CN114958139B - Flame retardant, preparation method, coating containing flame retardant and explosion-proof battery box containing flame retardant coating - Google Patents
Flame retardant, preparation method, coating containing flame retardant and explosion-proof battery box containing flame retardant coating Download PDFInfo
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- CN114958139B CN114958139B CN202210549097.6A CN202210549097A CN114958139B CN 114958139 B CN114958139 B CN 114958139B CN 202210549097 A CN202210549097 A CN 202210549097A CN 114958139 B CN114958139 B CN 114958139B
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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
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a flame retardant which is obtained by doping and modifying polyphosphoric acid amine by adopting one element or a combination of multiple elements in magnesium, aluminum, silicon, calcium or titanium. The invention also discloses a preparation method of the flame retardant, which comprises the following steps: mixing aluminum chloride and/or magnesium chloride and/or silicon chloride and/or calcium chloride and/or titanium chloride with ammonium polyphosphate, adding water and a pH regulator into the mixture, reacting at room temperature, filtering after the reaction, drying the precipitate, and calcining the precipitate at high temperature to obtain the modified ammonium polyphosphate flame retardant. The invention also discloses a flame-retardant aqueous epoxy resin coating containing the flame retardant, which comprises the following components in parts by weight: 20 to 50 parts of water-based epoxy resin, 20 to 50 parts of modified ammonium polyphosphate flame retardant, 10 to 30 parts of char forming agent, 0.1 to 0.5 part of wetting agent, 0.1 to 0.5 part of defoamer, 0.1 to 0.5 part of dispersing agent, 0.1 to 0.5 part of anti-settling agent, 0.6 to 2.0 parts of pigment and filler, 5 to 20 parts of curing agent and 10 to 30 parts of diluent. The invention finally discloses a flame-retardant explosion-proof battery box based on the flame-retardant waterborne epoxy resin coating.
Description
Technical Field
The invention relates to a flame retardant, a preparation method of the flame retardant, a flame-retardant waterborne epoxy resin coating containing the flame retardant, and finally a flame-retardant explosion-proof battery box based on the flame-retardant waterborne epoxy resin coating.
Background
Epoxy resin (EP) is used as a thermosetting polymer material, and has the advantages of mature production process, excellent dimensional stability, cohesiveness and strong corrosion environment adaptability. At present, epoxy resin coatings are generally divided into oily epoxy coatings and aqueous epoxy coatings. The aqueous epoxy resin is extremely easy to burn, a large amount of dense smoke and other toxic components can be generated in the burning process, serious pollution is caused to the environment, and molten drips generated in the burning process have the danger of igniting other combustible substances around, so that secondary fire is extremely easy to be initiated. Epoxy resins having flame retardant properties are therefore a rigid requirement. In order to achieve a better flame-retardant effect, the addition amount of the flame retardant in the aqueous epoxy resin is generally larger, the compatibility of the external flame retardant and the emulsion is often poor, and the problem of emulsion breaking of the aqueous epoxy resin emulsion is easily caused, so that the development of the flame-retardant aqueous epoxy resin is greatly limited.
Disclosure of Invention
The invention aims to: one of the purposes of the invention is to provide a modified ammonium polyphosphate flame retardant, which can maintain the stability of an aqueous epoxy resin system (no demulsification problem) and can effectively solve the problem that an aqueous epoxy resin coating is extremely easy to burn (improve the flame retardance) after being added into an aqueous epoxy resin emulsion; another object of the present invention is to provide a method for preparing the modified ammonium polyphosphate flame retardant, by which a desired element can be doped into the ammonium polyphosphate flame retardant, thereby improving the flame retardant property of the ammonium polyphosphate flame retardant; it is still another object of the present invention to provide a flame retardant aqueous epoxy resin coating containing the above modified ammonium polyphosphate flame retardant; the invention aims at providing a flame-retardant and explosion-proof battery box based on the flame-retardant aqueous epoxy resin coating, wherein the flame-retardant aqueous epoxy resin coating is coated on the inner surface of the box body to form a heat-insulating layer, when the battery is abnormal, particularly when the battery burns, the temperature in the battery box is increased, and the heat-insulating layer in the box body can be foamed and expanded to form a porous carbonaceous layer which is tens times thicker than the original coating. The foaming process absorbs a large amount of heat, and the formed porous carbonaceous layer has high heat insulation performance and forms a heat insulation barrier, so that the explosion caused by the rapid temperature rise of the battery box is prevented, and the thermal runaway fire hazard of the battery pack is further effectively reduced.
