Flame-retardant and wear-resistant composite material for fire hose and preparation method of flame-retardant and wear-resistant composite material

Abstract

The invention relates to a flame-retardant and wear-resistant composite material for a fire hose and a preparation method of the composite material, and belongs to the technical field of high polymer materials, the composite material comprises the following raw materials: 40-50 parts of modified polyvinyl chloride resin, 20-25 parts of chloroprene rubber, 3-6 parts of a stabilizer, 0.5-1 part of an antioxidant, 0.4-0.6 part of a lubricant and 0.1-0.3 part of a vulcanizing agent; according to the technical scheme, the hyperbranched compound is obtained by combining the bio-based plasticizer with the glycidol; combining the hyperbranched compound with the silanized composite material to obtain a reinforced material; a reinforcing material is subjected to epoxidation modification and then combined with a compound flame retardant, and the flame-retardant reinforcing material is obtained. The flame-retardant reinforcing material is combined with the polyvinyl chloride resin to obtain the modified polyvinyl chloride resin; the modified polyvinyl chloride resin can effectively improve the flame retardant property, wear resistance and mechanical property of the composite material for the fire hose, and overall improves the comprehensive performance of the composite material for the fire hose.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and specifically relates to a composite material for fire hoses with flame retardant and wear-resistant properties and a preparation method thereof. Background Art

[0002] Fire hoses are the most common type of fire fighting equipment, which are hoses used to transport high-pressure water or flame retardant liquids such as foam. They are convenient to lay during use and have become one of the most important fire extinguishing tools in daily life. An ideal fire hose needs to have both excellent flame retardant properties and high strength characteristics. In a high-temperature fire scene, good flame retardant properties can prevent the fire hose from being quickly burned out, ensuring the continuity and stability of water supply and winning precious time for fire fighting operations. In addition, fire hoses must have sufficient mechanical strength and wear resistance to withstand the impact of high-pressure water flow and wear in complex rescue environments, ensuring that they can still maintain stable performance and intact structure under harsh conditions. However, traditional fire hose materials often have difficulty meeting these strict requirements simultaneously. Therefore, there is an urgent need to develop a composite material for fire hoses that can combine excellent flame retardant properties with good mechanical strength and wear resistance to meet the demanding requirements of fire fighting and rescue.

[0003] In the prior art, most traditional composite materials for fire hoses use polyvinyl chloride resin as the matrix. Although they have certain flexibility, they have problems such as insufficient flame retardancy, poor wear resistance, and easy migration of plasticizers. Moreover, after adding a large amount of plasticizer to polyvinyl chloride resin, its flame retardant performance will be greatly reduced, and a large amount of smoke and toxic and harmful gases will be generated during its combustion. In addition, by adding inorganic flame retardants (such as aluminum hydroxide, ammonium polyphosphate) or wear-resistant fillers (such as silicon carbide, nano-silica) to modify polyvinyl chloride resin, it is easy to cause a decrease in the mechanical properties of the composite material for fire hoses, and problems such as filler agglomeration and poor compatibility with the matrix will occur, affecting the final quality of the product. Summary of the Invention

[0004] The purpose of the present invention is to provide a composite material for fire hoses with flame retardant and wear-resistant properties and a preparation method thereof. By combining a bio-based plasticizer with glycidyl, a hyperbranched composite is obtained; the hyperbranched composite is combined with a silanized composite material to obtain a reinforcing material; after the reinforcing material is epoxidized and modified, it is combined with a compound flame retardant to obtain a flame retardant reinforcing material; by combining the flame retardant reinforcing material with polyvinyl chloride resin, a modified polyvinyl chloride resin is obtained; the modified polyvinyl chloride resin, chloroprene rubber, stabilizer, antioxidant, lubricant, and vulcanizing agent are mixed, and then extruded and granulated to finally obtain a composite material for fire hoses with flame retardant and wear-resistant properties; overall, the flame retardant properties, wear resistance, thermal stability, and mechanical properties of the composite material for fire hoses are improved, its comprehensive performance is generally enhanced, and its service life is extended.

[0005] Technical problems to be solved by the present invention: In the prior art, most traditional composite materials for fire hoses use polyvinyl chloride resin as the matrix. Although it has certain flexibility, it has problems such as insufficient flame retardancy, poor abrasion resistance, and easy migration of plasticizers. Moreover, after adding a large amount of plasticizers to polyvinyl chloride resin, its flame retardant performance will be greatly reduced, and a large amount of smoke and toxic and harmful gases will be generated during its combustion. In addition, by adding inorganic flame retardants (such as aluminum hydroxide, ammonium polyphosphate) or wear-resistant fillers (such as silicon carbide, nano-silica) to modify polyvinyl chloride resin, it is easy to cause a decrease in the mechanical properties of the composite material for fire hoses, and problems such as filler agglomeration and poor compatibility with the matrix will occur, affecting the final quality of the product.

