Fireproof thermal insulation coating, preparation method and application thereof, and method for preparing fireproof thermal insulation coating of storage tank

Abstract

The present application relates to thermal insulation material technical field, disclose a fireproof thermal insulation coating and its preparation method and application, preparation method of fireproof thermal insulation coating of storage tank.The fireproof thermal insulation coating includes inner coating and outer coating, the outer coating is coated on the surface of inner coating;The inner coating contains hollow glass microsphere, polymer emulsion, inorganic filler A, flame retardant, water and aid A;Wherein, the flame retardant contains ammonium polyphosphate and / or expanded graphite;The outer coating contains unsaturated water-based polyurethane emulsion, curing agent, titanium white, modified boron nitride, mica powder, zinc borate, inorganic filler B, water and aid B.The fireproof thermal insulation coating of the present application, when the outer layer is locally overheated, the heat conduction coating of the outer layer can quickly spread the heat to the entire coating surface, and then reduce the heat received locally, so as to protect the local material from damage under the condition of overheating.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of thermal insulation materials, in particular to a fireproof thermal insulation coating, a preparation method and application thereof, and a method for preparing a fireproof thermal insulation coating of a storage tank. BACKGROUND

[0002] Petroleum products are a kind of flammable, explosive, toxic and volatile chemical hazardous goods, and their storage tanks and pipelines are also typical major industrial hazards. Evaporated oil gas not only causes serious environmental pollution, but also poses potential fire hazards to the storage tanks and pipelines and their surrounding areas. According to accident statistics, 101 out of 222 fire and explosion accidents were caused by oil vapor, accounting for 45.5%. The oil tank area is a storage point for oil, and has a certain fire hazard. Once a fire occurs, the heat radiation produced may affect the normal operation of other equipment and pipelines, causing a domino effect, and the scope and damage of the accident will continue to escalate over time, causing serious casualties and economic losses. Improving the fireproof and heat insulation of storage tanks and pipelines can not only reduce the VOC volatilization of storage tank oil and reduce the safety hazards of oil and gas fires, but also help to block the spread of fires and strengthen the fire resistance of equipment, delay the damage rate of high temperature on the structural strength of storage tanks and pipelines, and reduce the risk of fire and explosion.

[0003] Current thermal protection technologies for storage tanks mainly include water cooling, foaming insulation materials and heat-reflecting insulation coatings. Water cooling not only wastes a large amount of water resources, but also accelerates the aging rate of the tank body and induces corrosion of the storage tank. Foaming insulation materials generally have a large thickness and poor weather resistance due to poor adhesion to the surface of the storage tank steel. Heat-reflecting insulation coatings usually have high reflectivity to near-infrared radiation, but low reflectivity to infrared waves, and the coating material warms up significantly under external thermal radiation.

[0004] CN112500770B discloses a high-temperature aerogel heat-insulating fireproof coating, which exhibits good heat-insulating and heat-preserving performance, with a thermal conductivity as low as 0.098 W / m.K (150℃), but does not contribute much to fireproof performance.

[0005] CN109517470B discloses a water-based ultra-thin fireproof coating, which adds phosphorus-nitrogen-doped carbon nanotubes to improve the fireproof performance of the material, with a fire resistance time of up to 180 min. However, due to the addition of carbon nanotubes, the material appears obvious black-brown color, and the infrared thermal radiation absorption is obvious, which is not conducive to the heat-insulating performance of the storage tank.

[0006] CN114015338A discloses a durable weather-resistant insulating heat-reflective coating which uses titanium white powder, alumina and other inorganic materials to improve the heat conductivity and heat reflectivity of the coating, but does not study the fireproof performance of the material. SUMMARY

[0007] The purpose of the present application is to overcome the problem of poor technical effect of fireproof and heat preservation treatment of oil and gas storage tanks in the prior art, and to provide a fireproof and heat preservation coating, a preparation method and application thereof, and a method for preparing a fireproof and heat preservation coating of a storage tank.

[0008] To achieve the above-mentioned purpose, the present application provides a fireproof and heat preservation coating, which comprises an inner layer coating and an outer layer coating, and the outer layer coating is coated on the surface of the inner layer coating.

[0009] The inner layer coating contains hollow glass microbeads, polymer emulsion, inorganic filler A, flame retardant, water and additive A.

[0010] The weight ratio of the polymer emulsion, hollow glass microbeads, inorganic filler A, flame retardant, water and additive A is 1:0.15-0.6:0.05-0.5:0.15-0.45:0.8-2:0.02-0.1.

[0011] The flame retardant contains ammonium polyphosphate and / or expanded graphite.

[0012] The outer layer coating contains unsaturated water-based polyurethane emulsion, curing agent, titanium white powder, modified boron nitride, mica powder, zinc borate, inorganic filler B, water and additive B.

[0013] The weight ratio of the unsaturated water-based polyurethane emulsion, curing agent, titanium white powder, modified boron nitride, mica powder, zinc borate, inorganic filler B, water and additive B is 1:0.05-0.2:0.2-0.7:0.02-0.15:0.05-0.4:0.02-0.4:0.02-0.2:0.8-1.5:0.02-0.1.

[0014] Preferably, the polymer emulsion is selected from one or more of styrene-acrylic emulsion, silicone-acrylic emulsion and pure acrylic emulsion.

[0015] Preferably, the inorganic filler A is selected from one or more of expanded perlite powder, fumed silica, calcium carbonate, talc powder and zinc borate.

[0016] Preferably, the flame retardant further contains one or more of pentaerythritol, dipentaerythritol, urea, starch, chlorinated paraffin, melamine and antimony trioxide.

[0017] Preferably, the auxiliary agent A is selected from one or more of tributyl phosphate, ethylene glycol, hydroxymethyl cellulose, and wet dispersant RD9000.

[0018] Preferably, the curing agent is selected from one or more of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl phenyl phosphonate ethyl ester, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.

