Non-intumescent epoxy-based ceramicizable fireproof coating material and preparation method thereof

Abstract

The application discloses a non-intumescent epoxy-based porcelainizable fireproof coating material and a preparation method thereof, and belongs to the technical field of fireproof coating materials. The non-intumescent epoxy-based porcelainizable fireproof coating material is composed of two components A and B. The component A comprises, in terms of weight fractions, 10-20 parts of epoxy resin, 5-10 parts of a curing agent and 0.04-0.06 parts of an accelerator. The component B comprises, in terms of weight fractions, 10-20 parts of zinc phytate hybrid two-dimensional burn-resistant fillers, 15-25 parts of alkaline earth metal glass powder and 5-10 parts of a modified porcelainization aid. The modified porcelainization aid is a mixture of one or both of modified ammonium polyphosphate and modified melamine polyphosphate. The mass ratio of the components A and B is 1:1.1-1.5. The non-intumescent epoxy-based porcelainizable fireproof coating material has the characteristics of high-temperature resistance, fire resistance, heat insulation, smoke suppression and environmental friendliness, and can be widely applied to the surface fireproofing of wood, metal and polymer composite materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of fireproof coating, and particularly relates to a non-intumescent epoxy-based porcelainizable fireproof coating material and a preparation method thereof. BACKGROUND

[0002] With the development of science and technology, a large number of traditional materials in life have been replaced by lightweight polymer materials, and the latter has great potential for performance improvement to make up for its own performance defects, and some traditional materials are still in service in specific fields, and their performance shortcomings cannot be made up by modification like polymer materials, such as fireproof performance. Analysis of fire accidents in recent years shows that a large part of them are caused by flammable materials, which cause great harm to humans.

[0003] Nowadays, new energy vehicle battery pack fireproof materials, oil pipelines, decorative materials, etc. need to be away from high temperature and open flame during normal service, but in actual application, high temperature and open flame are not controlled by humans, so these battery pack fireproof materials, oil pipelines and decorative materials have the risk of causing fire and even explosion. In order to maximize the safety of their normal application, it is necessary to carry out fireproof treatment. In this regard, using fireproof coating on the surface of the substrate is a good fireproof means.

[0004] The stability of fireproof coating material before and after burning is the key to its good fireproof effect. Since the fireproof filler is mostly water-absorbing material, the fireproof coating is prone to cracking and even falling off, thereby losing its fireproof effect. In addition, the adhesion between the residue produced after the fireproof coating material is ablated by the flame and the substrate is also particularly important. Good adhesion will not cause the protective layer to fall off, so that the base material is exposed to the flame, which can effectively prevent or delay the spread of the flame and gain rescue time for fire rescue. Although many fireproof coating materials have been developed at present, there are still many problems in their use. Under the ablation of high-temperature flame, the poor adhesion between the coating material and the substrate causes them to fall off, and the base material is ablated by the flame; the intumescent fireproof coating expands significantly under the ablation of the flame, and the strength of the expanded barrier layer is often poor, and it is limited in the thermal protection material of new energy vehicle battery pack due to space reasons; the complicated preparation process and long preparation period cannot meet the requirements of industrialization; when the flame ablates the coating, a large amount of smoke is produced, which is not environmentally friendly and is difficult to apply to the market, especially the huge consumer market. Therefore, in actual life application, only the requirement of fireproof performance cannot meet the needs of people, so the adhesion of the coating material, the mechanical strength of the fireproof barrier layer and the environmental friendliness are also increasingly concerned by people.

[0005] Epoxy resin is one of the most versatile thermosetting polymer materials, which is widely used in coating and bonding fields due to its excellent adhesion, satisfactory chemical resistance and good mechanical stability. At present, the fireproof coating materials in many inventions choose epoxy resin as the matrix, and achieve the purpose of flame retardant and fireproof by high temperature expansion and release of non-flammable gas mechanism. Chinese patent CN109504232A discloses an epoxy intumescent fireproof coating reinforced by a variety of carbon-based materials. A series of flame retardant (char-forming agent, foaming agent) fillers and auxiliary fillers are added to the epoxy resin. The coating foams and expands at high temperature to achieve the purpose of fireproof and heat insulation. The thick barrier layer formed by foaming and expansion has poor strength. Chinese patent CN109929379A develops a fireproof and flame-resistant anticorrosive coating. The preparation process in this invention is to add a series of flame retardants and phosphates to the epoxy resin, so as to improve the flame retardant and fireproof properties and adhesion performance. However, this coating material cannot adapt to high temperature environment of 1000 ℃ and above, which limits its application range. Chinese patent CN109880423A publishes a new type of flame-retardant thermal-insulating protective coating and its preparation method. The preparation process disclosed in this patent is to functionalize the resin with fireproof function in advance, and then uniformly disperse a series of char-forming agents, flame retardants and heat insulating agents in the resin. However, this process is complex and adds many fillers, which significantly reduces the strength of the coating material. Especially in some special fields, such as strong scouring fire, the strong scouring action of flame or other particles will cause the expansion coating to fall off, thus losing the function of fireproof and heat insulation. In recent years, a ceramifiable technology has emerged, which is to add ceramic filler (such as low-melting-point glass powder and high-melting-point filler) to the polymer matrix. Under the ablation of flame, the low-melting-point glass powder will melt, and then bond the decomposition products and fillers in the system, forming a sintered body similar to ceramic. Chinese patent CN109796870A discloses a ceramifiable ablation-resistant silicone rubber composite coating material and its preparation method. A certain amount of ceramic filler and ceramic auxiliary agent are added to the silicone rubber. However, the silicone rubber composite material cannot be directly used as a coating material. In this document, it is dissolved in solvents such as xylene, and then coated on the surface of the workpiece by spraying to form a fireproof coating. Although its fireproof performance is excellent, this preparation method has certain pollution to the environment. Chinese patent CN105623486A discloses a high-temperature ceramifiable flame-retardant water-based alkyd resin coating and its preparation method. A certain amount of ceramifiable filler and fluxing agent are added to the water-based alkyd resin, and deionized water is used as the solvent to ensure the environmental non-pollution. However, the preparation process includes modification and grinding, which is complex.Chinese patent CN109970388A discloses a foaming type ceramicizable polyolefin composite material and its preparation method, which is prepared by adding low-melting glass powder into EVA matrix. Although the fire resistance and heat insulation performance are greatly improved, a large amount of foaming agent is added in the material, which significantly reduces the erosion resistance and density of the material, which is not suitable for fire retardant coating field. Chinese patent CN105884267 discloses a flame-retardant, drip-free and ceramicizable silicone rubber and its preparation method. The invention has simple process and easily available raw materials, but the document does not mention the heat insulation of ablation residue. There are many such inventions, but most of them are applied to thermoplastic resin matrix, and the application of thermosetting resin is rarely reported. The difficulty lies in the fire retardant coating of thermosetting resin matrix, which generates only a small amount of residual carbon during ablation. This is also the reason why the development of thermosetting resin fire retardant coating material has been dominated by intumescent type for nearly 30 years. Therefore, the first difficulty to overcome in developing non-intumescent ceramicizable thermosetting resin coating is how to increase the amount of residual carbon in the thermosetting resin material during pyrolysis.