[0006] The object of the present invention can be achieved by the following technical solutions: A composite material for fire hoses with flame retardant and wear-resistant properties, comprising the following raw materials in parts by weight: 40-50 parts of modified polyvinyl chloride resin, 20-25 parts of chloroprene rubber, 3-6 parts of stabilizer, 0.5-1 part of antioxidant, 0.4-0.6 part of lubricant, and 0.1-0.3 part of vulcanizing agent; The preparation method of the modified polyvinyl chloride resin comprises the following steps: S1: Combine a bio-based plasticizer with glycidyl to obtain a hyperbranched composite; S2: Combine the hyperbranched composite with a silanized composite material to obtain a reinforcing material; S3: After epoxidizing the reinforcing material, combine it with a compound flame retardant to obtain a flame retardant reinforcing material; S4: Combine the flame retardant reinforcing material with polyvinyl chloride resin to obtain a modified polyvinyl chloride resin.

[0007] Further, step S1 is specifically as follows: Mix the bio-based plasticizer and glycidyl evenly, stir for 15-25 min under a nitrogen atmosphere, then carry out a heating reaction. After the reaction is completed, cool to room temperature, filter, wash with deionized water, and finally vacuum dry at 50-60 °C to obtain a hyperbranched composite.

[0008] During the above reaction process, the bio-based plasticizer has a hydroxyl group, and glycidyl has an epoxy group. The hydroxyl group in the bio-based plasticizer can be combined with the epoxy group in glycidyl through a ring-opening reaction, combining the bio-based plasticizer with glycidyl, and finally obtaining a hyperbranched composite.

[0009] Further, the mass ratio of the bio-based plasticizer to glycidyl is 4.4-4.6:7.6-7.8.

[0010] Further, the bio-based plasticizer is composed of propargylated cardanol and castor oil mixed in a mass ratio of 1 - 1.2:0.5 - 0.6.

[0011] Further, the heating reaction is as follows: first, stir at 75 - 85°C for 1.5 - 2.5 h, then stir at 95 - 105°C for 3.5 - 4.5 h, and finally stir at 115 - 125°C for 1.5 - 2.5 h.

[0012] Further, the preparation method of the propargylated cardanol includes the following steps: Mix cardanol, propargyl bromide solution and potassium carbonate, then add them into acetone and stir evenly. Stir at 60 - 70°C for 11 - 13 h, filter, wash with deionized water, remove acetone by rotary evaporation, and finally dry under vacuum at 45 - 55°C to obtain propargylated cardanol.

[0013] During the above reaction process, there is a phenolic hydroxyl group in cardanol and a bromine atom in propargyl bromide. The phenolic hydroxyl group in cardanol can combine with the bromine atom in propargyl bromide to bind propargyl bromide and cardanol together, and finally obtain propargylated cardanol.

[0014] Further, the mass ratio of cardanol, propargyl bromide solution, potassium carbonate, and acetone is 2.8 - 3.2:1.2 - 1.4:1.4 - 1.6:45 - 55.

[0015] Further, step S2 is specifically as follows: Heat the hyperbranched composite in step S1 to 65 - 70°C, then add the silanized composite material and mix evenly, then add p-toluenesulfonic acid, and stir and react at 70 - 75°C for 2 - 3 h. After the reaction is completed, cool to room temperature, wash with xylene and ethyl acetate, remove xylene and ethyl acetate by rotary evaporation, and finally dry under vacuum at 50 - 60°C to obtain the reinforcing material.

[0016] During the above reaction process, there is a hydroxyl group in the hyperbranched composite and an anhydride group in the silanized composite material. The hydroxyl group in the hyperbranched composite can combine with the anhydride group in the silanized composite material to bind the silanized composite material and the hyperbranched composite together, and finally obtain the reinforcing material.

[0017] Further, the mass ratio of the hyperbranched composite, the silanized composite material, and p-toluenesulfonic acid is 0.8 - 1:1 - 1.2:0.04 - 0.06.

[0018] Further, the preparation method of the silanized composite material includes the following steps: Add the composite material into deionized water and ethanol, and stir at 45 - 55 °C for 25 - 35 min to obtain a dispersion. Add the silane coupling agent into the mixed solution of ethanol and deionized water, and mix evenly to obtain a silane solution. Add the silane solution into the dispersion, then add acetic acid to adjust the pH value of the system, raise the temperature to 85 - 95 °C, and maintain for 22 - 24 h under a nitrogen atmosphere. After filtration, wash with deionized water, and finally dry in vacuum at 75 - 80 °C to obtain the silanized composite material.

[0019] During the above reaction process, the composite material has hydroxyl groups, and the silane coupling agent produces silanol groups after hydrolysis. The hydroxyl groups in the composite material can combine with the silanol groups in the silane coupling agent to graft the silane coupling agent onto the composite material, and finally obtain the silanized composite material.

[0020] Furthermore, the mass ratio of the composite material, deionized water, and ethanol is 0.8 - 1.2 : 70 - 80 : 20 - 30.

