CN114773960B - Water-based intumescent epoxy fireproof anticorrosive paint - Google Patents

Abstract

The invention discloses a water-based intumescent epoxy fireproof anticorrosive paint which comprises a component A and a component B, wherein the component A comprises 15-25% of water-based epoxy emulsion with high epoxy equivalent, 10-20% of water-based epoxy emulsion with low epoxy equivalent, 0.1-1% of defoaming agent, 0.5-2% of viscosity regulator and 5-30% of fireproof filler by mass percentage; the high epoxy equivalent weight aqueous epoxy emulsion is a nonionic emulsion with the epoxy equivalent weight of 555-1200, and the low epoxy equivalent weight aqueous epoxy emulsion is a nonionic emulsion with the epoxy equivalent weight of 180-410; the component B comprises 15-30% of water, 5-20% of a curing agent, 15-30% of a flame-retardant foaming system, 0.2-2% of a dispersing agent, 3-5% of a nano filler and 0.5-1.5% of a reinforcing fiber.

Description

Water-based intumescent epoxy fireproof anticorrosive paint

Technical Field

The present invention relates generally to an aqueous intumescent epoxy fire and corrosion protective coating, and in particular to an aqueous intumescent epoxy fire and corrosion protective coating that may be advantageously applied to battery packs such as electric vehicles, steel structure buildings or construction scenes.

Background

The new energy electric automobile replaces the traditional fuel oil automobile and is a great trend of the development of the automobile industry at present. New energy electric vehicles typically use aluminum alloys as the housing for the battery pack. Due to poor heat resistance of aluminum alloy, it is usually necessary to coat the surface of the aluminum alloy battery pack with a fireproof heat-insulating material to improve its fire resistance and safety.

The steel structure is increasingly used in construction engineering and various industrial facilities due to the advantages of high strength, good toughness, fast construction and the like. However, the steel structure has a large thermal conductivity, and when a fire occurs, the temperature of the steel structure rapidly increases in a short time, and the mechanical strength of the steel structure gradually decreases with the increase of the temperature, and particularly when the temperature reaches 500 ℃ or more, the steel structure loses the supporting force due to the rapid decrease of the mechanical strength, and finally the building collapses. The fireproof protection of the reinforced steel structure further improves the fireproof performance of the reinforced steel structure, not only wins time for rescue, but also reduces various losses caused by fire to the maximum extent. In addition, because the steel structure is exposed in the air for a long time and is easy to be corroded by chemical particles such as acid, alkali, salt and the like in the air, the steel structure is seriously corroded, and the fireproof anticorrosive paint can be coated on steel structures in different forms, is not limited by space and shape, and is an ideal fireproof anticorrosive material for the steel structure.

The fireproof paint is a special functional paint which is coated on the surface of a base material, can prevent fire, delay the ignition time and the spread of fire of the base material, or increase the heat insulation property to delay the structural damage time of the base material, and has the protection functions of corrosion resistance, rust resistance and the like and the decoration function. The fireproof paint can be mainly divided into steel structure fireproof paint and finishing type fireproof paint according to different coating materials. National standards GB14907-2018 Steel Structure fireproof paint and GB12441-2018 finishing type fireproof paint stipulate technical requirements to be met by various types of fireproof paint and test methods for detecting various properties.

The water-based intumescent epoxy fire-retardant coating is a coating with a fire-retardant function by taking water as a dispersion medium, taking epoxy resin as a film-forming substance, taking a fire-retardant system material as an intumescent fire-retardant material and adding various functional additives or fillers. Under the action of high temperature, the film forming matter and the fire-retardant system material are subjected to a series of complex processes of melting, decomposition, acid formation, catalytic crosslinking, esterification, carbon formation, gas generation and the like to finally form a porous expanded foam carbon layer which is dozens of to dozens of times thicker than the original coating. The foam carbon layer can play a good role in oxygen resistance, heat insulation and heat conduction reduction, and further play a fireproof function. In addition, after the epoxy resin is formed into a film, the anticorrosion function of the base material can be greatly improved due to the excellent sealing property and chemical corrosion resistance of the epoxy resin.

Chinese patent publication No. CN104130671A discloses an aqueous ultrathin intumescent fire retardant coating for steel structures, which comprises the following components: 10-35 parts of modified water-based epoxy emulsion, and a curing agent: 1-8 parts of styrene-acrylic emulsion or silicone-acrylic emulsion, 5-15 parts of ammonium polyphosphate, 6-12 parts of melamine, 8-16 parts of pentaerythritol, 5-15 parts of flame retardant, 5-15 parts of pigment and filler, 2-8 parts of auxiliary agent and 15-35 parts of water; wherein the modified waterborne epoxy emulsion is bisphenol A epoxy resin emulsion, the solid content is 40wt% -55 wt%, and the epoxy equivalent is 1500-2000; the curing agent is any one of amidated polyamine, polyamide and polyamine-epoxy adduct; the pigment and filler is any three or more than four of titanium dioxide, precipitated barium sulfate, kaolin, wollastonite powder, talcum powder, diatomite, sepiolite, vitrified micro bubbles and expanded vermiculite; the flame retardant is a mixture of any two or more than three of aluminum hydroxide, magnesium oxide, zinc borate, antimony trioxide, tributyl phosphate, ammonium phosphate, chlorinated paraffin, tetrabromobisphenol A and decabromodiphenyl ether. The fireproof coating has the characteristics of low cost of raw materials, simple preparation process, environmental protection and the like.

