Basalt fiber fireproof plate based on carbon-based protective layer and preparation method of basalt fiber fireproof plate

Abstract

The invention relates to the technical field of fireproof plates, in particular to a basalt fiber fireproof plate based on a carbon-based protective layer and a preparation method of the basalt fiber fireproof plate, and the basalt fiber fireproof plate comprises the following raw materials in parts by weight: 90-100 parts of epoxy resin, 20-30 parts of a curing agent, 15-25 parts of modified basalt fibers, 10-20 parts of filler, 40-60 parts of a flame retardant, 1-2 parts of a coupling agent and 0.5-1 part of a defoaming agent. According to the preparation method, the basalt fiber is prepared through multi-step reaction of pretreatment, impregnation, pre-oxidation and carbonization, the basalt fiber is impregnated in treatment liquid with polyacrylonitrile as a precursor, polymer molecules are effectively attached, and the interface debonding phenomenon at high temperature is effectively inhibited through subsequent pre-oxidation and carbonization treatment under specific atmosphere and temperature programming; the excellent mechanical property stability of the material is kept in a long-term high-temperature environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fireproof plate, in particular to basalt fiber fireproof plate based on carbon-based protective layer and a preparation method thereof. BACKGROUND

[0002] As a new high-performance inorganic fiber, basalt fiber has attracted much attention due to its excellent temperature resistance, non-combustibility and chemical stability. The basalt fiber fireproof plate is a composite plate prepared by adding basalt fiber, flame-retardant filler and various additives to an epoxy resin matrix and then hot-pressing. It is mainly used in the fields of building fireproof isolation and ship bulkhead fireproofing.

[0003] Due to the insufficient interfacial bonding force between the fiber and the resin matrix in the existing basalt fiber fireproof plate, the material is prone to interfacial debonding in long-term high-temperature environment, resulting in unstable performance of the material under high-temperature conditions. Based on this, the present application provides a basalt fiber fireproof plate based on a carbon-based protective layer and a preparation method thereof. SUMMARY

[0004] The present application aims to provide a basalt fiber fireproof plate based on a carbon-based protective layer and a preparation method thereof to solve the problems raised in the background art.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical solution: a basalt fiber fireproof plate based on a carbon-based protective layer, comprising the following raw materials by weight: 90-100 parts of epoxy resin, 20-30 parts of curing agent, 15-25 parts of modified basalt fiber, 10-20 parts of filler, 40-60 parts of flame retardant, 1-2 parts of coupling agent and 0.5-1 part of defoaming agent. The modified basalt fiber is prepared by the following method: S1: basalt fiber pretreatment, selecting basalt fiber as raw material, pretreating the basalt fiber to obtain a crude material, which is ready for use; S2: immersion treatment, immersing the crude material to obtain a preliminary material, which is ready for use; S3: temperature rising treatment, temperature rising treatment of the preliminary material to obtain modified basalt fiber; Preferably, the method for pretreating the basalt fiber is as follows: the basalt fiber is immersed in a sodium hydroxide solution with a concentration of 1-3 mol / L and treated at 60-80℃ for 40-60 min, then washed with deionized water until neutral and dried at 80-100℃ for 2-4 h, then immersed in a nitric acid solution with a concentration of 2-5 mol / L and treated at 50-80℃ for 80-120 min, then washed with deionized water until neutral and dried at 80-100℃ for 2-4 h, thereby completing the pretreatment of the basalt fiber and obtaining the crude material.

[0006] Preferably, the method of the impregnation treatment is as follows: the raw material is immersed in the treatment solution, taken out after 20-30 min, dried in the fume hood at room temperature for 30-40 min, and then vacuum dried at 60-80℃ for 2-4 h to complete the impregnation treatment, and obtain the preliminary material.

[0007] Preferably, the treatment solution is prepared by mixing polyacrylonitrile, urea and dimethyl sulfoxide, wherein the mass fraction of polyacrylonitrile is 7-8%, the mass fraction of urea is 0.5-0.7%, and the rest is supplemented with dimethyl sulfoxide to 100%.