[0006] In summary, the existing fire retardant coating technology still has many problems, such as poor structure stability before and after burning, poor carbon formation performance, poor high temperature resistance, poor erosion resistance, poor adhesion, poor smoke suppression, defects in intumescent barrier structure, complex process, and environmental pollution in construction process. At present, the ceramicizable technology is not widely used in the field of fire retardant coating, and the existing ceramicizable fire retardant coating has problems such as environmental pollution (toxic solvents, etc.), complex process, etc. Therefore, it is of great significance to develop a ceramicizable fire retardant coating material without the above problems for the further development and application of ceramicizable technology. SUMMARY

[0007] In order to solve the problems existing in the prior art, the purpose of the present application is to provide an epoxy-based coating material with high temperature resistance, fire resistance, heat insulation, smoke suppression, environmental friendliness and other properties, which can be widely used in wood, metal, polymer composite surface fire protection. The present application also provides a preparation method of the above non-intumescent epoxy-based ceramicizable fire retardant coating material.

[0008] The present application is realized by the following technical solutions:

[0009] A non-intumescent epoxy-based ceramicizable fire retardant coating material is composed of two components A and B, and the A and B components are made of the following raw materials by weight fraction:

[0010] A component weight fraction

[0011] Epoxy resin 10~20

[0012] Curing agent 5~10

[0013] Accelerator 0.04~0.06

[0014] Component B Weight parts

[0015] Modified two-dimensional burn-resistant filler 10~20

[0016] Alkaline earth metal glass powder 15~25

[0017] Modified porcelain-forming auxiliary 5~10

[0018] The mass ratio of components A and B is 1:1.1~1.5.

[0019] Preferably, a non-intumescent epoxy-based porcelainizable fireproof coating material, which is composed of components A and B, is made of the following raw materials by weight parts:

[0020] Component A Weight parts

[0021] Epoxy resin 10

[0022] Curing agent 7.5

[0023] Accelerator 0.05

[0024] Component B Weight parts

[0025] Modified two-dimensional burn-resistant filler 10~20

[0026] Alkaline earth metal glass powder 19~23

[0027] Modified porcelain-forming auxiliary 6~9

[0028] The mass ratio of components A and B is 1:1.3~1.5.

[0029] In the present application, the epoxy resin in the further technical solution of the non-intumescent epoxy-based porcelainizable fireproof coating material is bisphenol A type epoxy resin, and the epoxy value is 0.44-0.51.

[0030] In the present application, the curing agent in the further technical solution of the non-intumescent epoxy-based porcelainizable fireproof coating material is methyl tetrahydrophthalic anhydride.

[0031] In the present application, the accelerator in the further technical solution of the non-intumescent epoxy-based porcelainizable fireproof coating material is one of 2-ethyl-4-methyl imidazole, 2-methyl imidazole urea, and 2-phenyl imidazole.

[0032] In the present application, the modified two-dimensional burn-resistant filler in the further technical solution of the non-intumescent epoxy-based porcelainizable fireproof coating material has a melting point of 1000℃ or higher and a particle size of about 10 microns. Preferably, it is a zinc phytate hybrid two-dimensional burn-resistant filler.

[0033] The non-intumescent epoxy-based porcelainizable fireproof coating material provided by the application further comprises a two-dimensional burn-resistant filler in the zinc phytate hybrid two-dimensional burn-resistant filler, and the two-dimensional burn-resistant filler is one or any combination of mica powder, talc powder, boron nitride and montmorillonite.