The Chinese patent with publication number CN101712840A discloses an ultrathin water-based epoxy resin intumescent fire-retardant coating, which comprises a component A and a component B; the component A comprises water, a curing agent, ammonium polyphosphate, a dispersing agent and a defoaming agent, and the component B comprises a water-based epoxy emulsion, a thickening agent and a defoaming agent. The water-based epoxy emulsion is an anionic emulsion, the solid content of the water-based epoxy emulsion is 45-55% by mass, the epoxy equivalent is 400-1100, and the pH value is 6-8. The curing agent is a water-based modified amine curing agent, the viscosity of the curing agent is 500-8000 mPa.s, the pH value is 7-9, and the equivalent of active hydrogen is 300-600. The fireproof coating has the advantages of simple preparation process, environmental protection and excellent performance, and can be used for fire safety protection in large steel structures such as buildings, ships, oil storage tanks and the like.

Chinese patent with publication number CN113444425A discloses a water-based epoxy fire-retardant coating, and a preparation method and application thereof. The water-based epoxy fireproof coating consists of a component A and a component B, wherein the component A comprises water-based epoxy emulsion, vinyl-epoxy emulsion, a carbon forming catalyst, a carbon forming agent, a foaming agent and a flame retardant, and the component B comprises a curing agent and a fireproof fiber. The waterborne epoxy emulsion is at least one of epoxy resin aqueous dispersion, polyester modified epoxy emulsion, polyether modified epoxy emulsion, aliphatic epoxy emulsion, alicyclic epoxy emulsion, polyfunctional epoxy emulsion, hyperbranched epoxy emulsion, modified epoxy emulsion A and modified epoxy emulsion B. The vinyl-epoxy emulsion is prepared from epoxy resin, vinyl monomer, emulsifier, catalyst A and deionized water. The water-based epoxy emulsion comprises 100 parts by weight of water-based epoxy emulsion and 0-100 parts by weight of vinyl-epoxy emulsion. The water-based epoxy fireproof coating has the advantages of excellent sealing performance of both the solvent-free epoxy fireproof coating and the high-solid-content epoxy fireproof coating, brings excellent corrosion resistance, UV irradiation resistance, water resistance and organic solvent resistance, and can be used in severe outdoor environments.

The fire-retardant coatings disclosed in publication nos. CN104130671A and CN101712840A use a single epoxy emulsion as a film-forming substance, and fail to achieve both flexibility (in physical and chemical properties, the adhesion strength) and hardness (in physical and chemical properties, the impact resistance) of the coating. The fire-retardant coating with publication number CN113444425A adopts single water-based epoxy emulsion or adopts water-based epoxy emulsion and self-made vinyl epoxy emulsion as film-forming substances, and still fails to take account of the problems of flexibility and hardness of the coating. In addition, there is still a need in the art for improvements and enhancements in formulation selection, physical and chemical properties, and fire resistance.

Disclosure of Invention

The invention provides a water-based intumescent epoxy fireproof anticorrosive coating with a new formula, which can solve the problems of flexibility and hardness of the coating and has excellent physical and chemical properties and fire resistance.

According to one aspect of the invention, the water-based intumescent epoxy fire-retardant anticorrosive paint comprises a component A and a component B, wherein the component A comprises 15-25% of water-based epoxy emulsion with high epoxy equivalent, 10-20% of water-based epoxy emulsion with low epoxy equivalent, 0.1-1% of defoaming agent, 0.5-2% of viscosity regulator and 5-30% of fire-retardant filler by mass percentage; the high-epoxy-equivalent water-based epoxy emulsion is a non-ionic emulsion with the epoxy equivalent of 555-1200, and the low-epoxy-equivalent water-based epoxy emulsion is a non-ionic emulsion with the epoxy equivalent of 180-410; the component B comprises 15-30% of water, 5-20% of a curing agent, 15-30% of a flame-retardant foaming system, 0.2-2% of a dispersing agent, 3-5% of a nano filler and 0.5-1.5% of a reinforcing fiber.

According to another aspect of the present invention, the high epoxy equivalent weight aqueous epoxy emulsion comprises at least one of GEM02 type aqueous epoxy resin emulsion (epoxy equivalent 850-1000) available from Shanghai green Jia aqueous paint Co., Ltd, K-030 type aqueous epoxy resin emulsion (epoxy equivalent 1150) and K-021 type aqueous epoxy resin emulsion (epoxy equivalent 1100-1200) available from Guangzhou epoxy materials science Co., Ltd, JT-WBE530 type aqueous epoxy resin emulsion (epoxy equivalent 930-1130) available from Guangzhou epoxy materials science Co., Ltd, GL-1900 type aqueous epoxy resin emulsion (epoxy equivalent 555-625) available from Guangzhou Ging New materials Co., Ltd, and the like.