[0008] Preferably, the method of the temperature rising treatment is as follows: the preliminary material is put into a muffle furnace, mixed gas of oxygen and nitrogen is introduced, the oxygen concentration is 15-20%, the gas flow rate is 1.5-2 L / min, the temperature rising rate is set to 1-3℃ / min, the temperature is raised to 220-300℃, and then kept for 80-120 min, nitrogen gas is introduced, the gas flow rate is 2-3 L / min, the temperature rising rate is set to 4-6℃ / min, the temperature is raised to 600-700℃, and then kept for 60-90 min, and then the temperature decreasing rate is set to 3-5℃ / min until the temperature decreases to room temperature, and the modified basalt fiber is prepared.

[0009] Preferably, the filler is prepared by the following method: aluminum hypophosphite and polyurea are mixed, dry ball milling treatment is carried out at 200-300 rpm for 2-4 h to obtain a base material, the base material, zinc borate, boron nitride, anhydrous calcium sulfate whisker and KH560 are added into a mixer, stirring treatment is carried out at 400-600 rpm for 30-40 min, the obtained product is heat treated at 85-95℃ for 60-80 min in a nitrogen atmosphere, and then sieved to 300 mesh after cooling to obtain the filler.

[0010] Preferably, the mass ratio of aluminum hypophosphite to polyurea is 10:1, and the mass ratio of the base material, zinc borate, boron nitride, anhydrous calcium sulfate whisker and KH560 is 10:3-4:1-2:1-2:0.1-0.2.

[0011] Preferably, the epoxy resin is bisphenol A type epoxy resin, the curing agent is T31 curing agent, the coupling agent is KH550, and the defoaming agent is organic silicon defoaming agent.

[0012] Preferably, the flame retardant is prepared by mixing aluminum hydroxide, ammonium polyphosphate and melamine, and the mass ratio of aluminum hydroxide, ammonium polyphosphate and melamine is 10:1-2:0.5-1.

[0013] Preferably, a preparation method of basalt fiber fireproof plate based on carbon-based protective layer comprises the following steps: weighing epoxy resin, curing agent, flame retardant, coupling agent and defoaming agent as needed and adding them into a mixer, setting 300-500 rpm stirring treatment for 10-20 min, then adding modified basalt fiber and filler, setting 400-600 rpm stirring treatment for 20-30 min, pouring the obtained product into a mold and laying it flat, and sending it into a hot press, heating to 140-160 DEG C at a temperature rising rate of 2-5 DEG C / min under a pressure of 1-2 MPa, and keeping the temperature and pressure for 1-2 h, so as to obtain the basalt fiber fireproof plate based on carbon-based protective layer.

[0014] Compared with the prior art, the basalt fiber fireproof plate based on carbon-based protective layer has the following advantages: 1. In the present application, the basalt fiber is prepared through a multi-step reaction of pretreatment, impregnation, pre-oxidation and carbonization, in the process, the basalt fiber is pretreated by nitric acid and sodium hydroxide solution, the surface roughness and chemical active sites are significantly increased, and the basalt fiber is impregnated in a treatment solution taking polyacrylonitrile as a precursor, so that the polymer molecules are effectively attached, and then the basalt fiber is subjected to pre-oxidation and carbonization treatment under a specific atmosphere and a programmed temperature rise, so that the polyacrylonitrile precursor on the surface of the basalt fiber undergoes cyclization, crosslinking and finally generates a dense and amorphous carbon layer, the carbon layer is firmly combined with the fiber matrix through chemical bonding and physical anchoring, and the interfacial adhesion between the carbon layer and the epoxy resin matrix is greatly enhanced, so that the interfacial debonding phenomenon under high temperature is effectively inhibited, and the material maintains excellent mechanical property stability in a long-term high-temperature environment.