The technical scheme is as follows: the flame retardant is obtained by doping and modifying the ammonium polyphosphate by adopting one element or a combination of multiple elements of magnesium, aluminum, silicon, calcium or titanium.
The ammonium polyphosphate is directly added into the aqueous epoxy resin emulsion, which is equivalent to adding electrolyte into the emulsion, breaking the double-electronic-layer structure of the emulsion, and is extremely easy to cause emulsion breaking of the aqueous epoxy resin emulsion, doping modification of the ammonium polyphosphate, improving the flame retardant capability of the ammonium polyphosphate, reducing the emulsion breaking influence of the ammonium polyphosphate on the aqueous epoxy resin emulsion through the change of the charge performance of the ammonium polyphosphate, and increasing the flame retardant performance of the aqueous epoxy resin emulsion.
The preparation method of the flame retardant comprises the following steps: mixing aluminum chloride and/or magnesium chloride and/or silicon chloride and/or calcium chloride and/or titanium chloride with ammonium polyphosphate, adding water and a pH regulator into the mixture, reacting at room temperature, filtering after the reaction, and calcining the precipitate at high temperature to obtain the modified ammonium polyphosphate flame retardant.
Wherein, the mixing mass ratio of the chloride to the ammonium polyphosphate is 1:2 to 10.
Wherein, the pH regulator regulates the reaction liquid to be alkaline, and the pH value is 8-11. Chlorides of magnesium, aluminum, silicon, calcium, and titanium can form hydroxides of magnesium, aluminum, silicon, calcium, and titanium at the corresponding pH.
Wherein the calcination temperature is 300-450 ℃.
The flame-retardant aqueous epoxy resin coating containing the flame retardant comprises the following components in parts by weight: 20 to 50 parts of water-based epoxy resin, 20 to 50 parts of modified ammonium polyphosphate flame retardant, 10 to 30 parts of char forming agent, 0.1 to 0.5 part of wetting agent, 0.1 to 0.5 part of defoamer, 0.1 to 0.5 part of dispersing agent, 0.1 to 0.5 part of anti-settling agent, 0.6 to 2.0 parts of pigment and filler, 5 to 20 parts of curing agent and 10 to 30 parts of diluent.
Wherein the char forming agent is one or a combination of more of starch, cyclodextrin, sucrose, glucose, pentaerythritol or dipentaerythritol; the wetting agent is one or a combination of a plurality of BYK-S706, BYK-306, BYK-359, BYK-361 or SN-4727A; the defoaming agent is one or a combination of more of organosilicon defoaming agent, polyether, mineral oil or SN-6710; the dispersing agent is one or a combination of a plurality of BYK-307, BYK-330, BYK-341, BYK-2150, BYK-2155, BYK-104S, SN-1728, SN-1728A, SN-1729, SN-1760, SN-1776, SN-1790A, SN-1791, SN-1792 or SN-1798; the anti-settling agent is one or a combination of more of polyethylene wax, bentonite or polyamide wax; the pigment and filler is one or a combination of more of iron oxide red, carbon black, chrome yellow, zinc oxide, titanium pigment, barium sulfate, talcum powder, calcium carbonate, mica powder, talcum powder or quartz powder; the curing agent is one or a combination of a plurality of triethylamine, diethylamine, triethylenediamine, tetraethylenetriamine, piperazine, pyridine or piperidine; the diluent is one or a combination of a plurality of No. 200 solvent gasoline, dimethylbenzene, water, methanol, ethanol, isopropanol, ethyl acetate or propylene glycol dimethyl ether.