[0034] Further, the preparation method of the modified two-dimensional burn-resistant filler is as follows:

[0035] S1, slowly add the two-dimensional burn-resistant filler to the zinc acetate aqueous solution and stir to uniformly disperse to obtain a suspension; wherein the mass concentration of the zinc acetate aqueous solution is 30 g / L, and the mass concentration of the two-dimensional burn-resistant filler in the suspension is 0.3-0.4 g / mL;

[0036] S2, dropwise add the phytic acid aqueous solution to the suspension and stir to perform ion exchange; perform suction filtration, washing and drying to obtain the zinc phytate hybrid two-dimensional burn-resistant filler; wherein the mass concentration of the phytic acid aqueous solution is 55 g / L, and the dropwise adding amount of the phytic acid aqueous solution is 0.25-0.26 times the volume of the zinc acetate aqueous solution.

[0037] The non-intumescent epoxy-based porcelainizable fireproof coating material provided by the application further comprises an alkaline earth metal glass powder, which is a low-melting-point glass powder containing an alkaline earth metal, has a softening temperature of 550-600 DEG C and a particle size of about 5 microns.

[0038] The non-intumescent epoxy-based porcelainizable fireproof coating material provided by the application further comprises a modified porcelainization aid, which is one or a combination of modified ammonium polyphosphate and modified melamine polyphosphate, and has a particle size of about 5 microns.

[0039] Further, the preparation method of the modified porcelainization aid is as follows:

[0040] S10, mix p-phenylenediamine, formaldehyde and dimethyl phosphite at room temperature, slowly heat to 80-100 DEG C, stir for 20-60 minutes, and naturally cool to room temperature; wherein the molar ratio of p-phenylenediamine, formaldehyde and dimethyl phosphite is 1:2:2;

[0041] S20, add formaldehyde and phosphoric acid, slowly heat to 60-80 DEG C, stir for 20-60 minutes, and naturally cool to room temperature; wherein the addition amount of formaldehyde is equal to the molar amount of formaldehyde in step S10; and the addition amount of phosphoric acid is equal to the molar amount of dimethyl phosphite in step S10;

[0042] S30, add deionized water to the reaction product of S20 to make the concentration 20 g / L to obtain a modified solution;

[0043] S40, taking the modified solution, adding the porcelainizing aid (ammonium polyphosphate or melamine polyphosphate), stirring for 60-120 minutes, at this point the ammonium radical in the porcelainizing aid and the phosphate radical in the reaction product in step S20 have strong interaction, and the modification of the porcelainizing aid is completed; the above product is washed with anhydrous ethanol and dried in an oven at 80 DEG C to obtain the modified porcelainizing aid.

[0044] The porcelainizing aid is a combination of one or both of ammonium polyphosphate and melamine polyphosphate, and the addition amount of the porcelainizing aid is 4 times the mass of the S20 reaction product in the modified solution.

[0045] The application also provides a preparation method of the non-intumescent epoxy-based porcelainizable fireproof coating material, comprising the following steps:

[0046] (1) preparing A and B components respectively:

[0047] According to the formula, the epoxy resin and the curing agent are weighed, and are uniformly stirred in an oil bath at 80-85 DEG C at low speed for 1-2 min, and the accelerator is added and uniformly stirred, and A component is obtained;

[0048] According to the formula, the modified two-dimensional burn-resistant filler, the alkaline earth metal glass powder and the modified porcelainizing aid are weighed and uniformly mixed after drying, and B component is obtained;

[0049] (2) preparation of a two-component mixture:

[0050] B component is added to A component in proportion and is uniformly stirred;

[0051] (3) coating, curing and forming:

[0052] The two-component mixture prepared in step (2) is coated on the surface of the preheated substrate, and is cured at 140-150 DEG C for 4-6 h to obtain the non-intumescent epoxy-based porcelainizable fireproof coating material.

[0053] Preferably, the coating machine is heated, and the wire bar is used to coat the surface of the preheated substrate, the single-coating thickness is controlled to be 20-40 mu m, and the total coating thickness is controlled to be about 2 mm.

[0054] Compared with the prior art, the application has the following beneficial effects:

[0055] ① The modified two-dimensional burn-resistant filler, due to the introduction of zinc phytate, promotes the pyrolysis of phosphides into carbon on the resin matrix with the transition metal zinc element as a catalyst, thereby increasing the carbon residue of the material. In addition, compared with the direct blending addition of zinc phytate, the addition of nanofiller avoids the contradiction that the viscosity of the coating is too large to meet the construction requirements, and the two-dimensional material provides sites for the deposition of zinc phytate due to its high specific surface area, thereby increasing the contact efficiency of zinc phytate with the resin matrix, realizing the in-situ catalytic carbonization of zinc phytate on the resin matrix; the modified ceramic-forming additive increases the amount of non-combustible gas generated after pyrolysis of the coating material at medium and low temperatures due to the introduction of phosphorus and nitrogen elements, thereby improving its gas-phase flame-retardant effect. It is well known that ammonium polyphosphate or melamine polyphosphate has strong water absorption, so the coating material has poor water resistance, unstable structure, and is easy to fall off, which is one of the reasons for the poor fire resistance of current fire-resistant coating materials. Compared with the unmodified ceramic-forming additive, the modified ceramic-forming additive has better water resistance due to the introduction of organic groups, thereby improving the water resistance of the resin-based coating material, and thus maintaining good fire resistance during service in an open environment. Most importantly, through the above two modifications, the latter introduces phosphoric acid groups, which is beneficial to the dehydration and carbonization of epoxy resin, and the introduction of transition metals in the former makes the carbonization process easier, so the synergistic effect of the two modifications greatly improves the pyrolysis and carbonization efficiency of the epoxy resin matrix.