Preferably, the high epoxy equivalent weight aqueous epoxy emulsion refers to a nonionic emulsion having an epoxy equivalent weight of 850 to 1200, and includes at least one of GEM02 type aqueous epoxy resin emulsion (epoxy equivalent weight 850 to 1000) available from Shanghai green water paint Co., Ltd, K-030 type aqueous epoxy resin emulsion (epoxy equivalent weight 1150) and K-021 type aqueous epoxy resin emulsion (epoxy equivalent weight 1100 to 1200) available from Guangzhou epoxy material science Co., Ltd, JT-WBE530 type aqueous epoxy resin emulsion (epoxy equivalent weight 930-1130) available from electrocoat science Co., Ltd, and the like.

According to another aspect of the present invention, the low epoxy equivalent aqueous epoxy emulsion comprises at least one of DS-5100 type aqueous epoxy resin emulsion (epoxy equivalent 410) available from Shanghai technetium Cheng New Material Co., Ltd, JT-851 type aqueous epoxy resin emulsion (epoxy equivalent 360. + -. 50) available from Foshan City New Material Co., Ltd, BH-644 type aqueous epoxy resin emulsion (epoxy equivalent 220 to 280) available from Guangdong chemical products Co., Ltd, BH-653 type aqueous epoxy resin emulsion (epoxy equivalent 180 to 230) and BH-655 type aqueous epoxy resin emulsion (epoxy equivalent 180 to 240).

Preferably, the low epoxy equivalent waterborne epoxy emulsion is a nonionic emulsion with an epoxy equivalent of 180-280. Alternatively, the low epoxy equivalent aqueous epoxy emulsion comprises at least one of BH-644 type aqueous epoxy resin emulsion (epoxy equivalent 220-280), BH-653 type aqueous epoxy resin emulsion (epoxy equivalent 180-230) and BH-655 type aqueous epoxy resin emulsion (epoxy equivalent 180-240) available from Guanguan Chemicals, Inc.

According to the water-based intumescent epoxy fireproof anticorrosive paint disclosed by the invention, the epoxy resin is used as a film forming substance, and the anticorrosive function of the paint can be greatly improved due to excellent sealing property and chemical corrosion resistance after film forming. Meanwhile, the fireproof anticorrosive coating provided by the invention adopts the combination of two kinds of water-based epoxy emulsion with different epoxy equivalent weights as a film forming material, so that the molecular weight distribution of epoxy resin in the coating is wider, the molecular chain of the epoxy resin can be more flexible due to high molecular weight, the flexibility and toughness of the coating are further improved, the cross-linking point of the molecular chain of the epoxy resin can be increased due to low molecular weight, and the hardness of the coating is further improved. The fireproof anticorrosive paint provided by the invention not only solves the problem that the flexibility and the hardness of the paint can not be considered simultaneously when a single epoxy emulsion is used as a film forming substance, but also solves the problems of reduced epoxy sealing effect and poor corrosion resistance caused by compounding of the epoxy emulsion and other emulsions.

According to another aspect of the present invention, the antifoaming agent includes, but is not limited to, at least one of polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxypropylene glycerol ether, polydimethylsiloxane, and the like. The defoaming agent can inhibit bubbles and defoams generated in the stirring process of the coating, so that the shrinkage cavity defect generated in the film forming process of the coating is avoided. Alternatively, the antifoaming agent is a modesty DF6800 antifoaming agent or a VP-6510 antifoaming agent of hamming corporation, a TEGO-8030 antifoaming agent or a TEGO-810 antifoaming agent of digo corporation, germany, and the like.

According to another aspect of the present invention, the viscosity modifier includes, but is not limited to, at least one of attapulgite clay, organobentonite, sodium carboxymethyl cellulose, expandable graphite, diatomaceous earth, and the like.

According to another aspect of the invention, the refractory filler comprises at least two of titanium dioxide, silica, zinc oxide, alumina, aluminum hydroxide, anhydrous zinc borate, and the like. Preferably, the appearance of the refractory filler is white powder, and the particle size is 0.1-10 μm.

According to another aspect of the invention, the refractory filler comprises at least titanium dioxide. Titanium dioxide has excellent opacity, whiteness and brightness, and is widely used as a white pigment. In the fireproof paint, titanium dioxide not only can be used as a white pigment to play a role in covering, but also can react with phosphate in a flame-retardant foaming system at high temperature to generate a ceramic-like titanium pyrophosphate protective layer which plays a role in protecting and supporting a carbon layer.