[0019] Preferably, the inorganic filler B is selected from one or more of aluminum hydroxide, magnesium hydroxide, and aluminum oxide.

[0020] Preferably, the auxiliary agent B is selected from one or more of tributyl phosphate, ethylene glycol, hydroxymethyl cellulose, and wet dispersant RD9000.

[0021] Preferably, the method for preparing the unsaturated aqueous polyurethane emulsion comprises:

[0022] (1) weighing the macromolecular diol, and heating to 60-100°C under nitrogen protection;

[0023] (2) adding MDI50 and reacting for 1-4h;

[0024] (3) adding dimethylol butyric acid and reacting for 1-4h;

[0025] (4) adding hydroxyethyl acrylate and reacting for 2-4h;

[0026] (5) cooling to room temperature, adding triethylamine and reacting for 1-3h;

[0027] (6) adding water, and stirring at a speed of 600-800rpm for 30-60min;

[0028] The macromolecular diol is selected from one or more of polycaprolactone diol, polyethylene glycol, polypropylene glycol, and polydimethylsiloxane diol.

[0029] Preferably, the weight ratio of the macromolecular diol, MDI50, dimethylol butyric acid, hydroxyethyl acrylate, triethylamine, and water is 15-25:8-12:1-1.5:1.5-2.5:1:70-100.

[0030] Preferably, the method for preparing the modified boron nitride comprises:

[0031] (a) mixing boron nitride with anhydrous ethanol, and then performing ultrasonic dispersion;

[0032] (b) adding silane coupling agent KH570 to the material obtained in step (a), and performing reaction under stirring, and then performing filtration, and drying the solid obtained by filtration to obtain modified boron nitride.

[0033] Preferably, the weight ratio of the boron nitride, the anhydrous ethanol and the silane coupling agent KH570 is 1:90-110:0.01-0.03.

[0034] Preferably, in step (a), the ultrasonic dispersion is performed for 0.5-1.5h.

[0035] Preferably, in step (b), the stirring speed is 200-300rpm.

[0036] Preferably, the reaction is performed at a temperature of 50-70℃ for 0.5-2h.

[0037] Preferably, the drying is performed at a temperature of 90-110℃ for 20-30h.

[0038] The second aspect of the present application provides a preparation method of the fireproof and thermal insulation coating, and the preparation method comprises the following steps:

[0039] S1: stirring a polymer emulsion, water and an additive A for 30-60min, and then adding a flame retardant and an inorganic filler A, and stirring at a speed of 600-800rpm for 1-2h;

[0040] S2: adding hollow glass microspheres to the material obtained in step S1, and stirring at a speed of 100-200rpm for 30-60min to obtain an inner layer coating;

[0041] S3: stirring an unsaturated water-based polyurethane emulsion, water and an additive B for 30-60min, and then adding titanium white, modified boron nitride, mica powder, zinc borate and an inorganic filler B, and stirring at a speed of 600-800rpm for 1-2h;

[0042] S4: adding a curing agent to the material obtained in step S3, and stirring for 30-60min to obtain an outer layer coating.

[0043] The third aspect of the present application provides an application of the fireproof and thermal insulation coating in a fireproof and thermal insulation coating of a storage tank.

[0044] The fourth aspect of the present application provides a preparation method of a fireproof and thermal insulation coating of a storage tank, and the preparation method comprises the following steps:

[0045] (I) polishing a metal substrate to remove rust, and then spraying a water-based epoxy primer; (II) spraying the fireproof and thermal insulation coating of the present application on the metal substrate; and

[0046] (II) brushing a fireproof thermal insulation coating on the surface of the waterborne epoxy primer;

[0047] (III) after the inner layer coating dries, spraying an outer layer coating of the fireproof thermal insulation coating on the surface of the inner layer coating;

[0048] wherein the fireproof thermal insulation coating is the fireproof thermal insulation coating described above.

[0049] The fireproof thermal insulation coating described in the present application can quickly spread the heat to the entire surface of the coating when the outer layer is locally overheated, thereby reducing the local heat and protecting the local material from damage under the condition of overheating. Compared with the existing thermal insulation materials, the thermal insulation material of the present application disperses the local heat by conduction, rather than just insulating the heat in the traditional sense. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 is a schematic diagram of the fireproof thermal insulation coating described in the present application blocking heat conduction;

[0051] Figure 2 is a photograph before and after spraying the outer layer coating of Example 2. DETAILED DESCRIPTION

[0052] The specific embodiments of the present application are described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0053] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and the values are approximate values and should be understood as including values approximately near these ranges and values within these ranges. For ranges of values, the endpoints of the ranges are combined with the individual points to form new ranges of values that are not specifically disclosed.

[0054] The first aspect of the present application provides a fireproof thermal insulation coating, the fireproof thermal insulation coating comprising an inner layer coating and an outer layer coating, the outer layer coating being coated on the surface of the inner layer coating;

[0055] The inner layer coating contains hollow glass microbeads, a polymer emulsion, inorganic filler A, a flame retardant, water and an auxiliary A;

[0056] The weight ratio of the polymer emulsion, hollow glass microbeads, inorganic filler A, flame retardant, water and auxiliary A is 1:0.15-0.6:0.05-0.5:0.15-0.45:0.8-2:0.02-0.1;

[0057] The flame retardant contains ammonium polyphosphate and / or expanded graphite;

[0058] The outer layer coating contains unsaturated water-based polyurethane emulsion, curing agent, titanium white powder, modified boron nitride, mica powder, zinc borate, inorganic filler B, water and auxiliary agent B;

[0059] The weight ratio of the unsaturated water-based polyurethane emulsion, the curing agent, the titanium white powder, the modified boron nitride, the mica powder, the zinc borate, the inorganic filler B, the water and the auxiliary agent B is 1:0.05-0.2:0.2-0.7:0.02-0.15:0.05-0.4:0.02-0.4:0.02-0.2:0.8-1.5:0.02-0.1.