[0056] ② Based on the multi-scale structure design of the system components, i.e. limiting the size of the two-dimensional material and the size of the alkaline earth metal glass powder, a barrier system similar to the "brick-sand" structure is formed inside the coating material system. At medium and low temperatures (300-600 ℃), the polymer matrix and the modified ceramic-forming additive are first pyrolyzed and melted, and then flow between the modified two-dimensional burn-resistant filler and the ceramic-forming filler. At the same time, the phosphides after the pyrolysis of the modified additive promote the melting of the alkaline earth metal glass powder. Through solid-phase sintering reaction at medium and high temperatures (600-800 ℃), the two form a dense ceramic-like physical barrier in cooperation with the modified two-dimensional burn-resistant filler, which plays a role in isolating oxygen, heat and combustible materials. With further temperature rise, the modified two-dimensional burn-resistant filler finally participates in the ceramicization reaction at high temperatures (800-1000 ℃) and forms a dense ceramic with certain strength, thereby showing excellent fire resistance (fire resistance temperature above 1000 ℃).

[0057] ③ The controlled orientation of the modified two-dimensional burn-resistant filler in the coating system is realized by using a wire bar coating tool (30 microns per coating) on a heated coating machine. The controlled orientation of the two-dimensional synergistic filler forms a barrier in the material system, effectively delaying the rapid decomposition of the coating itself and its internal matrix, and improving the stability of the barrier layer after ablation of the material.

[0058] (4) The modified ceramic-forming auxiliary agent first produces non-combustible gases, ammonia and water vapor, during the decomposition process, which further plays a role in diluting air, achieving gas-phase flame retardation. At the same time, phosphoric acid is formed after decomposition, and the phosphoric acid coats the coke decomposed from the epoxy resin, forming a phosphoric acid-carbon layer structure. This dense phosphoric acid-carbon layer structure can act as a barrier to fire and isolate oxygen, etc., and has a great improvement effect on the flame retardation, fire resistance, smoke suppression, etc. of the coating. The ammonia and water vapor produced during the decomposition of the system promote the migration of the phosphorus-carbon mixture in the system. Because the bond energy of phosphorus-alkaline earth metal is higher than that of silicon-alkaline earth metal, the alkaline earth metal in the alkaline earth metal glass powder migrates to the phosphate phase during the migration of the phosphorus-carbon mixture, and is converted into a phosphate phase. After the migration of the alkaline earth metal element, a silicon-rich region is formed in the original glass powder, and the Si-O non-bridging oxygen bond is converted into a Si-O bridging oxygen bond at high temperature. The amorphous silicon dioxide in this region is converted into cristobalite crystal phase. Therefore, the content of the crystal phase in the system is improved, which has a certain improvement effect on the strength, deformation resistance, and erosion resistance of the ablation residue. With further temperature rise, the modified two-dimensional ablation-resistant filler will also have a eutectic reaction with the amorphous glass powder and the phosphoric acid phase to form a ceramic barrier layer.

[0059] In summary, the non-intumescent epoxy-based ceramifiable fireproof coating material in the present application has many advantages compared to the prior art, such as promoting the pyrolysis of the resin matrix into carbon, and the coating can withstand high temperatures of 1000°C and above while maintaining a certain strength; when the flame is ablated, the coating material exhibits good deformation resistance and erosion resistance; in actual use, the smoke suppression effect is excellent; unlike existing ceramifiable fireproof coatings, the epoxy-based fireproof coating material in the present application does not require the use of any toxic solvents, ensuring environmental non-pollution; the raw materials used are environmentally friendly, the preparation process is simple, the preparation period is short, and the production can be scaled up. BRIEF DESCRIPTION OF DRAWINGS

[0060] Figure 1 The left graph is the micro-morphology of pure montmorillonite, and the right graph is the micro-morphology of zinc phytate hybrid montmorillonite.

[0061] Figure 2 The left graph is the micro-morphology of pure ammonium polyphosphate, and the right graph is the micro-morphology of modified ammonium polyphosphate.

[0062] Figure 3 The XRD graph (A) of the epoxy-based fireproof coating (Comparative Example 1) with only alkaline earth metal glass powder after ablation at different temperatures and the XRD graph (B) of the epoxy-based fireproof coating (Example 3) of the present application after ablation at different temperatures. DETAILED DESCRIPTION

[0063] The present application will be described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present application.

[0064] Example 1

[0065] Preparation of modified two-dimensional burn-resistant filler: prepare a zinc acetate aqueous solution with a concentration of 30 g / L; slowly add 10 g of two-dimensional burn-resistant filler montmorillonite to the above 30 ml zinc acetate aqueous solution and stir to disperse, stirring for 30 minutes; prepare a phytic acid aqueous solution with a concentration of 55 g / L; add 8 g of the prepared phytic acid aqueous solution in step ③ dropwise to the uniformly dispersed system in step ②, stir for 30 minutes for sufficient ion exchange; finally, after suction filtration, washing and drying, the zinc phytate hybrid montmorillonite is obtained. Figure 1 The left image is the micro-morphology of pure montmorillonite, and the right image is the micro-morphology of zinc phytate hybrid montmorillonite. From Figure 1 It can be seen that the surface of pure montmorillonite is relatively smooth, while the surface of zinc phytate hybrid montmorillonite is obviously deposited with flocculent zinc phytate.

[0066] According to this method, mica powder, talc powder, and talc powder + boron nitride two-dimensional burn-resistant fillers are used as raw materials to prepare modified two-dimensional burn-resistant fillers. The melting points of the prepared modified two-dimensional burn-resistant fillers are all above 1000 ℃, and the particle sizes are about 10 microns.