[0021] Furthermore, the mass ratio of the silane coupling agent, ethanol, and the mixed solution of deionized water is 0.4 - 0.6 : 45 - 55.

[0022] Furthermore, the silane coupling agent is 3-(triethoxysilyl)propyl succinic anhydride.

[0023] Furthermore, the mass ratio of the silane solution to the dispersion is 2 : 1.

[0024] Furthermore, the acetic acid adjusts the pH value of the system to 2.8 - 3.2.

[0025] Furthermore, the preparation method of the composite material includes the following steps: Mix magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water evenly to obtain a mixed solution. Add the nanomaterial into the mixed solution, and ultrasonically treat for 25 - 35 min, then heat to 75 - 85 °C, add sodium hydroxide solution to adjust the pH value of the system, continue to stir for 2 - 3 h, age at 75 - 85 °C for 10 - 12 h, filter through a filter membrane, wash with deionized water, and finally dry at 75 - 80 °C to obtain the composite material.

[0026] During the above reaction process, magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, and sodium chloride can form layered double hydroxides after mixing. The nanomaterial and the layered double hydroxides are combined by the coprecipitation method to combine the nanomaterial and the layered double hydroxides together, and finally obtain the composite material.

[0027] Further, the mass ratio of magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water is 1.8 - 2.2: 1.8 - 2.2: 0.8 - 1.2: 3.8 - 4.2: 280 - 320.

[0028] Further, the mass ratio of the nanomaterial to the mixed solution is 2.8 - 3.2: 7 - 7.5.

[0029] Further, the nanomaterial is composed of graphene oxide and molybdenum disulfide nanosheets mixed in a mass ratio of 0.7 - 0.8: 0.3 - 0.4.

[0030] Further, the pH value of the system is adjusted to 10 - 10.5 with the sodium hydroxide solution.

[0031] Further, the filter membrane is a 0.45 μm polyethersulfone membrane.

[0032] Further, step S3 is specifically as follows: A1: Mix the reinforcing material in step S2 with formic acid, then add it to the hydrogen peroxide aqueous solution, and react at 55 - 65 °C for 5 - 7 h. After the reaction, add it to dichloromethane, wash it with deionized water, saturated sodium bicarbonate aqueous solution, and saturated sodium chloride solution, dry it with anhydrous sodium sulfate, filter it, and finally vacuum dry it at 55 - 65 °C to obtain the epoxidized reinforcing material; A2: Mix the epoxidized reinforcing material and toluene evenly, then add the compound flame retardant and triphenylphosphine, and stir at 35 - 45 °C for 0.5 - 1 h, then continue to stir at 70 - 80 °C for 3.5 - 4 h. After the reaction, cool to room temperature, filter it, wash it with deionized water, then wash it with sodium hydroxide solution, remove the residual moisture by rotary evaporation, and finally vacuum dry it at 50 - 60 °C to obtain the flame-retardant reinforcing material.

[0033] In the above reaction process, in step A1, there are carbon-carbon double bonds in the reinforcing material. Under the action of hydrogen peroxide, the carbon-carbon double bonds in the reinforcing material are oxidized to epoxy groups to obtain the epoxidized reinforcing material; in step A2, there are hydroxyl groups in the compound flame retardant, and there are epoxy groups in the epoxidized reinforcing material. The hydroxyl groups in the compound flame retardant can be combined with the epoxy groups in the epoxidized reinforcing material through ring-opening reaction to combine the compound flame retardant with the epoxidized reinforcing material, and finally obtain the flame-retardant reinforcing material.

[0034] Further, in step A1, the mass ratio of the reinforcing material, formic acid, hydrogen peroxide aqueous solution, and dichloromethane is 1.8 - 2.2: 0.6 - 0.8: 1.6 - 1.8: 40 - 50.

[0035] Further, in step A2, the mass ratio of the epoxy strengthening material, toluene, compound flame retardant, and triphenylphosphine is 2.4 - 2.6: 3.9 - 4.1: 0.7 - 0.9: 0.005 - 0.01.

[0036] Further, in step A2, the compound flame retardant is composed of (diphenyl) 4 - hydroxyphenyl phosphate and (diphenyl) 2,5 - dihydroxyphenylphosphine oxide, which are mixed in a mass ratio of 0.8 - 0.9: 0.5 - 0.6.

[0037] Further, step S4 is specifically as follows: Mix polyvinyl chloride resin, sodium azide, and N,N - dimethylformamide, and stir at 25 - 35°C for 22 - 24 h, then precipitate into a mixed solution of water and methanol, and vacuum - dry at 40 - 50°C to obtain component A. Add component A, the flame - retardant strengthening material in step S3, cuprous bromide, and 2,2 - bipyridine into N,N - dimethylformamide, mix evenly, stir at 25 - 35°C for 22 - 24 h, cool to room temperature, then filter, precipitate into a mixed solution of water and methanol, and finally vacuum - dry at 40 - 50°C to obtain the modified polyvinyl chloride resin.