[0060] The schematic diagram of the heat conduction barrier of the fireproof thermal insulation coating is shown in the figure. Figure 1 The inner layer coating has excellent flame retardant and thermal insulation properties, preventing heat from being transmitted to the internal storage tank; the outer layer coating has excellent heat conduction and heat reflection properties, which can reflect external high-temperature heat radiation and conduct local heat; when the inner and outer layer coatings are in contact with high-temperature flame, the organic silicon and mica, glass microbeads and the like in the material will form a ceramic structure on the surface layer, greatly improving the fireproof performance of the material.

[0061] In the present application, ammonium polyphosphate and expanded graphite have a significant effect on the fireproof performance of the material; when the content of ammonium polyphosphate or expanded graphite in the finished product is insufficient or absent, the fire resistance time of the coating is significantly reduced, which is difficult to meet the fireproof requirements, and therefore it is necessary to add ammonium polyphosphate and / or graphite to ensure the final fireproof performance.

[0062] In the present application, when the amount of hollow glass microbeads in the inner layer coating is small, the fireproof thermal insulation performance of the final product is poor; when the amount of hollow glass microbeads is too large, the coating has poor construction performance, which is difficult to meet the fireproof thermal insulation performance requirements, and therefore it is necessary to reasonably control the proportion of each raw material in the inner layer coating.

[0063] In the preferred case, in the inner layer coating, the weight ratio of the polymer emulsion, the hollow glass microbeads, the inorganic filler A, the flame retardant, the water and the auxiliary agent A is 1:0.2-0.5:0.1-0.4:0.15-0.4:0.8-1.7:0.02-0.1.

[0064] In the specific embodiment, in the inner layer coating, the weight ratio of the polymer emulsion, the hollow glass microbeads, the inorganic filler A, the flame retardant, the water and the auxiliary agent A can be 1:0.5:0.25:0.3:1:0.0625, 1:0.33:0.4:0.33:1.67:0.1, 1:0.2:0.1:0.26:0.8:0.02 or 1:0.375:0.2:0.375:1.5:0.05.

[0065] In a preferred case, the polymer emulsion is selected from one or more of styrene-acrylate emulsion, silicone-acrylate emulsion and pure-acrylate emulsion.

[0066] In a preferred case, the inorganic filler A is selected from one or more of expanded perlite powder, fumed silica, calcium carbonate, talcum powder and zinc borate.

[0067] Preferably, the flame retardant further contains one or more of pentaerythritol, di-pentaerythritol, urea, starch, chlorinated paraffin, melamine and antimony trioxide.

[0068] Preferably, the auxiliary A is selected from one or more of tributyl phosphate, ethylene glycol, hydroxymethyl cellulose and wet dispersant RD9000.

[0069] In the present application, the outer coating can maintain excellent high-energy near-infrared reflection ability of the coating by controlling reasonable component ratio, can reflect and block the influence of high-temperature radiation on the equipment such as storage tank, and has obvious synergistic effect on fire prevention with the inner coating when fire occurs, and can obviously improve the fire resistance time.

[0070] In a preferred case, in the outer coating, the weight ratio of the unsaturated water-based polyurethane emulsion, the curing agent, the titanium white powder, the modified boron nitride, the mica powder, the zinc borate, the inorganic filler B, the water and the auxiliary B is 1:0.075-0.2:0.3-0.7:0.03-0.14:0.075-0.35:0.03-0.35:0.07-0.2:1-1.5:0.06-0.1.

[0071] In a specific embodiment, in the outer coating, the weight ratio of the unsaturated water-based polyurethane emulsion, the curing agent, the titanium white powder, the modified boron nitride, the mica powder, the zinc borate, the inorganic filler B, the water and the auxiliary B can be 1:0.125:0.375:0.1:0.15:0.15:0.075:1:0.0625, 1:0.075:0.375:0.05:0.075:0.125:0.075:1:0.075, 1:0.17:0.67:0.13:0.17:0.033:0.17:1.33:0.083 or 1:0.1:0.33:0.033:0.33:0.33:0.1:1.33:0.083.

[0072] Preferably, the curing agent is selected from one or more of 2-hydroxy-2-methyl-1- phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4- (methylthio)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6- trimethylbenzoyl ethyl phenylphosphonate, 2-dimethylamino-2-benzyl-1-[4-(4- morpholinyl)phenyl]-1-butanone, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]- 1-propanone; further preferably, the curing agent is 2-hydroxy-2-methyl-1-phenylpropanone.

[0073] Preferably, the inorganic filler B is selected from one or more of aluminum hydroxide, magnesium hydroxide, and aluminum oxide.

[0074] Preferably, the auxiliary agent B is selected from one or more of tributyl phosphate, ethylene glycol, hydroxymethyl cellulose, and wet dispersant RD9000.

[0075] In a preferred embodiment, the method for preparing the unsaturated aqueous polyurethane emulsion comprises:

[0076] (1) weighing the macromolecular diol, and heating to 60-100°C under nitrogen protection;

[0077] (2) adding MDI50 and reacting for 1-4h;

[0078] (3) adding dimethylol butyric acid and reacting for 1-4h;

[0079] (4) adding hydroxyethyl acrylate and reacting for 2-4h;

[0080] (5) cooling to room temperature, adding triethylamine and reacting for 1-3h;

[0081] (6) adding water, and stirring at a speed of 600-800rpm for 30-60min;

[0082] The macromolecular diol is selected from one or more of polycaprolactone diol, polyethylene glycol, polypropylene glycol, and polydimethylsiloxane diol.

[0083] In a preferred embodiment, the operations of steps (2)-(6) are all performed under nitrogen protection.

[0084] In a specific embodiment, in step (1), the temperature of the heating can be 60°C, 70°C, 80°C, 90°C, or 100°C.

[0085] In a specific embodiment, in step (2), the reaction time can be 1h, 2h, 3h, or 4h.