[0067] Example 2

[0068] Preparation of modified porcelain-forming additive:

[0069] (1) Mix p-phenylenediamine, formaldehyde and dimethyl phosphite in a molar ratio of 1:2:2 at room temperature, slowly heat to 90°C, and stir for 30 minutes;

[0070] (2) Reduce the above reaction system to room temperature, continue to add the same molar fraction of formaldehyde and phosphoric acid as in step (1), slowly heat to 70°C, and stir for 30 minutes;

[0071] (3) Reduce the above reaction system to room temperature, add deionized water to adjust the concentration of the above solution to 20 g / L;

[0072] (4) Take 500 ml of the above solution, add 40 g of porcelain-forming additive (ammonium polyphosphate or melamine polyphosphate) to it, stir for 60 minutes, and here the ammonium in the porcelain-forming additive and the phosphate groups in the product in step (2) have a strong interaction, thereby completing the modification of the porcelain-forming additive;

[0073] (5) Finally, wash the above product with anhydrous ethanol and dry it in an oven at 80°C to obtain the modified porcelain-forming additive.

[0074] Figure 2 The left image is the micro-morphology of pure ammonium polyphosphate, and the right image is the micro-morphology of modified ammonium polyphosphate. From Figure 2It can be seen that the surface of pure ammonium polyphosphate is relatively smooth, while the surface of modified ammonium polyphosphate becomes rough.

[0075] Example 3

[0076] Specific method for preparing the non-intumescent epoxy-based porcelainizable fireproof coating material:

[0077] ① Preparation of component B: The modified two-dimensional burn-resistant filler, alkaline earth metal glass powder (purchased from Foshan Jinggu Materials Technology Co., Ltd., model 2688177-016), and modified porcelain-forming auxiliary were subjected to drying treatment at 60 ℃ for 6 h. Then 10 parts of modified two-dimensional burn-resistant filler (modified talc powder), 19 parts of alkaline earth metal glass powder, and 6 parts of modified porcelain-forming auxiliary (modified ammonium polyphosphate) were mixed uniformly.

[0078] ② Preparation of component A: 10 parts of epoxy resin (E44) and 7.5 parts of curing agent (methyl tetrahydrophthalic anhydride) were weighed and mixed, and then subjected to mechanical stirring at 85 ℃ for 2 min. 0.05 parts of accelerator (2-ethyl-4-methylimidazole) was added, and the stirring was continued for 2-3 min.

[0079] ③ The prepared component B was uniformly added to component A, and the stirring was continued for 20 min

[0080] ④ The substrate was preheated at 60 ℃ for 3 min, and then the stirred mixture was coated on the surface of the substrate by using a heated coater with a wire bar. The single coating thickness was controlled at 30 μm, and the total coating thickness was controlled at about 2 mm. The non-intumescent epoxy-based porcelainizable fireproof coating material was obtained by curing at 145 ℃ for 4 h.

[0081] The mass ratio of components A and B was 1:1.4.

[0082] The coating performance is shown in Table 1.

[0083]

[0084] Example 4

[0085] Specific method for preparing the non-intumescent epoxy-based porcelainizable fireproof coating material:

[0086] ① Preparation of component B: The modified two-dimensional burn-resistant filler, alkaline earth metal glass powder (purchased from Shanggao Mingzheng Plastic Co., Ltd., model D250), and modified porcelain-forming auxiliary were subjected to drying treatment at 60 ℃ for 6 h. Then 15 parts of modified two-dimensional burn-resistant filler (modified montmorillonite powder), 21 parts of alkaline earth metal glass powder, and 7.5 parts of modified porcelain-forming auxiliary (modified melamine polyphosphate) were mixed uniformly.

[0087] Preparation of component A: 10 parts of epoxy resin (E44), 7.5 parts of curing agent (methyl tetrahydrophthalic anhydride) were weighed and mixed, and then mechanically stirred at 85°C for 2 min. 0.05 parts of accelerator (2-methyl imidazole urea) was added and stirred for 2-3 min.

[0088] Preparation of component B: 20 parts of modified two-dimensional refractory filler (modified talc powder 10 parts + modified boron nitride 10 parts), 23 parts of alkaline earth metal glass powder and 9 parts of modified porcelain forming auxiliary (modified ammonium polyphosphate 4.5 parts + modified melamine polyphosphate 4.5 parts) were weighed and mixed uniformly.

[0089] Preparation of component B: 20 parts of modified two-dimensional refractory filler (modified talc powder 10 parts + modified boron nitride 10 parts), 23 parts of alkaline earth metal glass powder and 9 parts of modified porcelain forming auxiliary (modified ammonium polyphosphate 4.5 parts + modified melamine polyphosphate 4.5 parts) were weighed and mixed uniformly.

[0090] The mass ratio of components A and B is 1:1.3.

[0091] Test the performance of the coating Table 2.

[0092]

[0093] Example 5

[0094] Preparation of non-expanding epoxy-based porcelainizable fireproof coating material:

[0095] Preparation of component B: 20 parts of modified two-dimensional refractory filler (modified talc powder 10 parts + modified boron nitride 10 parts), 23 parts of alkaline earth metal glass powder and 9 parts of modified porcelain forming auxiliary (modified ammonium polyphosphate 4.5 parts + modified melamine polyphosphate 4.5 parts) were weighed and mixed uniformly.

