃, filtering to remove filtrate, drying a filter cake for 20min at the vacuum degree of 0.1MPa and the temperature of 95 ℃, heating to 120 ℃, and continuously drying for 40min to prepare a modified carrier;
step A3: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions of 150r/min and 15 ℃, reacting for 1.5h under the condition of 40 ℃ to obtain an intermediate 1, adding the intermediate 1, iron powder and ethanol into the reaction kettle, performing reflux reaction for 5h under the condition of 80 ℃, adding a hydrochloric acid solution for 20min, continuously reacting for 5h, adjusting the pH value of a reaction solution to 8 to obtain an intermediate 2, mixing the intermediate 2 with deionized water, and refluxing for 15min under the condition of 110 ℃ to obtain an intermediate 3;
step A4: adding the intermediate 3, paraformaldehyde, N-dimethylacetamide and xylene into a reaction kettle, stirring for 20min at the rotation speed of 150r/min and the temperature of 25 ℃, adding p-aminophenol, reacting for 5h at the temperature of 130 ℃ to obtain an intermediate 4, adding the intermediate 4, phthalic anhydride and acetone into the reaction kettle, reacting for 1.5h at the rotation speed of 150r/min and the temperature of 0 ℃ to obtain an intermediate 5, adding the intermediate 5, p-toluenesulfonic acid and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 5h at the temperature of 150 ℃ to obtain an intermediate 6;
step A5: adding the intermediate 6, hydroxylamine hydrochloride and an ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotation speed of 200r/min and the temperature of 30 ℃, reacting for 5 hours, heating to the temperature of 70 ℃, refluxing for 8 minutes, adding the hydrochloric acid solution, stirring for 5 minutes to prepare an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 5 hours under the conditions of the rotation speed of 300r/min and the temperature of 40 ℃, cooling to the temperature of 0 ℃, adding ammonia water and a sodium hydroxide solution, reacting for 50 minutes under the temperature of 25 ℃ to prepare an intermediate 8, dispersing the modified carrier prepared in the step A2 in deionized water, adding oxalic acid and concentrated sulfuric acid, refluxing for 3 hours under the temperature of 110 ℃, adding the intermediate 8 and 1-hydroxybenzotriazole, reacting for 5h at the temperature of 50 ℃, filtering to remove filtrate, and drying a filter cake to obtain the reinforcing filler.
Example 4
A high heat-resistant coating for a storage battery shell comprises the following raw materials in parts by weight: 60 parts of epoxy resin E44, 15 parts of reinforcing filler, 5 parts of graphene, 5 parts of talcum powder, 30 parts of ethanol, 30 parts of ethylene glycol ethyl ether, 5 parts of propylene glycol butyl ether, 3 parts of polydimethylsiloxane and 10 parts of diethylenetriamine;
the high heat-resistant coating is prepared by the following steps:
step S1: adding ethanol, ethylene glycol ethyl ether and propylene glycol butyl ether into a stirring kettle, stirring for 30min at the rotation speed of 500r/min, adding epoxy resin E44, and continuously stirring for 1.5h to obtain a first mixture;
step S2: adding the first mixture prepared in the step S1 and polydimethylsiloxane into a stirring kettle, and stirring for 1.5 hours at the rotation speed of 1000r/min to prepare a second mixture;
step S3: and (4) adding the second mixture prepared in the step (S2), the reinforcing filler, the talcum powder, the graphene and the diethylenetriamine into a stirring kettle, and carrying out ultrasonic treatment for 50min under the condition that the frequency is 10MHz to prepare the high-heat-resistance coating.
The reinforcing filler is prepared by the following steps:
step A1: drying quartz powder at 180 ℃ for 50min, soaking the quartz powder in an ammonia water solution at a rotation speed of 500r/min and a temperature of 80 ℃ for 3h to prepare active quartz powder;
step A2: adding dimethyldiethoxysilane, methyltriethoxysilane and xylene into a reaction kettle, stirring for 15min at the rotation speed of 200r/min and the temperature of 70 ℃, dropwise adding a hydrochloric acid solution for 60min, adding the active quartz prepared in the step A1 after dropwise adding, reacting for 5h at the temperature of 80 ℃, filtering to remove filtrate, drying a filter cake for 20min at the vacuum degree of 0.1MPa and the temperature of 100 ℃, heating to the temperature of 130 ℃, and continuously drying for 40min to prepare a modified carrier;
step A3: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions of 200r/min and 15 ℃, reacting for 1.5h under the condition of 45 ℃ to obtain an intermediate 1, adding the intermediate 1, iron powder and ethanol into the reaction kettle, performing reflux reaction for 5h under the condition of 85 ℃, adding a hydrochloric acid solution for 20min, continuing to react for 8h, adjusting the pH value of a reaction solution to 8 to obtain an intermediate 2, mixing the intermediate 2 with deionized water, and refluxing for 15min under the condition of 120 ℃ to obtain an intermediate 3;
step A4: adding the intermediate 3, paraformaldehyde, N-dimethylacetamide and xylene into a reaction kettle, stirring for 30min at the rotation speed of 200r/min and at the temperature of 25 ℃, adding p-aminophenol, reacting for 7h at the temperature of 130 ℃ to obtain an intermediate 4, adding the intermediate 4, phthalic anhydride and acetone into the reaction kettle, reacting for 3h at the rotation speed of 150r/min and at the temperature of 0 ℃ to obtain an intermediate 5, adding the intermediate 5, p-toluenesulfonic acid and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 8h at the temperature of 150 ℃ to obtain an intermediate 6;
step A5: adding the intermediate 6, hydroxylamine hydrochloride and an ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotating speed of 200r/min and the temperature of 35 ℃, reacting for 5 hours, heating to the temperature of 80 ℃, refluxing for 8 minutes, adding the hydrochloric acid solution, stirring for 10 minutes to prepare an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 5 hours under the conditions of the rotating speed of 300r/min and the temperature of 50 ℃, cooling to the temperature of 0 ℃, adding ammonia water and a sodium hydroxide solution, reacting for 50 minutes under the temperature of 30 ℃ to prepare an intermediate 8, dispersing the modified carrier prepared in the step A2 in deionized water, adding oxalic acid and concentrated sulfuric acid, refluxing for 3 hours under the temperature of 120 ℃, adding the intermediate 8 and 1-hydroxybenzotriazole, reacting for 5h at the temperature of 60 ℃, filtering to remove filtrate, and drying a filter cake to obtain the reinforcing filler.