[0015] 2. In the present application, the filler is a composite base material formed by ball milling aluminum hypophosphite and polyurea, and then the composite base material is compounded with zinc borate, boron nitride, anhydrous calcium sulfate whisker and other components under the action of silane coupling agent KH560, and is activated by heat treatment, and under high temperature, the components synergistically act, the aluminum hypophosphite and polyurea act as an acid source and a gas source to promote the expansion into carbon, the zinc borate forms a glassy covering layer, and the boron nitride and calcium sulfate whisker act as a reinforcing phase to improve the strength and density of the carbon layer, so that a stable and firm expanded carbon layer is finally formed, which effectively resists the impact of flame and airflow scouring and prevents the early damage of the carbon layer, thereby ensuring that the fireproof plate obtains efficient and durable flame retardant protection.

[0016] 3. In the present application, the principle of "structure transformation" for preparing carbon fiber is applied to the modification of basalt fiber, and through the "precursor impregnation-pre-oxidation-carbonization" process, a carbon layer firmly combined with the matrix is successfully grown in situ on the surface of the fiber, the carbon layer is like a suit of armor for the fiber, which can fundamentally block the internal penetration of oxygen, thereby greatly improving the service life and performance stability of the basalt fiber product in a high-temperature aerobic environment, and a fireproof plate with uniform structure and reliable performance is obtained. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1A flow chart of a preparation method of a basalt fiber fireproof plate based on a carbon-based protective layer is provided. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0019] It should be noted that the raw materials used in the following embodiments are all commercially available raw materials.

[0020] Embodiment 1 A basalt fiber fireproof plate based on a carbon-based protective layer comprises the following raw materials by weight: 90 parts of epoxy resin, 20 parts of curing agent, 15 parts of modified basalt fiber, 10 parts of filler, 40 parts of flame retardant, 1 part of coupling agent and 0.5 part of defoaming agent. The epoxy resin is selected from bisphenol A type epoxy resin, the curing agent is selected from T31 curing agent, the coupling agent is selected from KH550, and the defoaming agent is selected from organic silicon defoaming agent. The raw materials of the filler include aluminum hypophosphite, polyurea, zinc borate, boron nitride, anhydrous calcium sulfate whisker and KH560. The filler is prepared by the following method: aluminum hypophosphite and polyurea are mixed at a mass ratio of 10:1, then dry ball milling treatment is performed at 200 rpm for 2 h to obtain a base material, the base material, zinc borate, boron nitride, anhydrous calcium sulfate whisker and KH560 are added into a mixer at a mass ratio of 10:3:1:1:0.1, stirring treatment is performed at 400 rpm for 30 min, the obtained product is heated at 85℃ for 60 min under nitrogen atmosphere, and then sieved to 300 meshes after cooling to obtain the filler. The flame retardant is prepared by mixing aluminum hydroxide, ammonium polyphosphate and melamine, and the mass ratio of aluminum hydroxide, ammonium polyphosphate and melamine is 10:1:0.5. The modified basalt fiber is prepared by the following method: S1: Basalt fiber pretreatment, basalt fiber is selected as a raw material, and the basalt fiber is pretreated to obtain a crude material, which is ready for use. The basalt fiber pretreatment method is as follows: the basalt fiber is immersed in a sodium hydroxide solution with a concentration of 1 mol / L, treated at 60 DEG C for 40 min, washed with deionized water to neutral after treatment, and dried at 80 DEG C for 2 h, then treated with a nitric acid solution with a concentration of 2 mol / L at 50 DEG C for 80 min, washed with deionized water to neutral after treatment, and dried at 80 DEG C for 2 h, to complete the basalt fiber pretreatment, and obtain the crude material; S2: immersion treatment, the crude material is subjected to immersion treatment to obtain the preliminary material, ready for use; The immersion treatment method is as follows: the crude material is immersed in a treatment solution, taken out after 20 min, dried in a fume hood at room temperature for 30 min, and then vacuum dried at 60 DEG C for 2 h to complete the immersion treatment, and obtain the preliminary material, wherein the treatment solution is prepared by mixing polyacrylonitrile, urea and dimethyl sulfoxide, the mass fraction of polyacrylonitrile is 7%, the mass fraction of urea is 0.5%, and the rest is supplemented with dimethyl sulfoxide to 100%; S3: temperature rising treatment, the preliminary material is subjected to temperature rising treatment to obtain the modified basalt fiber; The temperature rising treatment method is as follows: the preliminary material is put into a muffle furnace, mixed gas of oxygen and nitrogen is introduced, the oxygen concentration is 15%, the gas flow rate is 1.5 L / min, the temperature rising rate is set to 1 DEG C / min, the temperature is raised to 220 DEG C, and kept for 80 min, then nitrogen gas is introduced, the gas flow rate is 2 L / min, the temperature rising rate is set to 4 DEG C / min, the temperature is raised to 600 DEG C, and kept for 60 min, then the temperature lowering rate is set to 3 DEG C / min, and the temperature is lowered to room temperature, to obtain the modified basalt fiber.