The preparation method of the flame-retardant waterborne epoxy resin coating comprises the following steps:
(1) Adding the formula amount of aqueous epoxy resin into a reaction device, adding the formula amount of diluent into the reaction device, and stirring until vortex appears at the center of the liquid level;
(2) Slowly adding a wetting agent, a defoaming agent and a dispersing agent in the formula amount into a reaction device; adding the flame retardant and the char forming agent in the formula amount into a reaction device, and dispersing and stirring to fully mix the materials; finally, adding the pigment and filler and anti-settling agent in the formula amount into a reaction device, and dispersing and stirring again to fully mix the materials to obtain viscous emulsion;
(3) And adding a curing agent into the emulsion, and obtaining the flame-retardant coating under corresponding curing conditions. Curing occurs after the curing agent is added into the aqueous epoxy resin emulsion, and the temperature affects the time for complete curing. Wherein the curing temperature of the aqueous epoxy resin emulsion is 20-50 ℃ and the curing time is 36-48 h.
The flame-retardant explosion-proof battery box based on the flame-retardant waterborne epoxy resin coating comprises a box body and a flame-retardant waterborne epoxy resin coating coated on the inner surface of the box body, wherein the box body takes the flame-retardant coating as a heat insulation layer.
The beneficial effects are that: the epoxy resin coating obtained based on the modified ammonium polyphosphate flame retardant has excellent fireproof capacity and has the advantages of high adhesive force, good water resistance and strong weather resistance; when the battery is abnormal, particularly when the explosion happens, the temperature in the battery box is quickly increased, and at the moment, the flame-retardant coating can quickly absorb heat and foam to form a heat insulation layer, and the heat insulation layer can effectively absorb heat and insulate heat to prevent the explosion of the battery box, so that the thermal runaway fire hazard of the battery pack is effectively reduced.
Drawings
FIG. 1 is an infrared spectrum of an aluminum element doped ammonium polyphosphate flame retardant prepared in example 1;
FIG. 2 is an infrared spectrum of the silicon-doped ammonium polyphosphate flame retardant prepared in example 2;
FIG. 3 is an infrared spectrum of the magnesium-doped ammonium polyphosphate flame retardant prepared in example 3;
FIG. 4 is a graph showing the relationship between the battery temperature of a common battery box (without the flame-retardant aqueous epoxy resin heat-insulating layer of the invention) and the temperature of the outer wall of the battery box;
fig. 5 is a graph showing the relationship between the battery temperature of the flame-retardant and explosion-proof battery box (coated with the flame-retardant aqueous epoxy resin heat-insulating layer of example 2 of the present invention) and the temperature of the outer wall of the battery box.
Detailed Description
Example 1
The modified ammonium polyphosphate flame retardant is prepared by the following method: mixing 20g of aluminum chloride and 100g of ammonium polyphosphate, adding 200mL of water and a pH regulator (potassium hydroxide) into the mixture, regulating the pH of the reaction solution to 9-10, reacting for 4 hours at room temperature, filtering after the reaction, drying the filtered precipitate, and calcining at 400 ℃ to obtain the aluminum-doped ammonium polyphosphate flame retardant.
The flame-retardant aqueous epoxy resin coating containing the aluminum-doped ammonium polyphosphate flame retardant is prepared from the following raw materials in parts by weight: 45 parts of aqueous epoxy resin (E11 (commodity model) of Jiangsu Xingfeng chemical Co., ltd.), 25 parts of flame retardant (ammonium polyphosphate flame retardant doped with aluminum element), 10 parts of char forming agent (dipentaerythritol), 0.2 part of wetting agent (BYK-S706 (commodity model) of Pick brand, germany), 0.3 part of antifoaming agent (mineral oil), 0.2 part of dispersant (BYK-307 (commodity model) of Pick brand, germany), 0.5 part of anti-settling agent (bentonite), 1 part of pigment and filler (talcum powder), 5 parts of curing agent (Q15 (commodity model) of Jiangsu Xingfeng Co., ltd.) and 10 parts of diluent (water).