[0086] In a specific embodiment, in step (3), the reaction time can be 1 h, 2 h, 3 h or 4 h.

[0087] In a specific embodiment, in step (4), the reaction time can be 2 h, 3 h or 4 h.

[0088] In a specific embodiment, in step (5), the reaction time can be 1 h, 2 h or 3 h.

[0089] In a specific embodiment, in step (6), the stirring speed can be 600 rpm, 650 rpm, 700 rpm, 750 rpm or 800 rpm.

[0090] In a specific embodiment, in step (6), the stirring time can be 30 min, 40 min, 50 min or 60 min.

[0091] Normal temperature as used herein refers to 20-30℃.

[0092] Preferably, in the preparation of the unsaturated aqueous polyurethane emulsion, the weight ratio of the macromolecular diol, MDI50, dimethylol butanoic acid, hydroxyethyl acrylate, triethylamine and water is 15-25:8-12:1-1.5:1.5-2.5:1:70-100; further preferably 17-23:9-12:1.1-1.4:1.8-2.2:1:75-90.

[0093] In a specific embodiment, the weight ratio of the macromolecular diol, MDI50, dimethylol butanoic acid, hydroxyethyl acrylate, triethylamine and water is 20:11:1.2:1.9:1:80.

[0094] Preferably, the method for preparing the modified boron nitride comprises:

[0095] (a) mixing boron nitride with anhydrous ethanol, and then performing ultrasonic dispersion;

[0096] (b) adding silane coupling agent KH570 to the material obtained in step (a), and then performing reaction under stirring, and then performing filtration, and drying the solid obtained by filtration to obtain modified boron nitride.

[0097] In a preferred case, the weight ratio of the boron nitride, anhydrous ethanol and silane coupling agent KH570 is 1:90-110:0.01-0.03.

[0098] In a specific embodiment, the weight ratio of the boron nitride, anhydrous ethanol and silane coupling agent KH570 can be 1:100:0.02.

[0099] In a preferred embodiment, in step (a), the time for ultrasonic dispersion is 0.5-1.5h. Specifically, it can be 0.5h, 0.75h, 1h, 1.25h or 1.5h.

[0100] In a preferred embodiment, in step (b), the stirring speed is 200-300rpm. In a specific embodiment, the stirring speed can be 200rpm, 220rpm, 240rpm, 260rpm, 280rpm or 300rpm.

[0101] In a preferred embodiment, in step (b), the reaction temperature is 50-70℃ and the reaction time is 0.5-2h. Specifically, the reaction temperature can be 50℃, 55℃, 60℃, 65℃ or 70℃, and the reaction time can be 0.5h, 0.75h, 1h, 1.25h, 1.5h, 1.75h or 2h.

[0102] In a preferred embodiment, in step (b), the drying temperature is 90-110℃ and the drying time is 20-30h. In a specific embodiment, the drying temperature can be 90℃, 95℃, 100℃, 105℃ or 110℃, and the drying time can be 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h or 30h.

[0103] The second aspect of the present application provides a preparation method of the fireproof thermal insulation coating described above, which comprises the following steps:

[0104] S1: stirring the polymer emulsion, water and additive A for 30-60min, then adding the flame retardant and inorganic filler A, and stirring at a speed of 600-800rpm for 1-2h;

[0105] S2: adding the hollow glass microbeads to the material obtained in step S1, and stirring at a speed of 100-200rpm for 30-60min to obtain the inner layer coating;

[0106] S3: stirring the unsaturated waterborne polyurethane emulsion, water and additive B for 30-60min, then adding the titanium dioxide, modified boron nitride, mica powder, zinc borate and inorganic filler B, and stirring at a speed of 600-800rpm for 1-2h;

[0107] S4: adding the curing agent to the material obtained in step S3, and stirring for 30-60min to obtain the outer layer coating.

[0108] In a preferred embodiment, in step S1, in order to better disperse the raw materials, the flame retardant and inorganic filler A are both added in batches.

[0109] In a specific embodiment, in step S1, the stirring time of the polymer emulsion, water and the auxiliary A can be 30 min, 40 min, 50 min or 60 min.

[0110] In a specific embodiment, in step S1, after adding the flame retardant and the inorganic filler A, the stirring speed can be 600 rpm, 650 rpm, 700 rpm, 750 rpm or 800 rpm, and the stirring time can be 1 h, 1.5 h or 2 h.

[0111] In a preferred case, in step S2, in order to achieve better dispersion, the hollow glass beads are also added in batches.

[0112] In a specific embodiment, in step S2, the stirring speed can be 100 rpm, 120 rpm, 140 rpm, 160 rpm, 180 rpm or 200 rpm, and the stirring time can be 30 min, 40 min, 50 min or 60 min.

[0113] Similarly, in step S3, the titanium dioxide, modified boron nitride, mica powder, zinc borate and inorganic filler B are also added in batches.

[0114] In a specific embodiment, in step S3, the stirring time of the unsaturated water-based polyurethane emulsion, water and the auxiliary B can be 30 min, 40 min, 50 min or 60 min.

[0115] In a specific embodiment, in step S3, after adding the titanium dioxide, modified boron nitride, mica powder, zinc borate and inorganic filler B, the stirring speed can be 600 rpm, 650 rpm, 700 rpm, 750 rpm or 800 rpm, and the stirring time can be 1 h, 1.5 h or 2 h.

[0116] In a specific embodiment, in step S4, the stirring time can be 30 min, 40 min, 50 min or 60 min.

[0117] The third aspect of the present application provides an application of the above-mentioned fireproof and thermal insulation coating in a fireproof and thermal insulation coating of a storage tank.