[0038] During the above reaction process, there are chlorine atoms in the polyvinyl chloride resin, and the azide ions in sodium azide can react with the chlorine atoms in the polyvinyl chloride resin to obtain component A with an azide group. There is a carbon - carbon triple bond in the bio - based plasticizer in the flame - retardant strengthening material, which can react and combine with the azide group in component A, binding the flame - retardant strengthening material and the polyvinyl chloride resin together, and finally obtaining the modified polyvinyl chloride resin.

[0039] Further, the mass ratio of the polyvinyl chloride resin, sodium azide, N,N - dimethylformamide, and the mixed solution of water and methanol is 1.8 - 2.2: 1.8 - 2.2: 90 - 110: 45 - 55.

[0040] Further, the mass ratio of component A, the flame - retardant strengthening material, cuprous bromide, 2,2 - bipyridine, and N,N - dimethylformamide is 0.8 - 1.2: 0.2 - 0.4: 0.01 - 0.02: 0.02 - 0.03: 40 - 50.

[0041] A preparation method of a composite material for a fire - fighting water hose with flame - retardant and wear - resistant properties, comprising the following steps: Weigh raw materials in parts by mass, mix the modified polyvinyl chloride resin, chloroprene rubber, stabilizer, antioxidant, and lubricant, then put them into a kneader and knead for 3 - 5 min, add a vulcanizing agent, and continue to knead for 2 - 3 min. After discharging from the kneader, supplement and knead on an open mill for 1 - 2 min. Finally, extrude and pelletize and cool to room temperature to obtain the composite material for a fire - fighting water hose with flame - retardant and wear - resistant properties.

[0042] Further, the stabilizer is stabilizer YT-181 or dibutyltin dilaurate.

[0043] Further, the antioxidant is at least one of 2,6-di-tert-butyl-p-cresol, antioxidant 1076, and antioxidant 1010.

[0044] Further, the lubricant is at least one of stearic acid, zinc stearate, and calcium stearate.

[0045] Further, the vulcanizing agent is dicumyl peroxide or benzoyl peroxide.

[0046] Further, the mixing temperature is 105-115 °C and the rotation speed is 40-50 rpm.

[0047] Further, the temperature of the supplementary mixing is 90-100 °C and the rotation speed is 10-20 rpm.

[0048] Advantages of the present invention: (1) In the technical solution of the present invention, a hyperbranched composite is obtained by combining a bio-based plasticizer with glycidyl; the bio-based plasticizer is composed of a propargylated cardanol and castor oil, and the two have a synergistic effect and can be used as a plasticizer for polyvinyl chloride resin to enhance the flexibility and environmental friendliness of the polyvinyl chloride resin, and can provide reaction sites for subsequent reactions. Combining the bio-based plasticizer with glycidyl not only has good binding force, but also can form a hyperbranched composite, providing more grafting sites for subsequent reactions and further enhancing the performance of the polyvinyl chloride resin; combining the hyperbranched composite with a silanized composite material to obtain a reinforcing material; the silanized composite material is prepared by grafting a silane coupling agent onto a composite material, wherein the composite material is prepared by loading a nanomaterial on a layered double hydroxide, which can better improve the dispersibility of the composite material in the polyvinyl chloride resin, prevent its agglomeration, and increase the compatibility between the composite material and the polyvinyl chloride resin. The nanomaterial in the composite material is composed of a mixture of graphene oxide and molybdenum disulfide nanosheets, and the two play a synergistic effect, which can effectively improve the wear resistance, thermal stability and mechanical properties of the composite material for fire hoses. At the same time, it also has certain flame retardancy and lubricity, which can further improve the flame retardancy and wear resistance of the fire hose composite material. In addition, the layered double hydroxide loads the nanomaterial, which can also better improve the dispersibility of the nanomaterial, prevent its agglomeration, and make it play a better role.

[0049] (2) In the technical solution of the present invention, after the reinforcing material is epoxidized and modified, it is combined with the compound flame retardant to obtain the flame retardant reinforcing material; after the reinforcing material is epoxidized and modified, it can provide reaction sites for subsequent reactions and enhance the binding property between it and the compound flame retardant. The compound flame retardant is composed of a mixture of (diphenyl) 4-hydroxyphenylphosphate and (diphenyl) 2,5-dihydroxyphenylphosphine oxide. The two play a synergistic flame retardant role and can form a carbon layer during combustion to prevent the spread of flames, and preferably improve the flame retardancy and smoke suppression property of the polyvinyl chloride resin. Combining the epoxidized reinforcing material with the compound flame retardant increases the binding force between the compound flame retardant and the polyvinyl chloride resin, effectively improving the flame retardancy and thermal stability of the composite material for fire hoses; by combining the flame retardant reinforcing material with the polyvinyl chloride resin, a modified polyvinyl chloride resin is obtained; combining the flame retardant reinforcing material with the polyvinyl chloride resin can increase the dispersibility of the flame retardant reinforcing material in the polyvinyl chloride resin and enhance the compatibility between the two, further improving the flame retardancy, wear resistance, thermal stability and mechanical properties of the composite material for fire hoses; mixing the modified polyvinyl chloride resin, chloroprene rubber, stabilizer, antioxidant, lubricant and vulcanizing agent, and extruding and granulating to finally obtain the composite material for fire hoses with flame retardant and wear resistance properties.