The preparation method of the flame-retardant waterborne epoxy resin coating comprises the following steps:
(1) 45 parts of aqueous epoxy resin (E11) and 10 parts of diluent (water) are added into the reaction device, stirring is started, the stirring speed is 800-1000 rpm until vortex appears at the center of the liquid surface, and stirring is stopped;
(2) Slowly adding 0.2 parts by weight of wetting agent (BYK-S706), 0.3 parts by weight of defoamer (mineral oil) and 0.2 parts by weight of dispersant (BYK-307) into a reaction device; adding 25 parts by weight of ammonium polyphosphate flame retardant doped with aluminum element and 10 parts by weight of char forming agent (dipentaerythritol) into a reaction device, and dispersing and stirring for a period of time after the materials are added so as to fully mix the materials; finally, adding 1 part by weight of pigment and filler (talcum powder) and 0.5 part by weight of anti-settling agent (bentonite) into a reaction device, and dispersing and stirring for a period of time again to fully mix the materials to obtain emulsion; standing the emulsion for one year, and then observing, wherein layering phenomenon is not found;
(3) 5 parts by weight of a curing agent (Q15) is added into the emulsion, and the mixture is cured for 48 hours at 20 ℃ to obtain a flame-retardant waterborne epoxy resin cured product.
Example 2
The modified ammonium polyphosphate flame retardant is prepared by the following method: mixing 20g of silicon chloride and 100g of ammonium polyphosphate, adding 200mL of water and a pH regulator (potassium hydroxide) into the mixture, regulating the pH of the reaction solution to 8-9 by the potassium hydroxide, reacting for 4 hours at room temperature, filtering after the reaction, drying the filtered precipitate and calcining at 350 ℃ to obtain the silicon-doped ammonium polyphosphate flame retardant.
The flame-retardant aqueous epoxy resin coating containing the silicon-doped ammonium polyphosphate flame retardant is prepared from the following raw materials in parts by weight: 45 parts of aqueous epoxy resin (E62 (commodity model) of Jiangsu Xingfeng chemical Co., ltd.), 20 parts of flame retardant (ammonium polyphosphate flame retardant doped with silicon element), 12 parts of char forming agent (pentaerythritol), 0.3 part of wetting agent (BYK-306 (commodity model) of Pick brand, germany), 0.2 part of defoamer (polyether), 0.2 part of dispersant (SN-1729 (commodity model) of deep bamboo Co.), 0.3 part of anti-settling agent (polyethylene wax), 0.8 part of pigment and filler (talcum powder), 7 parts of curing agent (Q44 (commodity model) of Jiangsu Xingfeng Co.), and 15 parts of diluent (water).
The preparation method of the flame-retardant waterborne epoxy resin coating comprises the following steps:
(1) 45 parts of aqueous epoxy resin (E62) is added into the reaction device, 15 parts of diluent (water) is added into the reaction device, stirring is started, the stirring speed is 800-1000 revolutions per minute until vortex appears at the center of the liquid surface, and stirring is stopped;
(2) Slowly adding 0.3 parts by weight of wetting agent (BYK-306), 0.2 parts by weight of defoamer (polyether) and 0.2 parts by weight of dispersant (SN-1729) into a reaction device; adding 20 parts by weight of ammonium polyphosphate flame retardant doped with silicon element and 10 parts by weight of char forming agent (pentaerythritol) into a reaction device, and dispersing and stirring for a period of time after the materials are added so as to fully mix the materials; finally, adding 0.8 weight part of pigment and filler (talcum powder) and 0.3 weight part of anti-settling agent (polyethylene wax) into the reaction device, and dispersing and stirring again for a period of time to fully mix the materials to obtain emulsion; standing the emulsion for one year, and then observing, wherein layering phenomenon is not found;
(3) 7 parts by weight of a curing agent (Q44) is added into the emulsion, and the mixture is cured for 36 hours at 30 ℃ to obtain a flame-retardant waterborne epoxy resin cured product.
Example 3
The modified ammonium polyphosphate flame retardant is prepared by the following method: mixing 20g of magnesium chloride and 100g of ammonium polyphosphate, adding 200mL of water and a pH regulator (potassium hydroxide) into the mixture, regulating the pH of the reaction solution to 10-11 by the potassium hydroxide, reacting for 4 hours at room temperature, filtering after the reaction, drying the filtered precipitate and calcining at 400 ℃ to obtain the magnesium-doped ammonium polyphosphate flame retardant.