[0021] A preparation method of a basalt fiber fireproof plate based on a carbon-based protective layer, comprising the following steps: weighing epoxy resin, curing agent, flame retardant, coupling agent and defoaming agent as needed and adding them into a mixer, setting 300 rpm stirring treatment for 10 min, then adding modified basalt fiber and filler, setting 400 rpm stirring treatment for 20 min, pouring the obtained product into a mold, flattening, putting into a hot press, raising the temperature to 140 DEG C at a temperature rising rate of 2 DEG C / min under a pressure of 1 MPa, and keeping for 1 h, to obtain the basalt fiber fireproof plate based on the carbon-based protective layer.

[0022] Example 2: A basalt fiber fireproof plate based on a carbon-based protective layer, comprising the following raw materials by weight: 95 parts of epoxy resin, 25 parts of curing agent, 20 parts of modified basalt fiber, 15 parts of filler, 50 parts of flame retardant, 1.5 parts of coupling agent and 0.8 parts of defoaming agent; The epoxy resin is selected from bisphenol A type epoxy resin, the curing agent is selected from T31 curing agent, the coupling agent is selected from KH550, and the defoaming agent is selected from organic silicon defoaming agent; The raw material of the filler comprises aluminum hypophosphite, polyurea, zinc borate, boron nitride, calcium sulfate anhydrous whisker and KH560; The filler is prepared by the following method: aluminum hypophosphite and polyurea are mixed at a mass ratio of 10:1, and then dry ball milling treatment is performed at 250 rpm for 3 h to obtain a base material; the base material, zinc borate, boron nitride, calcium sulfate anhydrous whisker and KH560 are added into a mixer at a mass ratio of 10:3.5:1.5:1.5:0.15, and then stirring treatment is performed at 500 rpm for 35 min; the obtained product is heat treated at 90℃ for 70 min in a nitrogen atmosphere, and then sieved to 300 meshes after cooling to obtain the filler. The flame retardant is prepared by mixing aluminum hydroxide, ammonium polyphosphate and melamine, and the mass ratio of aluminum hydroxide, ammonium polyphosphate and melamine is 10:1.5:0.8. The modified basalt fiber is prepared by the following method: S1: basalt fiber pretreatment, basalt fiber is selected as raw material, and the basalt fiber is pretreated to obtain a crude material, which is ready for use; The method for pretreating the basalt fiber is as follows: the basalt fiber is immersed in a sodium hydroxide solution with a concentration of 2 mol / L, and treated at 70℃ for 50 min; after the treatment, the basalt fiber is washed with deionized water until neutral, and dried at 90℃ for 3 h; then the basalt fiber is immersed in a nitric acid solution with a concentration of 3 mol / L, and treated at 65℃ for 100 min; after the treatment, the basalt fiber is washed with deionized water until neutral, and dried at 90℃ for 3 h; thus the pretreatment of the basalt fiber is completed, and the crude material is obtained. S2: impregnation treatment, the crude material is subjected to impregnation treatment to obtain a preliminary material, which is ready for use; The method for impregnation treatment is as follows: the crude material is immersed in a treatment solution, taken out after 25 min, and dried in a fume hood at room temperature for 35 min; then vacuum drying treatment is performed at 70℃ for 3 h; thus the impregnation treatment is completed, and the preliminary material is obtained. The treatment solution is prepared by mixing polyacrylonitrile, urea and dimethyl sulfoxide, and the mass percentage of polyacrylonitrile is 7.5%, the mass percentage of urea is 0.6%, and the rest is supplemented with dimethyl sulfoxide to 100%. S3: temperature rising treatment, the preliminary material is subjected to temperature rising treatment to obtain the modified basalt fiber; The method for temperature rising treatment is as follows: the preliminary material is put into a muffle furnace, and mixed gas of oxygen and nitrogen is introduced, the oxygen concentration is 18%, the gas flow rate is 1.8 L / min, the temperature rising rate is set to 2℃ / min, the temperature is raised to 260℃, and the temperature is maintained for 100 min; then nitrogen is introduced, the gas flow rate is 2.5 L / min, the temperature rising rate is set to 5℃ / min, the temperature is raised to 650℃, and the temperature is maintained for 75 min; then the temperature is lowered to room temperature at a temperature lowering rate of 4℃ / min, and the modified basalt fiber is obtained.