Comparative example
The comparative example is a common high heat-resistant coating on the market.
The high heat-resistant coatings prepared in examples 1 to 4 and comparative example were subjected to a performance test, and the test results are shown in table 1 below;
TABLE 1
As is apparent from Table 1 above, the high heat resistant coatings obtained in examples 1 to 4 were all of grade 1 in adhesion, 1.03 to 1.05mm in flexibility and 50.9 to 51.3kg.cm in impact resistance, and no cracking or foaming occurred when heated at 450, 500 and 550 ℃ for 100 hours, while the high heat resistant coatings obtained in comparative examples were of grade 2 in adhesion, 43.5kg.cm in impact resistance and 0.76mm in flexibility, and were cracked and not foamed when heated at 450 ℃ for 100 hours, and were cracked and foamed when heated at 500 and 550 ℃ for 100 hours.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (1)
1. A high heat-resistant coating for a battery case is characterized in that: the feed comprises the following raw materials in parts by weight: 50-60 parts of epoxy resin E44, 10-15 parts of reinforcing filler, 3-5 parts of graphene, 3-5 parts of talcum powder, 20-30 parts of ethanol, 20-30 parts of ethylene glycol ethyl ether, 3-5 parts of film-forming assistant, 1-3 parts of defoaming agent and 8-10 parts of diethylenetriamine;
the high heat-resistant coating is prepared by the following steps:
step S1: adding ethanol, ethylene glycol ethyl ether and a film-forming additive into a stirring kettle, stirring for 20-30min under the condition that the rotation speed is 300-500r/min, adding epoxy resin E44, and continuously stirring for 1-1.5h to prepare a first mixture;
step S2: adding the first mixture prepared in the step S1 and a defoaming agent into a stirring kettle, and stirring for 1-1.5h under the condition that the rotating speed is 800-;
step S3: adding the second mixture prepared in the step S2, the reinforcing filler, the talcum powder, the graphene and the diethylenetriamine into a stirring kettle, and performing ultrasonic treatment for 30-50min under the condition that the frequency is 8-10MHz to prepare the high-heat-resistance coating;
the reinforcing filler is prepared by the following steps:
step A1: drying the quartz powder for 40-50min at the temperature of 160-180 ℃, soaking the quartz powder in an ammonia solution at the rotation speed of 300-500r/min at the temperature of 60-80 ℃ for 1.5-3h to prepare active quartz powder;
step A2: adding dimethyl diethoxy silane, methyl triethoxysilane and xylene into a reaction kettle, stirring for 10-15min under the conditions of the rotation speed of 150-200r/min and the temperature of 65-70 ℃, dropwise adding a hydrochloric acid solution for 40-60min, adding the active quartz prepared in the step A1 after dropwise adding, reacting for 3-5h under the condition of the temperature of 75-80 ℃, filtering to remove filtrate, drying a filter cake for 15-20min under the conditions of the vacuum degree of 0.08-0.1MPa and the temperature of 95-100 ℃, heating to the temperature of 120-130 ℃, and continuing to dry for 30-40min to prepare a modified carrier;
step A3: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions of conversion to 150-plus-one (200 r/min) and temperature of 10-15 ℃, reacting for 1-1.5h under the condition of temperature of 40-45 ℃ to obtain an intermediate 1, adding the intermediate 1, iron powder and ethanol into the reaction kettle, performing reflux reaction for 3-5h under the condition of temperature of 80-85 ℃, adding a hydrochloric acid solution for 20min, continuously reacting for 5-8h, adjusting the pH value of a reaction solution to 7-8 to obtain an intermediate 2, mixing the intermediate 2 with deionized water, and performing reflux for 10-15min under the condition of temperature of 110-plus-one (120 ℃) to obtain an intermediate 3;
step A4: adding the intermediate 3, paraformaldehyde, N-dimethylacetamide and xylene into a reaction kettle, stirring for 20-30min at the rotation speed of 150-;
step A5: adding the intermediate 6, hydroxylamine hydrochloride and ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of a rotation speed of 150-35 ℃ and a temperature of 30-35 ℃, reacting for 3-5h, heating to a temperature of 70-80 ℃, refluxing for 5-8min, adding hydrochloric acid solution, stirring for 5-10min to obtain an intermediate 7, dissolving the intermediate 7 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3-5h under the conditions of a rotation speed of 200-300r/min and a temperature of 40-50 ℃, cooling to a temperature of 0 ℃, adding ammonia water and sodium hydroxide solution, reacting for 30-50min under the condition of a temperature of 25-30 ℃ to obtain an intermediate 8, dispersing the modified carrier prepared in the step A2 in deionized water, adding oxalic acid and concentrated sulfuric acid, refluxing for 2-3h at the temperature of 110-120 ℃, adding the intermediate 8 and 1-hydroxybenzotriazole, reacting for 4-5h at the temperature of 50-60 ℃, filtering to remove filtrate, and drying a filter cake to obtain the reinforcing filler.
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