The flame-retardant aqueous epoxy resin coating containing the magnesium-doped ammonium polyphosphate flame retardant is prepared from the following raw materials in parts by weight: 45 parts of aqueous epoxy resin (E13 (commodity model) of Jiangsu Xingfeng chemical Co., ltd.), 25 parts of flame retardant (magnesium element doped ammonium polyphosphate flame retardant), 15 parts of char forming agent (starch), 0.4 part of wetting agent (BYK-359 (commodity model) of Pick brand, germany), 0.2 part of defoamer (SN-6710 (commodity model) of deep bamboo Co.), 0.3 part of dispersant (BYK-2155 (commodity model) of Pick brand, germany), 0.4 part of anti-settling agent (polyethylene wax), 0.6 part of pigment filler (mica powder), 10 parts of curing agent (Q65 (commodity model) of Jiangsu Xingfeng Co., ltd.) and 13 parts of diluent (water).
The preparation method of the flame-retardant waterborne epoxy resin coating comprises the following steps:
(1) Adding 45 parts of aqueous epoxy resin (E13) into a reaction device, adding 13 parts of diluent (water) into the reaction device, starting stirring at a speed of 800-1000 rpm until vortex appears at the center of the liquid surface, and stopping stirring;
(2) Slowly adding 0.4 parts by weight of wetting agent (BYK-359), 0.2 parts by weight of defoamer (SN-6710) and 0.3 parts by weight of dispersant (BYK-2155) into a reaction device; adding 25 parts by weight of ammonium polyphosphate flame retardant doped with magnesium element and 15 parts by weight of char forming agent (starch) into a reaction device, and dispersing and stirring for a period of time after the materials are added so as to fully mix the materials; finally, adding 0.6 weight part of pigment and filler (mica powder) and 0.4 weight part of anti-settling agent (polyethylene wax) into the reaction device, and dispersing and stirring again for a period of time to fully mix the materials to obtain emulsion; standing the emulsion for one year, and then observing, wherein layering phenomenon is not found;
(3) 10 parts by weight of a curing agent (Q65) is added into the emulsion, and the mixture is cured for 36 hours at 40 ℃ to obtain a flame-retardant waterborne epoxy resin cured product.
As can be seen from FIGS. 1 to 3, the preparation method of the flame retardant successfully mixes aluminum oxide, silicon oxide and magnesium oxide into an ammonium polyphosphate skeleton, the inorganic oxide has high fire resistance temperature, the flame retardance of ammonium polyphosphate can be greatly improved, and the demulsification influence of ammonium polyphosphate on aqueous epoxy resin emulsion is reduced through changing the charge property of the ammonium polyphosphate.
Comparative example 1
The aqueous epoxy resin coating containing the ammonium polyphosphate flame retardant is prepared from the following raw materials in parts by weight: 45 parts of aqueous epoxy resin (E62 (commodity model) of Jiangsu xing Feng chemical Co., ltd.), 20 parts of ammonium polyphosphate flame retardant (unmodified ammonium polyphosphate flame retardant), 12 parts of char forming agent (pentaerythritol), 0.3 part of wetting agent (BYK-306 (commodity model) of Pick brand, germany), 0.2 part of antifoaming agent (polyether), 0.2 part of dispersant (SN-1729 (commodity model) of deep bamboo Co., ltd.), 0.3 part of anti-settling agent (polyethylene wax), 0.8 part of pigment and filler (talcum powder), 7 parts of curing agent (Q44 (commodity model) of Jiangsu xing Feng Co., ltd.), and 15 parts of diluent (water).
The preparation method of the aqueous epoxy resin emulsion comprises the following steps:
(1) 45 parts of aqueous epoxy resin (E62) is added into the reaction device, 15 parts of diluent (water) is added into the reaction device, stirring is started, the stirring speed is 800-1000 revolutions per minute until vortex appears at the center of the liquid surface, and stirring is stopped;
(2) Slowly adding 0.3 parts by weight of wetting agent (BYK-306), 0.2 parts by weight of defoamer (polyether) and 0.2 parts by weight of dispersant (SN-1729) into a reaction device; adding 20 parts by weight of ammonium polyphosphate flame retardant and 10 parts by weight of char forming agent (pentaerythritol) into a reaction device, and dispersing and stirring for a period of time after the materials are added so as to fully mix the materials; finally, adding 0.8 weight part of pigment and filler (talcum powder) and 0.3 weight part of anti-settling agent (polyethylene wax) into the reaction device, and dispersing and stirring again for a period of time to fully mix the materials to obtain emulsion; after standing for 20 minutes, the emulsion was observed and the emulsion had delaminated.