[0023] A preparation method of basalt fiber fireproof plate based on carbon-based protective layer, comprising the following steps: weighing epoxy resin, curing agent, flame retardant, coupling agent and defoaming agent as needed and adding them into a mixer, setting 400 rpm stirring treatment for 15 min, then adding modified basalt fiber and filler, setting 500 rpm stirring treatment for 25 min, pouring the obtained product into a mold, flattening, and sending into a hot press, heating to 150 DEG C at a temperature rising rate of 3.5 DEG C / min under a pressure of 1.5 MPa, and keeping for 1.5 h, to obtain the basalt fiber fireproof plate based on carbon-based protective layer.

[0024] Example 3: A basalt fiber fireproof plate based on carbon-based protective layer, comprising the following raw materials by weight: 100 parts of epoxy resin, 30 parts of curing agent, 25 parts of modified basalt fiber, 20 parts of filler, 60 parts of flame retardant, 2 parts of coupling agent and 1 part of defoaming agent; Wherein, the epoxy resin is selected from bisphenol A type epoxy resin, the curing agent is selected from T31 curing agent, the coupling agent is selected from KH550, and the defoaming agent is selected from organic silicon defoaming agent; Wherein, the raw materials of the filler include aluminum hypophosphite, polyurea, zinc borate, boron nitride, anhydrous calcium sulfate whisker and KH560; Wherein, the filler is prepared by the following method: mixing aluminum hypophosphite and polyurea according to a mass ratio of 10:1, setting 300 rpm dry ball milling treatment for 4 h to obtain a base material, adding the base material, zinc borate, boron nitride, anhydrous calcium sulfate whisker and KH560 into a mixer according to a mass ratio of 10:4:2:2:0.2, setting 600 rpm stirring treatment for 40 min, and heat treating the obtained product at 95 DEG C for 80 min in a nitrogen atmosphere, and sieving 300 meshes after cooling to obtain the filler; Wherein, the flame retardant is prepared by mixing aluminum hydroxide, ammonium polyphosphate and melamine, and the mass ratio of aluminum hydroxide, ammonium polyphosphate and melamine is 10:2:1; Wherein, the modified basalt fiber is prepared by the following method: S1: basalt fiber pretreatment, selecting basalt fiber as raw material, pretreating the basalt fiber to obtain a coarse material, and waiting for use; Wherein, the method for pretreating the basalt fiber is: immersing the basalt fiber in a sodium hydroxide solution with a concentration of 3 mol / L, treating at 80 DEG C for 60 min, washing with deionized water to neutral after treatment, and drying at 100 DEG C for 4 h, then immersing the basalt fiber in a nitric acid solution with a concentration of 5 mol / L, treating at 80 DEG C for 120 min, washing with deionized water to neutral after treatment, and drying at 100 DEG C for 4 h, to complete the pretreatment of the basalt fiber and obtain the coarse material; S2: impregnation treatment, impregnating the coarse material to obtain a preliminary material, and waiting for use; The method of the impregnation treatment is that the coarse material is immersed in the treatment solution, taken out after 30 min, dried in a fume hood at room temperature for 40 min, and then vacuum dried at 80℃ for 4 h to complete the impregnation treatment, and the prepared material is obtained, wherein the treatment solution is prepared by mixing polyacrylonitrile, urea and dimethyl sulfoxide, the mass percentage of polyacrylonitrile is 8%, the mass percentage of urea is 0.7%, and the rest is supplemented with dimethyl sulfoxide to 100%; S3: temperature rising treatment, the prepared material is subjected to temperature rising treatment to obtain modified basalt fiber; The method of the temperature rising treatment is that the prepared material is sent into a muffle furnace, mixed gas of oxygen and nitrogen is introduced, the oxygen concentration is 20%, the gas flow rate is 2 L / min, the temperature rising rate is set to 3℃ / min, the temperature is raised to 300℃, and the temperature is kept for 120 min, then nitrogen gas is introduced, the gas flow rate is 3 L / min, the temperature rising rate is set to 6℃ / min, the temperature is raised to 700℃, and the temperature is kept for 90 min, then the temperature decreasing rate is set to 5℃ / min, and the temperature is decreased to room temperature, and the modified basalt fiber is obtained.