[0118] The fourth aspect of the present application provides a method for preparing a fireproof and thermal insulation coating of a storage tank, which comprises the following steps:

[0119] (I) polishing and rust-removing the metal substrate, and then spraying a water-based epoxy primer;

[0120] (II) brushing the inner coating of the fireproof and thermal insulation coating on the surface of the water-based epoxy primer;

[0121] (III) after the inner layer coating dries, spraying the outer layer coating in the fireproof thermal insulation coating on the surface of the inner layer coating;

[0122] The fireproof thermal insulation coating is the fireproof thermal insulation coating as described above.

[0123] In the specific embodiments, in the steps (II) and (III), the thicknesses of the inner layer coating and the outer layer coating are determined according to the actual working conditions.

[0124] The fireproof thermal insulation coating of the present application can protect the oil and gas storage tank facilities from the rapid and obvious increase of the temperature of the dangerous medium of the oil and gas storage tank in the case of sudden fire and other dangerous situations, and can prevent the combustion and explosion and other more dangerous situations. The fireproof thermal insulation coating can be applied in the fields of oil storage tank, chemical equipment, building external wall thermal insulation material, etc.

[0125] The present application will be described in detail through the following examples, but the protection scope of the present application is not limited to this.

[0126] In the following examples and comparative examples, the raw materials used are all commercially available products, except for the special instructions.

[0127] In the following examples and comparative examples, the normal temperature refers to 25℃.

[0128] Example 1

[0129] (1) The polymer emulsion, deionized water and additive A were added into a stirrer, stirred and mixed for 30 min, then the flame retardant and inorganic filler A (the flame retardant and inorganic filler A were pre-mixed, and then added in 5 equal portions) were added, and then stirred at a speed of 800 rpm for 1 h;

[0130] (2) The hollow glass microbeads were added into the material obtained in step (1) (the hollow glass microbeads were added in 5 equal portions), and then stirred at a speed of 100 rpm for 30 min to obtain the inner layer coating;

[0131] (3) The unsaturated waterborne polyurethane emulsion, deionized water and additive B were stirred for 30 min, then the titanium white, modified boron nitride, mica powder, zinc borate and inorganic filler B (the titanium white was added in 5 equal portions, the modified boron nitride was added in 2 equal portions, the mica powder was added in 2 equal portions, the zinc borate was added in 2 equal portions, and the inorganic filler B was added in 2 equal portions) were added, and then stirred at a speed of 700 rpm for 1 h;

[0132] (4) The curing agent was added into the material obtained in step (3), and then stirred at a speed of 600 rpm for 30 min to obtain the outer layer coating;

[0133] (5) The metal substrate (carbon steel) was polished and rusted, and then the waterborne epoxy primer was sprayed;

[0134] (6) repeatedly and uniformly brushing the inner layer coating obtained in step (2) on the surface of the aqueous epoxy primer until the thickness is 3 mm;

[0135] (7) after the inner layer coating is dried, spraying the outer layer coating obtained in step (4) on the surface of the inner layer coating, and the thickness of the outer layer coating is 100 um;

[0136] The preparation method of the unsaturated aqueous polyurethane emulsion in step (3) is as follows:

[0137] (a) 20 g of polycaprolactone diol (molecular weight 1000), 30 g of polyethylene glycol (molecular weight 1000), 30 g of polypropylene glycol (molecular weight 1000), and 20 g of polydimethylsiloxane diol (molecular weight 1000) are weighed into a reaction kettle, and heated to 80°C under nitrogen protection;

[0138] (b) 55 g of MDI50 is added and reacted for 2 h;

[0139] (c) 6 g of dimethylol butyric acid is added and reacted for 2 h;

[0140] (d) 9.5 g of hydroxyethyl acrylate is added and reacted for 3 h;

[0141] (e) cool to room temperature, add 5 g of triethylamine and react for 1 h;

[0142] (f) add 400 g of deionized water, stir at a speed of 600 rpm for 30 min, and filter;

[0143] The operations of steps (b) to (f) are all carried out under nitrogen protection;

[0144] The preparation method of the modified boron nitride in step (3) is as follows:

[0145] (i) 1 g of boron nitride is mixed with 100 g of anhydrous ethanol, and then ultrasonically dispersed for 1 h;

[0146] (ii) 0.02 g of silane coupling agent KH570 is added to the material obtained in step (i), and the reaction is carried out under stirring, the stirring speed is 200 rpm, the reaction temperature is 60°C, and the reaction time is 1 h, then filtered, and the solid obtained by filtration is dried at 100°C for 24 h, and then ground into fine powder with a three-roll grinder.

[0147] Example 2

[0148] (1) The polymer emulsion, deionized water and auxiliary A are added into the stirrer, stirred and mixed for 30 min, then the flame retardant and inorganic filler A (the flame retardant and inorganic filler A are pre-mixed, then added evenly for 5 times) are added, and then stirred at a speed of 600 rpm for 1 h;

[0149] (2) adding hollow glass microspheres (hollow glass microspheres are added averagely for 5 times) to the material obtained in step (1), and then stirring at a speed of 100 rpm for 30 min to obtain an inner coating;

[0150] (3) stirring unsaturated water-based polyurethane emulsion, deionized water and additive B for 30 min, and then adding titanium white, modified boron nitride, mica powder, zinc borate and inorganic filler B (titanium white is added averagely for 5 times, modified boron nitride is added averagely for 2 times, mica powder is added averagely for 2 times, zinc borate is added averagely for 2 times, and inorganic filler B is added averagely for 2 times), and then stirring at a speed of 800 rpm for 1 h;

[0151] (4) adding a curing agent to the material obtained in step (3), and then stirring at a speed of 600 rpm for 30 min to obtain an outer coating;

[0152] (5) polishing and rusting a metal substrate (carbon steel), and then spraying a water-based epoxy primer;

[0153] (6) uniformly brushing the inner coating obtained in step (2) on the surface of the water-based epoxy primer for multiple times until the thickness is 3 mm;

[0154] (7) after the inner coating is dried, spraying the outer coating obtained in step (4) on the surface of the inner coating, and the thickness of the outer coating is 100 um;