According to another aspect of the present invention, the refractory filler includes at least alumina and anhydrous zinc borate, wherein a mass ratio of the alumina to the anhydrous zinc borate is 1: 1-5.7: 1. the inventors have found that when alumina and anhydrous zinc borate are used as the refractory filler in the appropriate proportions, the flame resistance time of the coating is significantly increased. Preferably, the mass ratio of the alumina to the anhydrous zinc borate is 3: 1-4: 1.

according to another aspect of the present invention, the curing agent is preferably at least one of polyamide, polyetheramine, polyamine-modified curing agent, and the like. Preferably, the curing agent is a nonionic water-soluble modified epoxy polyamine adduct, the viscosity of the adduct is 3000-20000 mPa.s, and the equivalent of active hydrogen is 100-400. Preferably, the curing agent has a viscosity of 5000 to 15000mPa.s and an active hydrogen equivalent of 100 to 300. Optionally, the curing agent is a waterborne epoxy resin curing agent K-62 which is purchased from Guangzhou epoxy material science and technology limited company, the active hydrogen equivalent thereof is 225, and the viscosity thereof is 9500-15000 mPa.s.

According to another aspect of the invention, the flame retardant foam system is an N-P cage type macromolecular intumescent flame retardant system, wherein the nitrogen content is more than or equal to 11 percent and the phosphorus content is more than or equal to 8 percent. Alternatively, the flame-retardant foam system is an intumescent macromolecular flame retardant IFR101-A, IFR101-B type intumescent flame retardant, IFR101-C type intumescent flame retardant, IFR201-A type intumescent flame retardant or IFR201-B type intumescent flame retardant and the like which are available from Tokajoram New materials science and technology, Inc.

According to another aspect of the invention, the dispersant includes, but is not limited to, at least one of synthetic polymers, multivalent carboxylic acids, coupling agents, silicates, and the like. Alternatively, the dispersant is a BYK-110 type dispersant or a BYK-161 type dispersant from Pick, Germany, an EFKA-4071 type dispersant from Effka, the Netherlands, and the like.

According to another aspect of the invention, the nanofiller comprises at least one of magnesium hydroxide, composite ferrotitanium powder, expandable graphite powder, hydrotalcite, talc.

According to another aspect of the present invention, the reinforcing fiber includes at least one of carbon fiber, glass fiber, alumina fiber, aramid fiber, and the like. Preferably, the reinforcing fibers comprise a fiber with a diameter of 3-5 μm and an aspect ratio of 6: 1-8: 1 of glass fibers; more preferably, the reinforcing fiber comprises alumina fiber with the diameter of 3-3 μm and the length-diameter ratio of 3: 1-5: 1.

According to one aspect of the invention, the preparation process of the water-based intumescent epoxy fire-retardant anticorrosive paint comprises the following steps:

step 1: stirring and mixing the high-epoxy equivalent water-based epoxy emulsion, the low-epoxy equivalent water-based epoxy emulsion, the defoaming agent, the viscosity regulator and the refractory filler in a formula ratio in a ball mill at a low speed for 1-2 hours to obtain a component A of the fireproof anticorrosive coating;

step 2: adding water and a dispersing agent into a ball mill according to the formula proportion, sequentially adding a flame-retardant foaming system, a nano filler and reinforcing fibers, grinding for 1-2 hours, finally adding a curing agent, and continuously grinding for 0.5-1 hour to obtain a component B of the water-based intumescent epoxy fireproof anticorrosive coating.

According to one aspect of the invention, the application method of the water-based intumescent epoxy fire-retardant anticorrosive paint comprises the following steps of: the component B is mixed according to the mass ratio of 1-5: 0.6-2 and then fully stirred uniformly. The water-based intumescent epoxy fireproof anticorrosive paint can be prepared through the steps.

According to another aspect of the present invention, wherein one or more of the defoamer, the viscosity modifier and the refractory filler in the a-component are replaced into the B-component. Namely, one or more components of the defoaming agent, the viscosity regulator and the fire-resistant filler are removed from the component A, and one or more components of the defoaming agent, the viscosity regulator and the fire-resistant filler are added into the component B. For example, the fire-resistant filler is removed in the A component and the fire-resistant filler is added in the B component, so that the A component comprises the high epoxy equivalent weight aqueous epoxy emulsion, the low epoxy equivalent weight aqueous epoxy emulsion, the defoamer, the viscosity modifier; the component B comprises the water, the fire-resistant filler, the curing agent, the flame-retardant foaming system, the dispersing agent, the nano filler and the reinforcing fiber. For another example, the defoaming agent, the viscosity regulator and the fire-resistant filler are removed from the component A, and the defoaming agent, the viscosity regulator and the fire-resistant filler are added into the component B, so that the component A comprises the high epoxy equivalent aqueous epoxy emulsion and the low epoxy equivalent aqueous epoxy emulsion; the component B comprises the water, the defoaming agent, the viscosity regulator, the refractory filler, the curing agent, the flame-retardant foaming system, the dispersing agent, the nano filler and the reinforcing fiber.