[0050] (3) In the technical solution of the present invention, by combining a bio-based plasticizer with glycidyl, then combining with a silanized composite material, after epoxidation modification, then combining with a compound flame retardant, and finally combining with a polyvinyl chloride resin, a modified polyvinyl chloride resin is obtained. Mixing the modified polyvinyl chloride resin, chloroprene rubber, stabilizer, antioxidant, lubricant and vulcanizing agent, and extruding and granulating to finally obtain the composite material for fire hoses with flame retardant and wear resistance properties; the prepared composite material for fire hoses has good flame retardancy, wear resistance, thermal stability and mechanical properties, and extends its service life, and the overall comprehensive performance is good. Specific embodiments

[0051] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0052] The specific parameters of the raw materials used in the present invention are as follows: Cardanol, CAS No.: 501-24-6, provided by Zhongshan Dixin Chemical Co., Ltd.; castor oil, CAS No.: 8001-79-4, product number: C805202, provided by Shanghai Macklin Biochemical Co., Ltd.; glycidol, CAS No.: 556-52-5, product number: G823277, provided by Shanghai Macklin Biochemical Co., Ltd.; graphene oxide, with an average thickness of 1-3 nm, provided by Hangzhou Zeming New Materials Co., Ltd.; molybdenum disulfide nanosheets, with a purity of 98%, provided by Suzhou Kaifa New Materials Technology Co., Ltd.; 4-hydroxyphenyl diphenyl phosphate, CAS No.: 56806-74-7, product number: H993320, provided by Shanghai Macklin Biochemical Co., Ltd.; 2,5-dihydroxyphenyl diphenyl phosphine oxide, CAS No.: 13291-46-8, product number: D864936, provided by Shanghai Macklin Biochemical Co., Ltd.; polyvinyl chloride resin, grade: S-80, provided by Dongguan Baojia Plastic Co., Ltd.