[0096] Preparation of component A: 10 parts of epoxy resin (E44), 7.5 parts of curing agent (methyl tetrahydrophthalic anhydride) were weighed and mixed, and then mechanically stirred at 85°C for 2 min. 0.05 parts of accelerator (2-methyl imidazole urea) was added and stirred for 2-3 min.

[0097] Preparation of component B: 20 parts of modified two-dimensional refractory filler (modified talc powder 10 parts + modified boron nitride 10 parts), 23 parts of alkaline earth metal glass powder and 9 parts of modified porcelain forming auxiliary (modified ammonium polyphosphate 4.5 parts + modified melamine polyphosphate 4.5 parts) were weighed and mixed uniformly.

[0098] Preparation of component B: 20 parts of modified two-dimensional refractory filler (modified talc powder 10 parts + modified boron nitride 10 parts), 23 parts of alkaline earth metal glass powder and 9 parts of modified porcelain forming auxiliary (modified ammonium polyphosphate 4.5 parts + modified melamine polyphosphate 4.5 parts) were weighed and mixed uniformly.

[0099] The mass ratio of components A and B is 1:1.5.

[0100] The coating performance is tested in Table 3.

[0101]

[0102] Comparative Example 1

[0103] Specific method for preparing the non-intumescent epoxy-based porcelainizable fireproof coating material:

[0104] ① Preparation of component B: dry the alkaline earth metal glass powder (same as in Example 3) at 60 ℃ for 6 h. Then weigh 23 parts of the alkaline earth metal glass powder.

[0105] ② Preparation of component A: weigh 10 parts of epoxy resin (E44) and 7.5 parts of curing agent (methyltetrahydrophthalic anhydride), mix them, and mechanically stir at 85 ℃ for 2 min. Add 0.05 parts of accelerator (2-phenylimidazole) and continue stirring for 2-3 min.

[0106] ③ Add the prepared component B to component A and continue stirring for 20 min

[0107] ④ Preheat the substrate at 60 ℃ for 3 min, then use a heated coater to apply the stirred mixture to the surface of the substrate using a wire bar, with a single coating thickness of 30 um and a total coating thickness of about 2 mm. Curing is performed at 145 ℃ for 4 h to obtain the non-intumescent epoxy-based porcelainizable fireproof coating material.

[0108] The mass ratio of components A and B is 1:1.4.

[0109] The coating performance is tested in Table 4.

[0110]

[0111] Note: Since no complete coating was formed, the heat exposure resistance and water absorption rate could not be measured.

[0112] Comparative Example 2

[0113] Specific method for preparing the non-intumescent epoxy-based porcelainizable fireproof coating material:

[0114] ① Preparation of component B: dry the unmodified two-dimensional burn-resistant filler, alkaline earth metal glass powder (same as in Example 3), and unmodified porcelain-forming auxiliary at 60 ℃ for 6 h. Then mix 10 parts of unmodified two-dimensional burn-resistant filler (talcum powder), 19 parts of alkaline earth metal glass powder, and 6 parts of unmodified porcelain-forming auxiliary (ammonium polyphosphate) uniformly.

[0115] Preparation of component A: 10 parts of epoxy resin (E44), 7.5 parts of curing agent (methyl tetrahydrophthalic anhydride) were weighed and mixed, and then stirred mechanically at 85°C for 2 min. 0.05 parts of accelerator (2-ethyl-4-methyl imidazole) was added and stirred for another 2-3 min.

[0116] Preparation of component B: 15 parts of modified two-dimensional refractory filler (modified montmorillonite powder), 21 parts of alkaline earth metal glass powder and 7.5 parts of ceramic forming auxiliary (melamine polyphosphate) were weighed and mixed uniformly.

[0117] Preparation of component B: 15 parts of modified two-dimensional refractory filler (modified montmorillonite powder), 21 parts of alkaline earth metal glass powder and 7.5 parts of ceramic forming auxiliary (melamine polyphosphate) were weighed and mixed uniformly.

[0118] The mass ratio of components A and B is 1:1.4.

[0119] Test coating performance Table 5.

[0120]

[0121] Comparative Example 3

[0122] Preparation of non-expanding epoxy-based porcelainizable fireproof coating material

[0123] Preparation of component B: 15 parts of modified two-dimensional refractory filler (modified montmorillonite powder), 21 parts of alkaline earth metal glass powder and 7.5 parts of ceramic forming auxiliary (melamine polyphosphate) were weighed and mixed uniformly.

[0124] Preparation of component A: 10 parts of epoxy resin (E44), 7.5 parts of curing agent (methyl tetrahydrophthalic anhydride) were weighed and mixed, and then stirred mechanically at 85°C for 2 min. 0.05 parts of accelerator (2-ethyl-4-methyl imidazole) was added and stirred for another 2-3 min.

[0125] Preparation of component B: 15 parts of modified two-dimensional refractory filler (modified montmorillonite powder), 21 parts of alkaline earth metal glass powder and 7.5 parts of ceramic forming auxiliary (melamine polyphosphate) were weighed and mixed uniformly.

[0126] Preparation of component B: 15 parts of modified two-dimensional refractory filler (modified montmorillonite powder), 21 parts of alkaline earth metal glass powder and 7.5 parts of ceramic forming auxiliary (melamine polyphosphate) were weighed and mixed uniformly.

[0127] The mass ratio of components A and B is 1:1.4.

[0128] Test coating performance Table 6.