According to another aspect of the present invention, wherein one or more of the water, the flame retardant foaming system, the dispersant, the nanofiller, the reinforcing fibers in the B-side are replaced into the a-side. Namely, one or more of water, the flame-retardant foaming system, the dispersing agent, the nano filler and the reinforcing fiber are removed from the component B, and simultaneously, the corresponding water, the flame-retardant foaming system, the dispersing agent, the nano filler and the reinforcing fiber are added into the component B. For example, nanofillers are removed from the A-side and added to the A-side such that the A-side comprises the high epoxy equivalent aqueous epoxy emulsion, the low epoxy equivalent aqueous epoxy emulsion, the defoamer, the viscosity modifier, the fire resistant filler and the nanofillers; the component B comprises the water, the fire-resistant filler, the curing agent, the flame-retardant foaming system, the dispersing agent and the reinforcing fiber.

According to another aspect of the invention, the water-based intumescent epoxy fire-retardant anticorrosive coating is prepared by removing water, a flame-retardant foaming system, a dispersing agent, a nano filler and reinforcing fibers from the component B, and adding water, the flame-retardant foaming system, the dispersing agent, the nano filler and the reinforcing fibers to the component A, so that the component A comprises the high epoxy equivalent aqueous epoxy emulsion, the low epoxy equivalent aqueous epoxy emulsion, the defoaming agent, the viscosity regulator, the fire-retardant filler water, the flame-retardant foaming system, the dispersing agent, the nano filler and the reinforcing fibers; the component B comprises the curing agent. Preferably, the preparation process of the water-based intumescent epoxy fire-retardant anticorrosive paint comprises the following steps:

step 1: according to the formula proportion, water, a dispersing agent and a defoaming agent are sequentially added into a dispersing kettle, after 5-20 minutes of dispersion, a flame-retardant foaming system, a refractory filler, a nano filler and reinforcing fibers are sequentially added, then the mixture is stirred and dispersed at a low speed for 10-30 minutes, and finally the mixture is stirred and dispersed at a high speed for 30-60 minutes.

Step 2: and (4) transferring the dispersed materials into a grinding machine, and continuously grinding for 0.5-3 hours at the rotating speed of 600-1200 r/min.

And 3, step 3: and transferring the ground material into a stirring kettle, slowly adding the water-based epoxy emulsion in the stirring process in the stirring kettle, stirring for 30-60 minutes, continuously stirring, slowly adding the viscosity regulator, uniformly stirring, vacuumizing to-0.04- -0.10MPa, and continuously stirring for 30-60 minutes to obtain the component A of the water-based intumescent epoxy fireproof anticorrosive paint. In this step, the aqueous epoxy emulsion includes a high epoxy equivalent aqueous epoxy emulsion and a low epoxy equivalent aqueous epoxy emulsion, and these two aqueous epoxy emulsions may be added to the stirring tank separately, or the two aqueous epoxy emulsions may be mixed in advance, and then the mixed aqueous epoxy emulsion is added to the stirring tank. When the two waterborne epoxy emulsions are respectively added into the stirring kettle, the waterborne epoxy emulsion with high epoxy equivalent weight can be added firstly, and then the waterborne epoxy emulsion with low epoxy equivalent weight can be added; or the low epoxy equivalent waterborne epoxy emulsion can be added firstly, and then the high epoxy equivalent waterborne epoxy emulsion can be added; it is also possible to add the two emulsions alternately to the stirred tank.

And 4, step 4: the curing agent is used as the component B of the water-based intumescent epoxy fireproof anticorrosive paint.

According to the water-based intumescent epoxy fireproof anticorrosive paint disclosed by the invention, the combination of the epoxy resin with high epoxy equivalent and the epoxy resin with low epoxy equivalent is used as a film-forming material, so that the problems of flexibility and hardness of the paint can be solved, and the paint has excellent physical and chemical properties. Meanwhile, the combination of the alumina powder and the anhydrous zinc borate is used as the fireproof filler of the waterborne intumescent epoxy fireproof anticorrosive paint, so that the flame-retardant time of the paint and the fire resistance limit of the base material can be obviously improved under the condition that other components are basically the same, and the possibility that the base material is damaged in fire is greatly reduced.

The water-based intumescent epoxy fireproof anticorrosive paint has excellent physical and chemical properties and fire resistance, so that the water-based intumescent epoxy fireproof anticorrosive paint can be favorably applied to battery packs of new energy electric automobiles, steel structure buildings or construction scenes.

Detailed Description

For the present invention, the following terms are used in the present specification.

"to" includes two values before and after the "to" and, for example, 5 to 10 means 5 or more and 10 or less.

"mm" means a unit of length of millimeter, for example 1mm means 1 millimeter.

"μm" means a unit of length of micron, for example 1 μm means 1 micron.

"mL" means volume unit milliliter, e.g., 1mL means volume is 1 milliliter.

"h" represents the time unit hourly minutes, for example 1h represents 1 hour.

"min" means time unit minutes, for example 185min means 185 minutes.

For a better illustration of the invention, some examples are listed below, but it should be understood that these examples are not intended to limit the invention.

Table 1 attached later shows the formulation of the invention in examples 1 to 6 and comparative examples 1 and 2, and the details are as follows.

Example 1.