[0053] Example 1 To prepare a modified polyvinyl chloride resin, the specific steps are as follows: S1: According to the mass ratio of bio-based plasticizer to glycidol of 4.4:7.6, mix the bio-based plasticizer and glycidol evenly, and stir at a speed of 500 rpm in a nitrogen atmosphere for 25 min, then carry out a heating reaction. First, stir at 75 °C for 2.5 h, then stir at 95 °C for 4.5 h, and finally stir at 115 °C for 2.5 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 2 times the mass of glycidol), and finally vacuum dry at 50 °C for 12 h to obtain a hyperbranched composite. Among them, the bio-based plasticizer is composed of propargylated cardanol and castor oil mixed according to a mass ratio of 1:0.5; The preparation method of propargylated cardanol includes the following steps: According to the mass ratio of cardanol, propargyl bromide solution, potassium carbonate, and acetone of 2.8:1.2:1.4:45, mix cardanol, 80 wt% propargyl bromide solution and potassium carbonate, then add them to acetone and stir evenly. Stir at 60 °C for 11 h, filter, wash with deionized water (the mass of deionized water is 30% of the mass of acetone), remove acetone by rotary evaporation at 55 °C, and finally vacuum dry at 45 °C for 12 h to obtain propargylated cardanol; S2: Heat the hyperbranched complex in step S1 to 65 °C according to the mass ratio of the hyperbranched complex, silanized composite material, and p-toluenesulfonic acid of 0.8:1:0.04. Then add the silanized composite material and mix evenly. Next, add p-toluenesulfonic acid and stir and react at 70 °C for 2 h. After the reaction ends, cool to room temperature and wash 3 times with xylene and ethyl acetate in turn (each time the mass of xylene is 10 times the mass of the hyperbranched complex, and each time the mass of ethyl acetate is 8 times the mass of the hyperbranched complex). Remove xylene and ethyl acetate by rotary evaporation at 55 °C, and finally vacuum dry at 50 °C for 4 h to obtain the reinforcing material; Among them, the preparation method of the silanized composite material includes the following steps: According to the mass ratio of the composite material, deionized water, and ethanol of 0.8:70:20, add the composite material to deionized water and ethanol, and stir at 45 °C for 25 min to obtain a dispersion. According to the mass ratio of 3-(triethoxysilyl)propyl succinic anhydride, ethanol, and deionized water mixed solution of 0.4:45, add 3-(triethoxysilyl)propyl succinic anhydride to the ethanol and deionized water mixed solution (the volume ratio of ethanol to deionized water is 9:1), and mix evenly to obtain a silane solution. According to the mass ratio of the silane solution to the dispersion of 2:1, add the silane solution to the dispersion, then add acetic acid to adjust the pH value of the system to 2.8, raise the temperature to 85 °C, and maintain it for 22 h under a nitrogen atmosphere. After cooling to room temperature, filter, wash 3 times with deionized water (each time the mass of deionized water is 10 times the mass of the composite material), and finally vacuum dry at 75 °C for 24 h to obtain the silanized composite material; The preparation method of the composite material includes the following steps: According to the mass ratio of magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water of 1.8:1.8:0.8:3.8:280, mix magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water evenly to obtain a mixed solution. According to the mass ratio of the nanomaterial to the mixed solution of 2.8:7, add the nanomaterial to the mixed solution and ultrasonically treat for 25 min (ultrasonic power is 100 W, ultrasonic frequency is 40 kHz). Then heat to 75 °C, add 1 mol / L sodium hydroxide solution to adjust the pH value of the system to 10, continue to stir for 2 h, age at 75 °C for 10 h, filter through a 0.45 μm polyethersulfone membrane, wash with deionized water (the mass of deionized water is 5% of the mass of the above deionized water), and finally dry at 75 °C for 24 h to obtain the composite material, where the nanomaterial is composed of graphene oxide and molybdenum disulfide nanosheets mixed according to the mass ratio of 0.7:0.3; S3: Prepare the flame-retardant reinforcing material, and the specific steps are as follows: A1: Mix the reinforcing material in step S2 with formic acid according to the mass ratio of the reinforcing material, formic acid, aqueous hydrogen peroxide solution, and dichloromethane being 1.8:0.6:1.6:40. Then add it to a 30 wt% aqueous hydrogen peroxide solution and react at 55 °C for 5 h. After the reaction is completed, add it to dichloromethane and wash it 3 times each with deionized water, saturated sodium bicarbonate aqueous solution, and saturated sodium chloride solution (each time the mass of deionized water is 30% of the mass of dichloromethane, each time the mass of saturated sodium bicarbonate aqueous solution is 20% of the mass of dichloromethane, and each time the mass of saturated sodium chloride solution is 20% of the mass of dichloromethane). Dry it with anhydrous sodium sulfate, filter it, and finally vacuum dry it at 55 °C for 24 h to obtain the epoxidized reinforcing material; A2: Mix the epoxidized reinforcing material and toluene evenly according to the mass ratio of the epoxidized reinforcing material, toluene, compound flame retardant, and triphenylphosphine being 2.4:3.9:0.7:0.005. Then add the compound flame retardant and triphenylphosphine and stir at 35 °C for 0.5 h, and then continue to stir at 70 °C for 3.5 h. After the reaction is completed, cool it to room temperature, filter it, wash it 3 times with deionized water (each time the mass of deionized water is 3 times the mass of toluene), and then wash it with 1 mol / L sodium hydroxide solution until the pH value of the system reaches 7. Remove the residual water by rotary evaporation at 65 °C, and finally vacuum dry it at 50 °C for 12 h to obtain the flame-retardant reinforcing material, where the compound flame retardant is composed of bis(diphenyl) 4-hydroxyphenyl phosphate and diphenyl(2,5-dihydroxyphenyl)phosphine oxide mixed according to the mass ratio of 0.8:0.5; S4: Mix polyvinyl chloride resin, sodium azide, N,N-dimethylformamide, water, and methanol mixed solution according to the mass ratio of 1.8:1.8:90:45. Mix polyvinyl chloride resin, sodium azide, and N,N-dimethylformamide and stir at 25 °C for 22 h, then precipitate it into a water and methanol mixed solution (the volume ratio of water to methanol is 1:1), and vacuum dry it at 40 °C for 12 h to obtain component A. According to the mass ratio of component A, flame-retardant reinforcing material, cuprous bromide, 2,2'-bipyridine, N,N-dimethylformamide, water, and methanol mixed solution being 0.8:0.2:0.01:0.02:40:20, add component A, the flame-retardant reinforcing material in step S3, cuprous bromide, and 2,2'-bipyridine to N,N-dimethylformamide and mix evenly. Stir at 25 °C for 22 h, filter it, precipitate it into a water and methanol mixed solution (the volume ratio of water to methanol is 1:1), and finally vacuum dry it at 40 °C for 12 h to obtain the modified polyvinyl chloride resin; A composite material for a fire hose with flame-retardant and wear-resistant properties, comprising the following raw materials in parts by weight: 40 parts of modified polyvinyl chloride resin, 20 parts of chloroprene rubber, 3 parts of stabilizer YT-181, 0.5 part of 2,6-di-tert-butyl-p-cresol, 0.4 part of stearic acid, and 0.1 part of dicumyl peroxide; The preparation method comprises the following steps: Weigh raw materials in parts by mass. Mix modified polyvinyl chloride resin, chloroprene rubber, stabilizer YT-181, 2,6-di-tert-butyl-p-cresol and stearic acid, then put them into a mixer and knead for 3 min, then add dicumyl peroxide and continue to knead for 2 min. The kneading temperature is 105 °C and the rotation speed is 40 rpm. After discharging from the mixer, supplement the kneading on an open mill for 1 min. The temperature of the supplementary kneading is 90 °C and the rotation speed is 10 rpm. Finally, after extrusion granulation and cooling to room temperature, a composite material for fire hoses with flame retardant and wear-resistant properties is obtained.