[0129]

[0130] Comparative Example 4

[0131] Specific method for preparing non-intumescent epoxy-based porcelainizable fireproof coating material:

[0132] ① Preparation of component B: The unmodified two-dimensional refractory filler, alkaline earth metal glass powder (same as in Example 4), and modified porcelainization aid were subjected to drying treatment at 60 °C for 6 h. Then 15 parts of unmodified two-dimensional refractory filler (modified montmorillonite powder), 21 parts of alkaline earth metal glass powder, and 7.5 parts of modified porcelainization aid (modified melamine polyphosphate) were mixed uniformly.

[0133] ② Preparation of component A: 10 parts of epoxy resin (E44) and 7.5 parts of curing agent (methyltetrahydrophthalic anhydride) were weighed and mixed, and then 0.05 parts of accelerator (2-methylimidazole urea) was added under mechanical stirring at 85 °C for 2 min.

[0134] ③ The prepared component B was uniformly added to component A, and stirring was continued for 20 min

[0135] ④ The substrate was preheated at 60 °C for 3 min, and then the stirred mixture was coated on the surface of the substrate using a heated coater with a wire bar, with a single coating thickness controlled at 30 um, and the total coating thickness controlled at about 2 mm. The non-intumescent epoxy-based porcelainizable fireproof coating material was obtained by curing at 145 °C for 4 h.

[0136] The mass ratio of components A and B was 1:1.3.

[0137] Test coating performance Table 7.

[0138]

[0139] Comparative Example 5

[0140] Specific method for preparing non-intumescent epoxy-based porcelainizable fireproof coating material:

[0141] ① Preparation of component B: The modified two-dimensional refractory filler, alkaline earth metal glass powder (same as in Example 5), and modified porcelainization aid were subjected to drying treatment at 60 °C for 6 h. Then 20 parts of modified two-dimensional refractory filler (10 parts of modified talc powder + 10 parts of modified boron nitride), 23 parts of alkaline earth metal glass powder, and 9 parts of modified porcelainization aid (4.5 parts of modified ammonium polyphosphate + 4.5 parts of modified melamine polyphosphate) were mixed uniformly.

[0142] Preparation of component A: 10 parts of epoxy resin (E44) and 7.5 parts of curing agent (methyl tetrahydrophthalic anhydride) were weighed and mixed, and then 0.05 parts of accelerator (2-phenylimidazole) was added under mechanical stirring at 85°C for 2-3 min.

[0143] Preparation of component B: 10 parts of epoxy resin (E44) and 7.5 parts of curing agent (methyl tetrahydrophthalic anhydride) were weighed and mixed, and then 0.05 parts of accelerator (2-phenylimidazole) was added under mechanical stirring at 85°C for 2-3 min.

[0144] Preparation of component B: 10 parts of epoxy resin (E44) and 7.5 parts of curing agent (methyl tetrahydrophthalic anhydride) were weighed and mixed, and then 0.05 parts of accelerator (2-phenylimidazole) was added under mechanical stirring at 85°C for 2-3 min.

[0145] The mass ratio of components A and B is 1:1.5.

[0146] The coating performance is shown in Table 8.

[0147]

[0148] Note:

[0149] 1. The fire resistance test method in Tables 1, 2, 3, 4, 5, 6, 7, and 8 is as follows: a 1300°C flame spray gun (butane gas) is used to ablate the coating, and the ablation time of the coating is tested to evaluate its fire resistance. During the experiment, the distance between the spray nozzle and the sample is set to 10 cm.

[0150] 2. The ceramic effect in Tables 1, 2, 3, 4, 5, 6, 7, and 8 is based on whether a hard ceramic layer is formed.

[0151] 3. The adhesion performance in Tables 1, 2, 3, 4, 5, 6, 7, and 8 is evaluated based on whether the ablated coating material and the substrate fall off after ablation for a certain time.

[0152] 4. The heat insulation performance test method in Tables 1, 2, 3, 4, 5, 6, 7, and 8 is as follows: a 1300°C flame spray gun (butane gas) is used to ablate the surface of the coating material, and the real-time temperature change on the back of the substrate is monitored by an infrared thermal imager to evaluate the heat insulation performance of the coating material. During the experiment, the distance between the spray nozzle and the sample is set to 10 cm, and the distance between the infrared thermal imager and the sample is set to 30 cm.

[0153] 5. The heat resistance test method in Tables 1, 2, 3, 4, 5, 6, 7, and 8 is the same as the fire resistance test, and whether the fireproof coating cracks during ablation is used as the basis for evaluation.

[0154] 6. The water absorption test in Tables 1, 2, 3, 4, 5, 6, 7, 8 is tested according to the Archimedes principle, in accordance with the ASTM C373-88 standard.

[0155] 7. The residual rate test method at 800 oC in Tables 1, 2, 3, 4, 5, 6, 7, 8 is as follows: the sample is heated from room temperature to 800 oC, and after 30 min of heat preservation, the mass of the residue / the initial mass of the sample x 100%.

[0156] The maximum smoke release rate of Example 3 and Comparative Example 2 measured by the cone calorimeter is 1536.42 m2 / m2, 1874.55 m2 / m2, respectively. Compared with Comparative Example 2, the smoke release rate of Example 3 is significantly reduced, which is due to the formation of a similar "brick sand" structure by the oriented structure of the two-dimensional filler. Under high-temperature ablation, the "sand" phase filler melts and adheres between the "brick" two-dimensional fillers, playing a role in inhibiting smoke release.