[0155] The preparation method of the unsaturated water-based polyurethane emulsion in step (3) is as follows:

[0156] (a) putting 10 g of polycaprolactone diol (molecular weight is 1000), 40 g of polyethylene glycol (molecular weight is 1000), 20 g of polypropylene glycol (molecular weight is 1000) and 30 g of polydimethylsiloxane diol (molecular weight is 1000) into a reaction kettle, and heating to 80℃ under nitrogen protection;

[0157] (b) adding 55 g of MDI50 and reacting for 2 h;

[0158] (c) adding 6 g of dimethylol butyric acid and reacting for 2 h;

[0159] (d) adding 9.5 g of hydroxyethyl acrylate and reacting for 3 h;

[0160] (e) cooling to room temperature, adding 5 g of triethylamine and reacting for 1 h;

[0161] (f) adding 400 g of deionized water, stirring at a speed of 600 rpm for 30 min, and filtering;

[0162] The steps (b)-(f) are all operated under nitrogen protection.

[0163] The preparation method of the modified boron nitride in step (3) is as follows:

[0164] (i) 1 g of boron nitride is mixed with 100 g of anhydrous ethanol, and then ultrasonic dispersion is performed for 1 h;

[0165] (ii) 0.02 g of silane coupling agent KH570 is added to the material obtained in step (i), and the reaction is performed under stirring at a stirring speed of 200 rpm and a reaction temperature of 60°C for 1 h, then filtration is performed, and the solid obtained by filtration is dried at 100°C for 24 h, and then ground into fine powder by a three-roll grinder.

[0166] Example 3

[0167] (1) The polymer emulsion, deionized water and additive A are added into a stirrer, stirred and mixed for 30 min, then the flame retardant and inorganic filler A (the flame retardant and inorganic filler A are pre-mixed, and then added in 5 equal portions), and then stirred at a speed of 800 rpm for 1 h;

[0168] (2) The hollow glass microspheres (the hollow glass microspheres are added in 5 equal portions) are added to the material obtained in step (1), and then stirred at a speed of 100 rpm for 30 min to obtain an inner coating;

[0169] (3) The unsaturated waterborne polyurethane emulsion, deionized water and additive B are stirred for 30 min, then the titanium white, modified boron nitride, mica powder, zinc borate and inorganic filler B (the titanium white is added in 5 equal portions, the modified boron nitride is added in 2 equal portions, the mica powder is added in 2 equal portions, the zinc borate is added in 2 equal portions, and the inorganic filler B is added in 2 equal portions) are added, and then stirred at a speed of 800 rpm for 1 h;

[0170] (4) The curing agent is added to the material obtained in step (3), and then stirred at a speed of 600 rpm for 30 min to obtain an outer coating;

[0171] (5) The metal substrate (carbon steel) is polished to remove rust, and then sprayed with a waterborne epoxy primer;

[0172] (6) The inner coating obtained in step (2) is uniformly brushed on the surface of the waterborne epoxy primer for multiple times until the thickness is 3 mm;

[0173] (7) After the inner coating is dried, the outer coating obtained in step (4) is sprayed on the surface of the inner coating, and the thickness of the outer coating is 100 um;

[0174] The preparation method of the unsaturated waterborne polyurethane emulsion in step (3) is as follows:

[0175] (a) 30 g of polyethylene glycol (molecular weight 1000), 50 g of polypropylene glycol (molecular weight 1000), and 20 g of polydimethylsiloxane diol (molecular weight 1000) were weighed into a reaction kettle, and heated to 80°C under nitrogen protection;

[0176] (b) 55 g of MDI50 was added and reacted for 2 h;

[0177] (c) 6 g of dimethylol butyric acid was added and reacted for 2 h;

[0178] (d) 9.5 g of hydroxyethyl acrylate was added and reacted for 3 h;

[0179] (e) The temperature was lowered to room temperature, 5 g of triethylamine was added and reacted for 1 h;

[0180] (f) 400 g of deionized water was added, stirred at a speed of 700 rpm for 30 min, and filtered;

[0181] Wherein, the operations of steps (b)-(f) are carried out under nitrogen protection;

[0182] The preparation method of the modified boron nitride in step (3) is as follows:

[0183] (i) 1 g of boron nitride was mixed with 100 g of anhydrous ethanol, and then ultrasonically dispersed for 1 h;

[0184] (ii) 0.02 g of silane coupling agent KH570 was added to the material obtained in step (i), and reacted under stirring, the stirring speed was 200 rpm, the reaction temperature was 60°C, and the reaction time was 1 h, then filtered, and the solid obtained by filtration was dried at 100°C for 24 h, and then ground into fine powder with a three-roll grinder.

[0185] Example 4

[0186] (1) The polymer emulsion, deionized water and auxiliary agent A were added into a stirrer, stirred and mixed for 30 min, then the flame retardant and inorganic filler A (the flame retardant and inorganic filler A were pre-mixed, then added in 5 equal portions), then stirred at a speed of 800 rpm for 1 h;

[0187] (2) Hollow glass microspheres were added to the material obtained in step (1) (the hollow glass microspheres were added in 5 equal portions), then stirred at a speed of 100 rpm for 30 min, to obtain an inner coating;

[0188] (3) stirring the unsaturated waterborne polyurethane emulsion, deionized water and additive B for 30 min, then adding titanium dioxide, modified boron nitride, mica powder, zinc borate and inorganic filler B (titanium dioxide is added averagely for 5 times, modified boron nitride is added averagely for 2 times, mica powder is added averagely for 2 times, zinc borate is added averagely for 2 times, and inorganic filler B is added averagely for 2 times), and then stirring for 1 h at a speed of 700 rpm;

[0189] (4) adding a curing agent to the material obtained in step (3), and then stirring for 30 min at a speed of 600 rpm to obtain an outer coating;

[0190] (5) polishing and rusting a metal substrate (carbon steel), and then spraying a waterborne epoxy primer;