[0054] Example 2 Prepare modified polyvinyl chloride resin. The specific steps are as follows: S1: According to the mass ratio of bio-based plasticizer to glycidyl of 4.5:7.7, mix the bio-based plasticizer and glycidyl evenly, and stir at a rotation speed of 600 rpm for 20 min under a nitrogen atmosphere, then carry out a heating reaction. First, stir at 80 °C for 2 h, then stir at 100 °C for 4 h, and finally stir at 120 °C for 2 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 2 times the mass of glycidyl), and finally vacuum dry at 55 °C for 12 h to obtain a hyperbranched composite. Among them, the bio-based plasticizer is composed of propargylated cardanol and castor oil mixed according to the mass ratio of 1.1:0.55; The preparation method of propargylated cardanol comprises the following steps: According to the mass ratio of cardanol, propargyl bromide solution, potassium carbonate, and acetone of 3:1.3:1.5:50, mix cardanol, 80 wt% propargyl bromide solution and potassium carbonate, then add them into acetone and stir evenly. Stir at 65 °C for 12 h, filter, wash with deionized water (the mass of deionized water is 30% of the mass of acetone), remove acetone by rotary evaporation at 60 °C, and finally vacuum dry at 50 °C for 12 h to obtain propargylated cardanol; S2: According to the mass ratio of the hyperbranched composite, silanized composite material, and p-toluenesulfonic acid of 0.9:1.1:0.05, heat the hyperbranched composite in step S1 to 68 °C, then add the silanized composite material and mix evenly, then add p-toluenesulfonic acid, and stir and react at 72 °C for 2.5 h. After the reaction is completed, cool to room temperature, wash 3 times with xylene and ethyl acetate respectively (the mass of xylene each time is 10 times the mass of the hyperbranched composite, and the mass of ethyl acetate each time is 8 times the mass of the hyperbranched composite), remove xylene and ethyl acetate by rotary evaporation at 60 °C, and finally vacuum dry at 55 °C for 5 h to obtain a reinforcing material; Among them, the preparation method of the silanized composite material comprises the following steps: According to the mass ratio of the composite material, deionized water, and ethanol being 1:75:25, add the composite material to deionized water and ethanol, and stir at 50 °C for 30 min to obtain a dispersion. According to the mass ratio of 3-(triethoxysilyl)propyl succinic anhydride, ethanol, and deionized water mixed solution being 0.5:50, add 3-(triethoxysilyl)propyl succinic anhydride to the ethanol and deionized water mixed solution (the volume ratio of ethanol to deionized water is 9:1), and after mixing evenly, obtain a silane solution. According to the mass ratio of the silane solution to the dispersion being 2:1, add the silane solution to the dispersion, then add acetic acid to adjust the pH value of the system to 3, raise the temperature to 90 °C, and maintain it for 23 h under a nitrogen atmosphere. After cooling to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 10 times the mass of the composite material), and finally dry in vacuo at 78 °C for 24 h to obtain the silanized composite material; The preparation method of the composite material includes the following steps: According to the mass ratio of magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water being 2:2:1:4:300, mix magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water evenly to obtain a mixed solution. According to the mass ratio of the nanomaterial to the mixed solution being 3:7.2, add the nanomaterial to the mixed solution, and perform ultrasonic treatment for 30 min (ultrasonic power is 100 W, ultrasonic frequency is 40 kHz), then heat to 80 °C, and then add 1 mol / L sodium hydroxide solution to adjust the pH value of the system to 10.2, continue stirring for 2.5 h, age at 80 °C for 11 h, filter through a 0.45 μm polyethersulfone membrane, wash with deionized water (the mass of deionized water is 5% of the mass of the above deionized water), and finally dry at 78 °C for 24 h to obtain the composite material, where the nanomaterial is composed of graphene oxide and molybdenum disulfide nanosheets mixed according to the mass ratio of 0.75:0.35; S3: Prepare the flame-retardant reinforced material, and the specific steps are as follows: A1: According to the mass ratio of the reinforcing material, formic acid, hydrogen peroxide aqueous solution, and dichloromethane being 2:0.7:1.7:45, mix the reinforcing material in step S2 with formic acid, then add it to 30 wt% hydrogen peroxide aqueous solution, and react at 60 °C for 6 h. After the reaction is completed, add it to dichloromethane, and wash 3 times with deionized water, saturated sodium bicarbonate aqueous solution, and saturated sodium chloride solution in turn (the mass of deionized water each time is 30% of the mass of dichloromethane, the mass of saturated sodium bicarbonate aqueous solution each time is 20% of the mass of dichloromethane, and the mass of saturated sodium chloride solution each time is 20% of the mass of dichloromethane), dry with anhydrous sodium sulfate, filter, and finally dry in vacuo at 60 °C for 24 h to obtain the epoxidized reinforcing material; A2: According to the mass ratio of the epoxy reinforcing material, toluene, compound flame retardant, and triphenylphosphine being 2.5:4:0.8:0.008, mix the epoxy reinforcing material and toluene evenly, then add the compound flame retardant and triphenylphosphine, and stir at 40 °C for 0.7 h, then continue to stir at 75 °C for 3.8 h. After the reaction ends, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 3 times the mass of toluene), then wash with 1 mol / L sodium hydroxide solution until the pH value of the system reaches 7, remove the residual moisture by rotary evaporation at 70 °C, and finally vacuum dry at 55 °C for 12 h to obtain the flame retardant and reinforcing material. Among them, the compound flame retardant is composed of bis(diphenyl) 4-hydroxyphenyl phosphate and bis(diphenyl) 2,5-dihydroxyphenylphosphine oxide mixed according to the mass ratio of 0.85:0.55; S4: According to the mass ratio of polyvinyl chloride resin, sodium azide, N,N-dimethylformamide, water, and methanol mixed solution being 2:2:100:50, mix the polyvinyl chloride resin, sodium azide, and N,N-dimethylformamide, and stir at 30 °C for 23 h, then precipitate into the water and methanol mixed solution (the volume ratio of water to methanol is 1:1), and vacuum dry at 45 °C for 12 h to obtain component A. According to the mass ratio of component A, flame retardant and reinforcing material, cuprous bromide, 2,2'-bipyridine, N,N-dimethylformamide, water, and methanol mixed solution being 1:0.3:0.015:0.025:45:25, add component A, the flame retardant and reinforcing material in step S3, cuprous bromide, and 2,2'-bipyridine to N,N-dimethylformamide, and mix evenly, stir at 30 °C for 23 h, filter, precipitate into the water and methanol mixed solution (the volume ratio of water to methanol is 1:1), and finally vacuum dry at 45 °C for 12 h to obtain the modified polyvinyl chloride resin; A fire hose composite material with flame retardant and wear-resistant properties, comprising the following raw materials in parts by weight: 45 parts of modified polyvinyl chloride resin, 23 parts of chloroprene rubber, 5 parts of dibutyltin dilaurate, 0.8 part of antioxidant 1076, 0.5 part of zinc stearate, and 0.2 part of benzoyl peroxide; The preparation method comprises the following steps: Weigh the raw materials in parts by weight, mix the modified polyvinyl chloride resin, chloroprene rubber, dibutyltin dilaurate, antioxidant 1076, and zinc stearate, then put them into a kneader and knead for 4 min, then add benzoyl peroxide and continue to knead for 2.5 min. The kneading temperature is 110 °C and the rotation speed is 45 rpm. After discharging from the kneader, supplement the kneading on an open mill for 1.5 min. The temperature of the supplementary kneading is 95 °C and the rotation speed is 15 rpm. Finally, after extrusion granulation and cooling to room temperature, a fire hose composite material with flame retardant and wear-resistant properties is obtained.