[0157] Figure 3 The XRD patterns of the residues after ablation at different temperatures of the epoxy-based fireproof coating (Comparative Example 1) only adding alkaline earth metal glass powder (A) and the epoxy-based fireproof coating (Example 3) of the present application (B). Figure 3 (A) shows that the coating only adding alkaline earth metal glass powder is in an amorphous state at high temperature, and thus is prone to melt and fall off; Figure 3 (B) shows that the addition of the modified ceramic-forming agent and the modified two-dimensional burn-resistant filler promotes the transformation of the coating to a crystalline ceramic at high temperature, and thus the coating has certain strength and stability.

[0158] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, several improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A non-expanding epoxy-based ceramic-type fire-retardant coating material, characterized in that, It consists of two components, A and B. Component A is made from the following raw materials in parts by weight: 10-20 parts epoxy resin 5-10 parts of curing agent Accelerator 0.04~0.06 parts; Component B is made from the following raw materials in parts by weight: 10-20 parts of modified two-dimensional heat-resistant filler 15-25 parts of alkaline earth metal glass powder 5-10 parts of modified ceramic-forming additive; The weight ratio of component A to component B is 1:1.1~1.5; The modified two-dimensional sintered filler is a zinc phytate hybrid two-dimensional sintered filler, and the two-dimensional sintered filler is one or more of mica powder, talc powder, boron nitride, and montmorillonite; The modified ceramic-forming aid is prepared by the following method: S10. Mix p-phenylenediamine, formaldehyde, and dimethyl phosphite at room temperature, slowly heat to 80-100 °C, stir and react for 20-60 minutes, and then cool naturally to room temperature; wherein the molar ratio of p-phenylenediamine, formaldehyde, and dimethyl phosphite is 1:2:

2. S20. Add formaldehyde and phosphoric acid, slowly heat to 60-80 ℃, stir and react for 20-60 minutes, and then cool naturally to room temperature; wherein, the amount of formaldehyde added is equal to the molar amount of formaldehyde in step S10; and the amount of phosphoric acid added is equal to the molar amount of dimethyl phosphite in step S10. S30. Add deionized water to the reaction product of S20 to make its concentration 20 g / L to obtain a modified solution. S40. Take the modified solution, add the ceramic-forming aid, and stir for 60-120 minutes to complete the modification of the ceramic-forming aid; wherein, the ceramic-forming aid is one or a combination of ammonium polyphosphate and melamine polyphosphate, and the amount of ceramic-forming aid added is 4 times the mass of the S20 reaction product contained in the modified solution; the product is washed with anhydrous ethanol and dried to obtain the modified ceramic-forming aid.

2. The non-expansive epoxy-based ceramic-type fire-retardant coating material according to claim 1, characterized in that, The phytate-zinc hybrid two-dimensional heat-resistant filler has a melting point above 1000 ℃.

3. The non-expansive epoxy-based ceramic-type fire-retardant coating material according to claim 2, characterized in that, The preparation method of the zinc phytate hybrid two-dimensional heat-resistant filler includes the following steps: S1. The two-dimensional heat-resistant filler is slowly added to the zinc acetate aqueous solution and stirred to disperse it evenly to obtain a suspension; wherein, the mass concentration of the zinc acetate aqueous solution is 30 g / L, and the mass concentration of the two-dimensional heat-resistant filler in the suspension is 0.3~0.4 g / mL; S2. Add the phytic acid aqueous solution dropwise to the suspension and stir to carry out sufficient ion exchange; filter, wash and dry to obtain the phytic acid zinc hybrid two-dimensional heat-resistant packing; wherein the mass concentration of the phytic acid aqueous solution is 55 g / L, and the amount of phytic acid aqueous solution added is 0.25~0.26 times the volume of the zinc acetate aqueous solution.

4. The non-expansive epoxy-based ceramic-type fire-retardant coating material according to claim 1, characterized in that, The epoxy resin is a bisphenol A type epoxy resin with an epoxy value of 0.44~0.

51.

5. The non-expansive epoxy-based ceramic-type fire-retardant coating material according to claim 1, characterized in that, The curing agent is methyltetrahydrophthalic anhydride.

6. The non-expansive epoxy-based ceramic-type fire-retardant coating material according to claim 1, characterized in that, The accelerator is one of 2-ethyl-4-methylimidazole, 2-methylimidazole urea, and 2-phenylimidazole.

7. The non-expansive epoxy-based ceramic-type fire-retardant coating material according to claim 1, characterized in that, The alkaline earth metal glass powder is a low-melting-point glass powder containing alkaline earth metals, with a softening temperature of 550~600 ℃.

8. The method for preparing the non-expanding epoxy-based ceramic-type fire-retardant coating material according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Prepare components A and B separately: Weigh epoxy resin and curing agent according to the formula, stir them evenly in an oil bath at 80~85 ℃, add accelerator and continue stirring evenly, which is component A; Weigh modified two-dimensional sintered filler, alkaline earth metal glass powder and modified ceramic additive according to the formula, dry and mix evenly, which is component B. (2) Preparation of the two-component mixture: Add component B to component A in proportion and stir until homogeneous; (3) Coating and curing: The substrate is preheated, and the two-component mixture obtained in step (2) is coated on the preheated substrate surface and cured at 140~150 ℃ for 4~6 h to obtain a non-expanding epoxy ceramic fireproof coating material.

9. The method for preparing the non-expanding epoxy-based ceramic-type fire-retardant coating material according to claim 8, characterized in that, The coating is applied to the preheated substrate surface using a heated coating machine with a bar coating. The thickness of a single coating is controlled at 20~40 μm, and the total coating thickness is controlled at 2 mm.

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