[0025] A preparation method of basalt fiber fireproof plate based on carbon-based protective layer, comprising the following steps: weighing epoxy resin, curing agent, flame retardant, coupling agent and defoaming agent as needed and adding them into a mixer, setting 500 rpm stirring treatment for 20 min, then adding modified basalt fiber and filler, setting 600 rpm stirring treatment for 30 min, pouring the obtained product into a mold, flattening, sending into a hot press, raising the temperature to 160℃ at a temperature rising rate of 5℃ / min under a pressure of 2 MPa, and keeping the temperature and pressure for 2 h to obtain the basalt fiber fireproof plate based on carbon-based protective layer.

[0026] Comparative Example 1, the difference between this comparative example and Example 1 is that the same amount of unmodified basalt fiber is used instead of modified basalt fiber in this comparative example.

[0027] Comparative Example 2, the difference between this comparative example and Example 1 is that the same amount of aluminum hydroxide is used instead of filler in this comparative example.

[0028] Comparative Example 3, the difference between this comparative example and Example 1 is that the treatment solution used in the impregnation treatment of this comparative example only contains dimethyl sulfoxide.

[0029] Performance test: the fiber fireproof plates prepared in Examples 1-3 and Comparative Examples 1-3 are subjected to performance test; Bending strength test: the bending strength (MPa) is tested according to GB / T 9341-2008 standard and recorded in the following table; Limiting oxygen index test: the limiting oxygen index (LOI, %) is tested according to GB / T 2406.2-2009 standard and recorded in the following table; Vertical burning rating test: test the vertical burning rating according to GB / T 2408-2008 and record in the following table; Acid resistance test: test the mass change rate (%) according to GB / T 11547-2008 standard and record in the following table.

[0030] Table 1:

[0031] By analyzing and comparing the data in the table, it can be seen that the fiber fireproof plate prepared by the methods of examples 1-3 has better bending strength, limiting oxygen index, vertical burning rating and acid resistance than comparative examples 1-3. Through further analysis, it can be seen that: In the bending strength data, the performance of examples 1-3 is significantly better than that of comparative examples 1-3, which is due to the firm interface bonding. In the examples, a dense amorphous carbon protective layer is grown in situ on the surface of basalt fiber through the "pretreatment-impregnation-pre-oxidation-carbonization" process. The carbon layer is firmly combined with the fiber body and produces strong physical anchoring and chemical bonding with the epoxy resin matrix, thereby efficiently transferring and dispersing stress. The strength of comparative example 1 drops sharply, which illustrates the indispensability of the carbon layer. After the absence of the carbon layer, the smooth fiber surface has weak bonding force with the resin matrix, which becomes a stress concentration point and is prone to interface debonding. The strength of comparative example 3 is only better than that of comparative example 1, but is significantly lower than that of examples 1-3, which illustrates the key role of polyacrylonitrile and urea in the treatment liquid. Dimethyl sulfoxide cannot provide a carbon source, resulting in an incomplete and poor-quality carbon layer, which greatly reduces the interface enhancement effect. This also illustrates that successful fiber surface modification is the fundamental reason for obtaining excellent mechanical properties. In the limiting oxygen index and vertical burning rating tests of the flame retardant performance, the performance of examples 1-3 is excellent, which illustrates that aluminum hypophosphite and polyurea as acid source and gas source promote the expansion into carbon, zinc borate forms a glassy covering layer, boron nitride and calcium sulfate whiskers as reinforcing phase, improve the strength of carbon layer, and the combination of multiple parties forms a firm and dense expanded carbon layer, which can effectively isolate heat and oxygen. After the absence of fillers in comparative example 2, the flame retardant performance is the worst, which illustrates that ordinary aluminum hydroxide filler cannot form an effective protective carbon layer, and the flame retardant efficiency is low and there is a risk of dripping. It also illustrates the irreplaceability of the filler. The limiting oxygen index and burning rating of comparative examples 1 and 3 are similar, which shows that the carbon layer on the surface of the fiber itself also provides a certain barrier property, but its main advantage is in mechanical reinforcement. In the acid resistance test, the performance of examples 1-3 is excellent because of the dense carbon-based protective layer and excellent interface integrity, which together form a physical barrier that effectively prevents the penetration and erosion of acid liquid. Comparative example 1 has the worst acid resistance, which illustrates that after the absence of the carbon layer, the interface has defects, which become a fast channel for the penetration of acid liquid. Comparative example 3 has acid resistance only better than that of comparative example 1, which illustrates that the ineffective treatment liquid leads to poor quality of the carbon layer and reduces the protective effect.

[0032] In the description of the application, reference has been made to descriptive terms such as "one embodiment", "an example", "a specific example" or the like, meaning that a particular feature, structure, material or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. The illustrative discussion of these terms in the description is not intended to limit the scope of the application to only the specifically recited embodiment or example. Moreover, use of these terms does not necessarily mean that all transport refrigeration systems utilizing these features, structures, materials or characteristics are identical or similar.

[0033] The preferred embodiments of the application disclosed above are only to help explain the application. The preferred embodiments do not describe all the details of the application and limit the application to only the specific embodiments described. Obviously, many modifications and variations of the application can be made in light of the teachings above. The embodiments are chosen and described in order to best explain the principles of the application and its practical application and to enable others skilled in the art to best utilize the application. The application is limited only by the claims and their full scope and equivalents.

Claims

1. A basalt fiber fire rated panel based on carbon-based protective layer, characterized by: The raw materials include 90-100 parts of epoxy resin, 20-30 parts of curing agent, 15-25 parts of modified basalt fiber, 10-20 parts of filler, 40-60 parts of flame retardant, 1-2 parts of coupling agent and 0.5-1 part of defoaming agent; The modified basalt fiber is prepared by the following method: S1: basalt fiber pretreatment, selecting basalt fiber as raw material, pretreating the basalt fiber to obtain coarse material, and waiting for use; S2: dipping treatment, dipping the coarse material to obtain preliminary material, and waiting for use; S3: temperature rising treatment, treating the preliminary material to prepare modified basalt fiber.

2. The basalt fiber fireboard based on carbon-based protective layer according to claim 1, characterized in that, The method of the basalt fiber pretreatment is: the basalt fiber is immersed in a sodium hydroxide solution with a concentration of 1-3 mol / L, and treated at 60-80℃ for 40-60 min; after the treatment, the basalt fiber is washed with deionized water until neutral, and dried at 80-100℃ for 2-4 h; then the basalt fiber is treated with a nitric acid solution with a concentration of 2-5 mol / L at 50-80℃ for 80-120 min; after the treatment, the basalt fiber is washed with deionized water until neutral, and dried at 80-100℃ for 2-4 h; the basalt fiber pretreatment is completed, and the coarse material is obtained.