Comparative example 2
The aqueous epoxy resin coating of the ammonium polyphosphate flame retardant without the silicon element doped in the embodiment 2 is prepared from the following raw materials in parts by weight: 45 parts by weight of a water-based epoxy resin (E62 (commodity model) of Jiangsu xing Feng chemical technology Co., ltd.), 12 parts by weight of a char-forming agent (pentaerythritol), 0.3 part by weight of a wetting agent (BYK-306 (commodity model) of Pick brand, germany), 0.2 part by weight of a defoaming agent (polyether), 0.2 part by weight of a dispersing agent (SN-1729 (commodity model) of deep bamboo Co., ltd.), 0.3 part by weight of an anti-settling agent (polyethylene wax), 0.8 part by weight of a pigment and filler (talc), 7 parts by weight of a curing agent (Q44 (commodity model) of Jiangsu xing Feng Co., ltd.) and 15 parts by weight of a diluent (water).
The preparation method of the aqueous epoxy resin coating comprises the following steps:
(1) 45 parts of aqueous epoxy resin (E62) is added into the reaction device, 15 parts of diluent (water) is added into the reaction device, stirring is started, the stirring speed is 800-1000 revolutions per minute until vortex appears at the center of the liquid surface, and stirring is stopped;
(2) Slowly adding 0.3 parts by weight of wetting agent (BYK-306), 0.2 parts by weight of defoamer (polyether) and 0.2 parts by weight of dispersant (SN-1729) into a reaction device; adding 10 parts by weight of a char forming agent (pentaerythritol) into a reaction device, and dispersing and stirring for a period of time after the materials are added so as to fully mix the materials; finally, adding 0.8 weight part of pigment and filler (talcum powder) and 0.3 weight part of anti-settling agent (polyethylene wax) into the reaction device, and dispersing and stirring again for a period of time to fully mix the materials to obtain emulsion;
(3) 7 parts by weight of a curing agent (Q44) was added to the emulsion, and the mixture was cured at 30℃for 36 hours to obtain a cured product of an aqueous epoxy resin.
The properties of the flame-retardant epoxy resin cured products obtained in examples 1 to 3 and the aqueous epoxy resin cured product obtained in comparative example 2 were tested, and the test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the invention solves the problem that the aqueous epoxy resin is easy to burn, the prepared flame-retardant aqueous epoxy resin coating solves the fireproof problem and has excellent mechanical and physical properties of the epoxy resin, and the flame-retardant aqueous epoxy resin emulsion system has the advantages of high stability (no demulsification problem), stable storage, high adhesive force and strong weather resistance.
Uniformly coating the flame-retardant waterborne epoxy resin coating prepared in the embodiment 2 on the inner surface of a battery box, and curing to obtain an epoxy resin coating, wherein the specific steps are as follows: polishing the inner surface of the steel battery box body by using coarse sand paper to enable the inner surface to have certain roughness, flushing the inner surface of the box body by using water, and naturally airing; uniformly brushing the aqueous epoxy resin emulsion (with fluidity when fully cured) just added with the curing agent into the battery box body by using a natural fiber brush, wherein the coating thickness is 1-3mm; the battery is arranged in the box body.
And performing a thermal runaway experiment on the battery coated with the flame-retardant aqueous epoxy resin coating and the battery not coated with the flame-retardant aqueous epoxy resin coating, and observing the effect of the heat insulation layer. Experimental results: the battery coated with the flame-retardant waterborne epoxy resin coating does not fire within 2 hours after thermal runaway, the battery box body does not explode, and the battery which is not coated with the flame-retardant waterborne epoxy resin coating explodes after thermal runaway for 1-10 minutes.
As can be seen from the above data and fig. 4 to 5, the inner surface of the battery box is coated with the aqueous epoxy resin coating of the present invention as a heat insulation layer, and when the battery is thermally out of control, the heat insulation layer can foam, flame-retardant and heat-insulating, so as to prevent the battery box from burning and exploding, and effectively reduce the thermal-out fire hazard of the battery pack. When the flame-retardant waterborne epoxy resin coating is applied to the flame-retardant and explosion-proof battery box, the danger of the battery can be prevented from being in the box body when the battery is abnormal, particularly when the battery burns, and larger danger and loss are avoided.