The water-based intumescent epoxy fire-retardant anticorrosive coating comprises a component A and a component B, wherein the component A comprises 25% of GL-1900 water-based epoxy resin emulsion purchased from Guangzhou Georgi New materials GmbH, 10% of BBH-653 water-based epoxy resin emulsion purchased from Dongguan Guangtong chemical products GmbH, 0.5% of Hamming Siemens DF6800 defoaming agent, 1% of organic bentonite, 2.5% of titanium dioxide, 7.5% of aluminum oxide and 2.5% of anhydrous zinc borate by mass percentage.

The component B comprises 18 percent of water, 8 percent of waterborne epoxy resin curing agent K-62 which is bought from Guangzhou epoxy material technology Co., Ltd, 20 percent of IFR201-A type intumescent flame retardant which is bought from Sichuan tall Annean New material technology Co., Ltd, 0.8 percent of BYK-110 type dispersing agent which is bought from Germany Bike Co., Ltd, 3.2 percent of expandable graphite and 1 percent of alumina fiber.

The preparation process comprises the following steps: and stirring and mixing the component A in the proportion formula in a ball mill at a low speed for 90 minutes to obtain the component A of the water-based intumescent epoxy fireproof anticorrosive paint. And adding the water and the dispersant in the formula proportion of the component B into a ball mill, sequentially adding the IFR201-A type intumescent flame retardant, the expandable graphite and the alumina fiber, grinding for 100 minutes, and finally adding the curing agent K-62, and continuously grinding for 45 minutes to obtain the component B of the waterborne intumescent epoxy fireproof anticorrosive paint. The component A and the component B are mixed according to the mass ratio of 1: 1 and then are fully and uniformly stirred to obtain the water-based intumescent epoxy fireproof anticorrosive paint of the embodiment.

Example 2.

The aqueous intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the epoxy resin emulsion of the component A comprises 20% of GEM02 type aqueous epoxy resin emulsion from Shanghai green Jia aqueous paint company Limited and 15% of BBH-644 type aqueous epoxy resin emulsion from Dongguan Guantong chemical products company Limited in percentage by mass. The formulation of the defoamer, viscosity modifier and refractory filler in component a was the same as in example 1. The formulation of component B was the same as in example 1. The procedure is as in example 1.

Example 3.

The waterborne intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the epoxy resin emulsion of the component A comprises 15% of K-030 waterborne epoxy resin emulsion purchased from Guangzhou epoxy materials science and technology Limited and 20% of DS-5100 waterborne epoxy resin emulsion purchased from Shanghai technetium Cheng novel materials Limited in percentage by mass. The formulation of the defoamer, viscosity modifier and refractory filler in component A was the same as in example 1. The formulation of component B was the same as in example 1. The procedure is as in example 1.

Example 4.

The water-based intumescent epoxy fire-retardant anticorrosive coating comprises a component A and a component B, wherein the component A comprises 25% of GL-1900 type water-based epoxy resin emulsion purchased from Guangzhou George New materials Co., Ltd and 10% of BBH-644 type water-based epoxy resin emulsion purchased from Dongguan Guantong chemical products Co., Ltd in percentage by mass. The formulation of the defoamer, viscosity modifier and refractory filler in component a was the same as in example 1. The formulation of component B was the same as in example 1. The procedure was as in example 1.

Example 5.

The waterborne intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the epoxy resin emulsion of the component A comprises 20% of GEM02 type waterborne epoxy resin emulsion purchased from Shanghai green Jia waterborne paint Co., Ltd and 15% of DS-5100 type waterborne epoxy resin emulsion purchased from Shanghai technetium Cheng novel material Co., Ltd in percentage by mass. The formulation of the defoamer, viscosity modifier and refractory filler in component A was the same as in example 1. The formulation of component B was the same as in example 1. The procedure is as in example 1.

Example 6.

The aqueous intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the epoxy resin emulsion of the component A comprises 15% of K-030 type aqueous epoxy resin emulsion from Guangzhou epoxy material technology Co., Ltd and 20% of BBH-653 type aqueous epoxy resin emulsion from Dongguan Guangtong chemical products Co., Ltd in percentage by mass. The formulation of the defoamer, viscosity modifier and refractory filler in component A was the same as in example 1. The formulation of component B was the same as in example 1. The procedure was as in example 1.

Comparative example 1.

The aqueous intumescent epoxy fire-retardant anticorrosive paint of the comparative example comprises a component A and a component B, wherein the epoxy emulsion of the component A is 35 percent of K-030 type aqueous epoxy resin emulsion purchased from Guangzhou epoxy material science and technology company Limited in percentage by mass. The formulation of the defoamer, viscosity modifier and refractory filler in component a was the same as in example 1. The formulation of component B was the same as in example 1. The procedure was as in example 1.

Comparative example 2.

The water-based intumescent epoxy fire-retardant anticorrosive paint comprises a component A and a component B, wherein the epoxy emulsion of the component A is 35 percent of BBH-653 water-based epoxy resin emulsion which is purchased from Guanguan general chemical products Co., Ltd. The formulation of the defoamer, viscosity modifier and refractory filler in component a was the same as in example 1. The formulation of the B component was the same as in example 1. The procedure was as in example 1.