3. The basalt fiber fireboard based on carbon-based protective layer according to claim 1, characterized in that, The method of the dipping treatment is: the coarse material is immersed in a treatment liquid, taken out after 20-30 min, dried in a fume hood at room temperature for 30-40 min, and then vacuum dried at 60-80℃ for 2-4 h; the dipping treatment is completed, and the preliminary material is obtained.

4. The basalt fiber fireboard based on carbon-based protective layer according to claim 3, characterized in that, The treatment liquid is prepared by mixing polyacrylonitrile, urea and dimethyl sulfoxide, wherein the mass fraction of polyacrylonitrile is 7-8%, the mass fraction of urea is 0.5-0.7%, and the rest is supplemented by dimethyl sulfoxide to 100%.

5. The basalt fiber fireboard based on carbon-based protective layer according to claim 1, characterized in that, The method of the temperature rising treatment is: the preliminary material is put into a muffle furnace, mixed gas of oxygen and nitrogen is introduced, the oxygen concentration is 15-20%, the gas flow rate is 1.5-2 L / min, the temperature rising rate is set to 1-3℃ / min, the temperature is raised to 220-300℃, and the temperature is kept for 80-120 min; then nitrogen gas is introduced, the gas flow rate is 2-3 L / min, the temperature rising rate is set to 4-6℃ / min, the temperature is raised to 600-700℃, and the temperature is kept for 60-90 min; then the temperature decreasing rate is set to 3-5℃ / min, and the temperature is decreased to room temperature; the modified basalt fiber is prepared.

6. The basalt fiber fireboard based on carbon-based protective layer according to claim 1, characterized in that, The filler is prepared by the following method: aluminum hypophosphite and polyurea are mixed, dry ball milling treatment is carried out at 200-300 rpm for 2-4 h to obtain a base material, the base material, zinc borate, boron nitride, anhydrous calcium sulfate whisker and KH560 are added into a mixer, stirring treatment is carried out at 400-600 rpm for 30-40 min, the obtained product is heat treated at 85-95℃ for 60-80 min in a nitrogen atmosphere, and then sieved to 300 mesh after cooling to prepare the filler.

7. The basalt fiber fireboard based on a carbon-based protective layer according to claim 6, characterized in that, The mass ratio of aluminum hypophosphite to polyurea is 10:1, and the mass ratio of the base material, zinc borate, boron nitride, anhydrous calcium sulfate whisker and KH560 is 10:3-4:1-2:1-2:0.1-0.

2.

8. The basalt fiber fireboard based on carbon-based protective layer according to claim 1, characterized in that, The epoxy resin is selected from bisphenol A type epoxy resin, the curing agent is selected from T31 curing agent, the coupling agent is selected from KH550, and the defoaming agent is selected from organic silicon defoaming agent.

9. The basalt fiber fireboard based on carbon-based protective layer according to claim 1, characterized in that, The flame retardant is prepared by mixing aluminum hydroxide, ammonium polyphosphate and melamine, and the mass ratio of aluminum hydroxide, ammonium polyphosphate and melamine is 10:1-2:0.5-1.

10. The method for manufacturing a basalt fiber fireproof panel based on a carbon-based protective layer according to any one of claims 1 to 9, characterized in that, The method comprises the following steps: weighing epoxy resin, curing agent, flame retardant, coupling agent and defoaming agent as required, and adding them into a mixer, setting 300-500 rpm stirring treatment for 10-20 min, then adding modified basalt fiber and filler, setting 400-600 rpm stirring treatment for 20-30 min, pouring the obtained product into a mold, flattening, and sending into a hot press, heating to 140-160 DEG C at a heating rate of 2-5 DEG C / min under a pressure of 1-2 MPa, and keeping pressure and temperature for 1-2 h, so as to prepare a basalt fiber fireproof plate based on carbon-based protective layer.

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