Claims (5)
1. A flame retardant, characterized in that: the flame retardant is obtained by doping and modifying ammonium polyphosphate by adopting one element or a combination of multiple elements in magnesium, aluminum and silicon;
the preparation method of the flame retardant comprises the following steps: mixing aluminum chloride and/or magnesium chloride and/or silicon chloride with ammonium polyphosphate, adding water and a pH regulator into the mixture, reacting at room temperature, filtering after the reaction, calcining the precipitate at a high temperature, wherein the calcining temperature is 300-450 ℃, and obtaining a modified ammonium polyphosphate flame retardant; the mixing mass ratio of the aluminum chloride and/or the magnesium chloride and/or the silicon chloride to the ammonium polyphosphate is 1: 2-10; the pH regulator is potassium hydroxide, the reaction liquid is alkaline, and the pH of the reaction liquid is 8-11.
2. A flame retardant waterborne epoxy coating comprising the flame retardant of claim 1, characterized in that: the flame-retardant waterborne epoxy resin coating comprises the following components in parts by weight: 20-50 parts of aqueous epoxy resin, 20-50 parts of modified ammonium polyphosphate flame retardant, 10-30 parts of char forming agent, 0.1-0.5 part of wetting agent, 0.1-0.5 part of defoamer, 0.1-0.5 part of dispersing agent, 0.1-0.5 part of anti-settling agent, 0.6-2.0 parts of pigment and filler, 5-20 parts of curing agent and 10-30 parts of diluent.
3. The flame retardant waterborne epoxy coating of claim 2, wherein: the char forming agent is one or a combination of more of starch, cyclodextrin, sucrose, glucose, pentaerythritol or dipentaerythritol; the wetting agent is one or a combination of a plurality of BYK-S706, BYK-306, BYK-359, BYK-361 or SN-4727A; the defoaming agent is one or a combination of more of organosilicon defoaming agent, polyether, mineral oil or SN-6710; the dispersing agent is one or a combination of a plurality of BYK-307, BYK-330, BYK-341, BYK-2150, BYK-2155, BYK-104S, SN-1728, SN-1728A, SN-1729, SN-1760, SN-1776, SN-1790A, SN-1791, SN-1792 or SN-1798; the anti-settling agent is one or a combination of more of polyethylene wax, bentonite or polyamide wax; the pigment and filler is one or a combination of more of iron oxide red, carbon black, chrome yellow, zinc oxide, titanium pigment, barium sulfate, talcum powder, calcium carbonate, mica powder, talcum powder or quartz powder; the curing agent is one or a combination of a plurality of triethylamine, diethylamine, triethylenediamine, tetraethylenetriamine, piperazine, pyridine or piperidine; the diluent is one or a combination of a plurality of No. 200 solvent gasoline, dimethylbenzene, water, methanol, ethanol, isopropanol, ethyl acetate or propylene glycol dimethyl ether.
4. The method for preparing the flame-retardant waterborne epoxy resin coating according to claim 2, which is characterized by comprising the following steps:
(1) Adding the formula amount of aqueous epoxy resin into a reaction device, adding the formula amount of diluent into the reaction device, and stirring until vortex appears at the center of the liquid level;
(2) Slowly adding a wetting agent, a defoaming agent and a dispersing agent in the formula amount into a reaction device; adding the flame retardant and the char forming agent in the formula amount into a reaction device, and dispersing and stirring to fully mix the materials; finally, adding the pigment and filler and anti-settling agent in the formula amount into a reaction device, and dispersing and stirring again to fully mix the materials to obtain viscous emulsion;
(3) And adding a curing agent into the emulsion, and obtaining the flame-retardant waterborne epoxy resin cured coating under corresponding curing conditions.
5. The utility model provides a fire-retardant explosion-proof battery box which characterized in that: the flame-retardant explosion-proof battery box comprises a box body and a flame-retardant aqueous epoxy resin coating coated on the inner surface of the box body, wherein the flame-retardant aqueous epoxy resin coating is the flame-retardant aqueous epoxy resin coating of claim 2; the box takes the flame-retardant waterborne epoxy resin coating as a heat insulation layer, and the thickness of the heat insulation layer is 1-3 mm.
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