Table 2 attached later is the results of performance tests performed on the waterborne intumescent epoxy fire-retardant and anticorrosive coatings of examples 1 to 6 of the present invention and comparative examples 1 and 2 according to GB14907-2018 and GB 12441-2018.

As can be seen from the test results of table 2: the coatings according to examples 1 to 6 of the present invention did not show cracks in the initial dry cracking resistance, and had excellent adhesive strength (0.49 to 0.71 MPa) and impact resistance (49 to 58 cm). The coating according to comparative example 1, although comparable in initial drying crack resistance and adhesive strength to those of examples 1 to 6, was remarkably reduced in impact resistance. The coating according to comparative example 2 is significantly insufficient in initial dry cracking resistance and adhesive strength, although it has strong impact resistance. Through these tests, the inventors found that the first aspect of the present invention, that is, the use of a combination of an epoxy resin having a high epoxy equivalent and an epoxy resin having a low epoxy equivalent as a film-forming material, can achieve both the problems of flexibility and hardness of the coating material, so that the coating material has excellent physicochemical properties.

Table 3 attached below shows the formulation of the invention in examples 7 to 12 and comparative examples 3 and 4, and the details are as follows.

Example 7.

The aqueous intumescent epoxy fireproof and anticorrosive coating comprises a component A and a component B, wherein the epoxy resin emulsion of the component A comprises 20% of K-030 type aqueous epoxy resin emulsion from Guangzhou epoxy material science and technology Co., Ltd, 15% of BBH-644 type aqueous epoxy resin emulsion from Dongguan Guangtong general articles of manufacture Co., Ltd, 0.5% of hamming modesty DF6800 type defoaming agent, 1% of organic bentonite, 2.5% of titanium dioxide, 5% of aluminum oxide and 5% of anhydrous zinc borate by mass percentage. The formulation of the B component was the same as in example 1. The procedure was as in example 1.

Example 8.

The water-based intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the fireproof filler comprises 6% of alumina and 4% of anhydrous zinc borate by mass percent, and the epoxy resin emulsion, the defoaming agent and the viscosity regulator of the component A are the same as those of the component A in the embodiment 6; the formulation of component B was the same as in example 6. The procedure was as in example 1.

Example 9.

The water-based intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the fireproof filler comprises 7% of alumina and 3% of anhydrous zinc borate by mass percent, and the epoxy resin emulsion, the antifoaming agent and the viscosity regulator of the component A are the same as those of the component A in the embodiment 6; the formulation of component B was the same as in example 6. The procedure was as in example 1.

Example 10.

The water-based intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the fireproof filler comprises 7.5% of alumina and 2.5% of anhydrous zinc borate by mass percent, and the epoxy resin emulsion, the defoaming agent and the viscosity regulator of the component A are the same as those of the component A in the embodiment 6; the formulation of component B was the same as in example 6. The procedure is as in example 1.

Example 11.

The water-based intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the fireproof filler comprises 8% of alumina and 2% of anhydrous zinc borate by mass percent, and the epoxy resin emulsion, the defoaming agent and the viscosity regulator of the component A are the same as those of the component A in example 6; the formulation of component B was the same as in example 6. The preparation process is the same as example 1

Example 12.

The water-based intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the fireproof filler comprises 8.5% of alumina and 1.5% of anhydrous zinc borate by mass percent, and the epoxy resin emulsion, the defoaming agent and the viscosity regulator of the component A are the same as those of the component A in the embodiment 6; the formulation of component B was the same as in example 6. The procedure is as in example 1.

Comparative example 3.

The water-based intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the fireproof filler comprises 7.5% of alumina and 2.5% of 3.5% of zinc borate hydrate by mass percent, and the epoxy resin emulsion, the defoaming agent and the viscosity regulator of the component A are the same as those of the component A in the embodiment 6; the formulation of component B was the same as in example 6. The procedure was as in example 1.

Comparative example 4.

The water-based intumescent epoxy fireproof anticorrosive paint comprises a component A and a component B, wherein the fireproof filler comprises 7.5% of aluminum hydroxide and 2.5% of anhydrous zinc borate by mass percent, and the epoxy resin emulsion, the defoaming agent and the viscosity regulator of the component A are the same as those of the component A in the embodiment 6; the formulation of component B was the same as in example 6. The procedure was as in example 1.

Table 4 attached later is the results of performance tests performed on the waterborne intumescent epoxy fire-retardant and anticorrosive coatings of examples 7 to 12 of the present invention and comparative examples 3 and 4 according to GB 12441-2018.

As can be seen from the test results of table 4: examples 7 to 12 according to the present invention used alumina and anhydrous zinc borate in appropriate proportions as the refractory filler, and the coatings all had excellent flame-retardant time. In comparative example 3, when aluminum oxide was replaced with aluminum hydroxide, the flame-retardant time of the coating material was significantly reduced; when the anhydrous zinc borate was replaced with 3.5 hydrated zinc borate in comparative example 4, the flame resistance time of the coating was also significantly reduced. Through these tests, the inventors have found that the second aspect of the present invention, i.e., when a combination of alumina powder and anhydrous zinc borate is used as a refractory filler in an aqueous intumescent epoxy fire-retardant and corrosion-resistant coating, enables the coating to significantly improve the fire-retardant time of the coating and the fire-retardant limit of the substrate with the other components being substantially the same, thereby greatly reducing the possibility of the substrate being damaged in a fire.