[0191] (6) uniformly brushing the inner coating obtained in step (2) on the surface of the waterborne epoxy primer for multiple times until the thickness is 3 mm;

[0192] (7) after the inner coating is dried, spraying the outer coating obtained in step (4) on the surface of the inner coating, and the thickness of the outer coating is 100 um;

[0193] The preparation method of the unsaturated waterborne polyurethane emulsion in step (3) is as follows:

[0194] (a) placing 80 g of polycaprolactone diol (molecular weight is 1000) and 20 g of polydimethylsiloxane diol (molecular weight is 1000) into a reaction kettle, and heating to 80 °C under nitrogen protection;

[0195] (b) adding 55 g of MDI50 and reacting for 2 h;

[0196] (c) adding 6 g of dimethylol butyric acid and reacting for 2 h;

[0197] (d) adding 9.5 g of hydroxyethyl acrylate and reacting for 3 h;

[0198] (e) cooling to room temperature, adding 5 g of triethylamine and reacting for 1 h;

[0199] (f) adding 400 g of deionized water, stirring for 30 min at a speed of 700 rpm, and filtering;

[0200] The operations of steps (b)-(f) are all carried out under nitrogen protection;

[0201] The preparation method of the modified boron nitride in step (3) is as follows:

[0202] (i) mixing 1 g of boron nitride with 100 g of anhydrous ethanol, and then ultrasonic dispersing for 1 h;

[0203] (ii) adding 0.02 g of silane coupling agent KH570 to the material obtained in step (i), and carrying out the reaction under stirring at a stirring speed of 300 rpm and a reaction temperature of 60°C for 1 h, then filtering, drying the solid obtained by filtration at 100°C for 24 h, and then grinding to a fine powder using a three-roll grinder.

[0204] Comparative Example 1

[0205] The procedure of Example 1 was followed, except that the amount of hollow glass microbeads was 5 g, i.e. the weight ratio of polymer emulsion, hollow glass microbeads, inorganic filler A, flame retardant, water and adjuvant A in the inner coating was 1 : 0.125 : 0.25 : 0.3 : 1 : 0.0625.

[0206] Comparative Example 2

[0207] The procedure of Example 1 was followed, except that no ammonium polyphosphate was used in step (1) and no zinc borate was used in step (3), and the amounts of the individual materials were as shown in Table 1. The weight ratio of polymer emulsion, hollow glass microbeads, inorganic filler A, flame retardant, water and adjuvant A in the inner coating was 1 : 0.5 : 0.25 : 0.15 : 1 : 0.0625, and the weight ratio of unsaturated waterborne polyurethane emulsion, curing agent, titanium dioxide, modified boron nitride, mica powder, zinc borate, inorganic filler B, water and adjuvant B in the outer coating was 1 : 0.125 : 0.375 : 0.1 : 0.15 : 0 : 0.075 : 1 : 0.0625. The remaining procedure was as in Example 1.

[0208] Comparative Example 3

[0209] The procedure of Example 1 was followed, except that the same weight of unmodified boron nitride was used instead of modified boron nitride.

[0210] Comparative Example 4

[0211] The procedure of Example 1 was followed, except that only the inner coating was used, and the procedure was as follows:

[0212] (1) The polymer emulsion, deionized water and adjuvant A were added to a stirrer and stirred and mixed for 30 min, then the flame retardant and inorganic filler A (the flame retardant and inorganic filler A were pre-mixed and then added in five equal portions) were added, and then stirred at a speed of 800 rpm for 1 h;

[0213] (2) The hollow glass microbeads were added to the material obtained in step (1) (the hollow glass microbeads were added in five equal portions), and then stirred at a speed of 100 rpm for 30 min to obtain the inner coating;

[0214] (3) polishing the metal substrate (carbon steel) to remove rust, and then spraying a water-based epoxy primer;

[0215] (4) uniformly brushing the inner layer coating obtained in step (2) on the surface of the water-based epoxy primer for multiple times until the thickness is 3 mm.

[0216] The raw materials and amounts used in Examples 1-4 and Comparative Examples 1-4 are shown in Table 1, wherein the curing agent is selected from 2-hydroxy-2-methyl-1-phenylpropanone.

[0217] Table 1

[0218]

[0219]

[0220] Test Example 1

[0221] The appearance of the sample before and after spraying the outer layer coating of Example 2 was observed using a digital camera, as shown in Figure 2 , wherein Figure 2 the left side is the appearance when only the inner layer coating is brushed, and the right side is the appearance when the outer layer coating is sprayed on the inner layer coating, according to Figure 2 , it can be seen that the inner layer coating is a matte gray-black color, and the outer layer coating is a high-gloss white color, so the outer layer coating has a very good effect of reflecting high-temperature radiation.

[0222] Test Example 2

[0223] The thermal conductivity, infrared reflectance, heat insulation temperature difference decay, fire resistance time, and water resistance of the samples obtained in Examples 1-4 and Comparative Examples 1-4 were detected, respectively;

[0224] Thermal conductivity test: GB / T 10294-2008;

[0225] Infrared reflectance test: JG / T235-2014;

[0226] Heat insulation temperature difference decay test: in a 275W baking lamp test box, the temperature difference between the light receiving surface and the back surface of the metal plate sprayed with the coating was tested after 30 min of heat preservation;

[0227] Fire resistance time test: GB12441-2005;

[0228] Water resistance test: GB / T1733-1993;

[0229] The test results are shown in Table 2.

[0230] Table 2

[0231]

[0232] As can be seen from the results in Table 2, the outer layer material of the present application has a higher thermal conductivity, which can dissipate heat from the high-temperature heat source outside, and the inner layer material has a lower thermal conductivity, which can prevent the high-temperature outside from penetrating the coating material, and the mutual superposition of the two different materials can significantly improve the heat insulation temperature difference decay and fire resistance time of the coating material.