Although the present invention has been described in connection with the above specific embodiments, it should be understood that the foregoing description does not limit the scope of the present invention to the above specific embodiments, but rather the foregoing description is intended to indicate that the scope of the present invention as defined by the claims encompasses the above specific embodiments and their equivalents.

Claims (10)

1. A water-based intumescent epoxy fireproof anticorrosive paint is characterized in that: the coating comprises a component A and a component B, wherein the component A comprises 15-25% of high epoxy equivalent aqueous epoxy emulsion, 10-20% of low epoxy equivalent aqueous epoxy emulsion, 0.1-1% of defoaming agent, 0.5-2% of viscosity regulator and 5-30% of refractory filler by mass percentage; the high-epoxy-equivalent water-based epoxy emulsion is a non-ionic emulsion with the epoxy equivalent of 555-1200, and the low-epoxy-equivalent water-based epoxy emulsion is a non-ionic emulsion with the epoxy equivalent of 180-360; the component B comprises 15-30% of water, 5-20% of a curing agent, 15-30% of a flame-retardant foaming system, 0.2-2% of a dispersing agent, 3-5% of a nano filler and 0.5-1.5% of a reinforcing fiber.

2. The aqueous intumescent epoxy fire-retardant anticorrosive coating of claim 1, characterized in that: wherein the high epoxy equivalent weight aqueous epoxy emulsion is a nonionic emulsion with the epoxy equivalent weight of 850-1200.

3. The aqueous intumescent epoxy fire-retardant anticorrosive coating of claim 1, characterized in that: the low epoxy equivalent water-based epoxy emulsion is a nonionic emulsion with the epoxy equivalent of 180-280.

4. An aqueous intumescent epoxy fire protection and corrosion protection coating as claimed in any of claims 1 to 3, characterized in that: the refractory filler comprises at least two of titanium dioxide, silicon dioxide, zinc oxide, aluminum hydroxide and anhydrous zinc borate.

5. The aqueous intumescent epoxy fire-retardant anticorrosive coating of claim 4, characterized in that: the refractory filler comprises alumina and anhydrous zinc borate, wherein the mass ratio of the alumina to the anhydrous zinc borate is 1: 1-5.7: 1.

6. the aqueous intumescent epoxy fire-retardant anticorrosive coating of claim 5, characterized in that: wherein the mass ratio of the aluminum oxide to the anhydrous zinc borate is 3: 1-4: 1.

7. an aqueous intumescent epoxy fire protection and corrosion protection coating as claimed in any of claims 1 to 3, characterized in that: the application method of the water-based intumescent epoxy fireproof anticorrosive paint comprises the following steps: according to the component A: the component B is mixed and stirred uniformly according to the mass ratio of 1-5: 0.6-2.

8. The aqueous intumescent epoxy fire retardant anticorrosive coating of any one of claims 1 to 3, characterized in that: wherein one or more of the defoamer, the viscosity modifier, the refractory filler in the A-side are replaced into the B-side.

9. The aqueous intumescent epoxy fire retardant anticorrosive coating of any one of claims 1 to 3, characterized in that: wherein one or more of the water in the B-side, the flame retardant foaming system, the dispersant, the nanofiller, the reinforcing fiber are replaced into the A-side.

10. The water-based intumescent epoxy fire-retardant anticorrosive coating of claim 9, wherein the water in the B component, the flame-retardant foaming system, the dispersant, the nanofiller, and the reinforcing fiber are all replaced in the A component, characterized in that: the preparation process of the water-based intumescent epoxy fireproof anticorrosive paint comprises the following steps:

step 1: according to the formula proportion, sequentially adding water, a dispersing agent and a defoaming agent into a dispersing kettle, dispersing for 5-20 minutes, sequentially adding a flame-retardant foaming system, a refractory filler, a nano filler and reinforcing fibers, stirring at a low speed for dispersing for 10-30 minutes, and finally stirring at a high speed for dispersing for 30-60 minutes;

step 2: transferring the dispersed materials into a grinding machine, and continuously grinding for 0.5-3 hours at the rotating speed of 600-1200 r/min;

and step 3: transferring the ground material into a stirring kettle, slowly adding the aqueous epoxy emulsion in the stirring process in the stirring kettle, stirring for 30-60 minutes, continuously stirring, slowly adding the viscosity regulator, uniformly stirring, vacuumizing to-0.04-0.10 MPa, and continuously stirring for 30-60 minutes to obtain a component A of the aqueous intumescent epoxy fireproof anticorrosive paint;

and 4, step 4: the curing agent is used as the component B of the water-based intumescent epoxy fireproof anticorrosive paint.