[0233] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and belong to the protection scope of the present application.

Claims

1. A fireproof thermal insulation coating, characterized by, The fireproof thermal insulation coating comprises an inner layer coating and an outer layer coating, and the outer layer coating is coated on the surface of the inner layer coating; The inner layer coating contains hollow glass microbeads, polymer emulsion, inorganic filler A, flame retardant, water and additive A; The weight ratio of the polymer emulsion, hollow glass microbeads, inorganic filler A, flame retardant, water and additive A is 1:0.15-0.6:0.05-0.5:0.15-0.45:0.8-2:0.02-0.1; The flame retardant contains ammonium polyphosphate and / or expanded graphite; The inorganic filler A is selected from one or more of expanded perlite powder, fumed silica, calcium carbonate, talc powder and zinc borate; The additive A is selected from one or more of tributyl phosphate, ethylene glycol, hydroxymethyl cellulose and wet dispersant RD9000; The outer layer coating contains unsaturated water-based polyurethane emulsion, curing agent, titanium white powder, modified boron nitride, mica powder, zinc borate, inorganic filler B, water and additive B; The weight ratio of the unsaturated water-based polyurethane emulsion, curing agent, titanium white powder, modified boron nitride, mica powder, zinc borate, inorganic filler B, water and additive B is 1:0.05-0.2:0.2-0.7:0.02-0.15:0.05-0.4:0.02-0.4:0.02-0.2:0.8-1.5:0.02-0.1; The inorganic filler B is selected from one or more of aluminum hydroxide, magnesium hydroxide and aluminum oxide; The additive B is selected from one or more of tributyl phosphate, ethylene glycol, hydroxymethyl cellulose and wet dispersant RD9000; The preparation method of the modified boron nitride comprises: (a) mixing boron nitride with anhydrous ethanol, and then performing ultrasonic dispersion; (b) adding silane coupling agent KH570 to the material obtained in step (a), and performing reaction under stirring, and then performing filtration, and drying the solid obtained by filtration to obtain modified boron nitride, and the weight ratio of the boron nitride, anhydrous ethanol and silane coupling agent KH570 is 1:90-110:0.01-0.

03.

2. The fireproof thermal insulation coating according to claim 1, characterized in that, The polymer emulsion is selected from one or more of styrene-acrylic emulsion, silicone-acrylic emulsion and pure acrylic emulsion.

3. The fireproof thermal insulation paint according to claim 1, characterized in that, The flame retardant further contains one or more of pentaerythritol, di-pentaerythritol, urea, starch, chlorinated paraffin, melamine and antimony trioxide.

4. The fireproof thermal insulation paint according to claim 1 or 2, characterized in that, The curing agent is selected from one or more of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl phenyl phosphonate ethyl, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.

5. The fireproof thermal insulation paint according to claim 1, characterized in that, The preparation method of the unsaturated water-based polyurethane emulsion comprises: (1) weighing macromolecular diol, and heating to 60-100℃ under nitrogen protection; (2) adding MDI50 for 1-4h; (3) adding dimethylol butyric acid for 1-4h; (4) adding hydroxyethyl acrylate for 2-4h; (5) cooling to room temperature, adding triethylamine for 1-3h; (6) adding water, stirring at a speed of 600-800rpm for 30-60min; The macromolecular diol is selected from one or more than two of polycaprolactone diol, polyethylene glycol, polypropylene glycol and polydimethylsiloxane diol.

6. The fireproof thermal insulation coating according to claim 5, characterized in that, The weight ratio of the macromolecular diol, MDI50, dimethylol butyric acid, hydroxyethyl acrylate, triethylamine and water is 15-25:8-12:1-1.5:1.5-2.5:1:70-100.

7. The fireproof thermal insulation paint according to claim 1, characterized in that, In step (a), the time for ultrasonic dispersion is 0.5-1.5h.

8. The fireproof thermal insulation paint according to claim 1, characterized in that, In step (b), the stirring speed is 200-300rpm.

9. The fireproof thermal insulation paint according to claim 1, characterized in that, In step (b), the reaction temperature is 50-70℃ and the reaction time is 0.5-2h.

10. The fireproof thermal insulation paint according to claim 1, characterized in that, In step (b), the drying temperature is 90-110℃ and the drying time is 20-30h.

11. A method for preparing the fireproof thermal insulation coating according to any one of claims 1-10, characterized in that, The preparation method comprises the following steps: S1: stirring the polymer emulsion, water and auxiliary A for 30-60min, then adding the flame retardant and inorganic filler A, stirring at a speed of 600-800rpm for 1-2h; S2: adding hollow glass microspheres to the material obtained in step S1, stirring at a speed of 100-200rpm for 30-60min to obtain an inner layer coating; S3: stirring the unsaturated waterborne polyurethane emulsion, water and auxiliary B for 30-60min, then adding titanium white, modified boron nitride, mica powder, zinc borate and inorganic filler B, stirring at a speed of 600-800rpm for 1-2h; S4: adding the curing agent to the material obtained in step S3, stirring for 30-60min to obtain an outer layer coating.

12. The application of the fireproof thermal insulation coating in any one of claims 1-10 or the fireproof thermal insulation coating prepared by the preparation method of the fireproof thermal insulation coating of claim 11 in a storage tank fireproof thermal insulation coating.

13. A method of preparing a fireproof thermal insulation coating for a storage tank, characterized by, The method comprises the following steps: (I) polishing and rust removing the metal substrate, then spraying a waterborne epoxy primer; (II) brushing the inner layer coating in the fireproof thermal insulation coating on the surface of the waterborne epoxy primer; (III) after the inner layer coating is dried, spraying the outer layer coating in the fireproof thermal insulation coating on the surface of the inner layer coating; The fireproof thermal insulation coating is the fireproof thermal insulation coating in any one of claims 1-10 or the fireproof thermal insulation coating prepared by the preparation method of the fireproof thermal insulation coating of claim 11.

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