[0055] Example 3 Prepare a modified polyvinyl chloride resin, and the specific steps are as follows: S1: Mix the bio-based plasticizer and glycidyl in a mass ratio of 4.6:7.8 evenly, and stir at a speed of 700 rpm for 15 min under a nitrogen atmosphere, then carry out a heating reaction. First, stir at 85 °C for 1.5 h, then stir at 105 °C for 3.5 h, and finally stir at 125 °C for 1.5 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 2 times the mass of glycidyl), and finally vacuum dry at 60 °C for 12 h to obtain a hyperbranched composite. Among them, the bio-based plasticizer is composed of propargylated cardanol and castor oil mixed in a mass ratio of 1.2:0.6; The preparation method of propargylated cardanol includes the following steps: Mix cardanol, 80 wt% propargyl bromide solution and potassium carbonate in a mass ratio of 3.2:1.4:1.6:55, then add them to acetone and stir evenly. Stir at 70 °C for 13 h, filter, wash with deionized water (the mass of deionized water is 30% of the mass of acetone), remove acetone by rotary evaporation at 65 °C, and finally vacuum dry at 55 °C for 12 h to obtain propargylated cardanol; S2: Heat the hyperbranched composite in step S1 to 70 °C according to a mass ratio of 1:1.2:0.06 of the hyperbranched composite, silanized composite material, and p-toluenesulfonic acid, then add the silanized composite material and mix evenly, and then add p-toluenesulfonic acid, and stir and react at 75 °C for 3 h. After the reaction is completed, cool to room temperature, wash 3 times with xylene and ethyl acetate respectively (the mass of xylene each time is 10 times the mass of the hyperbranched composite, and the mass of ethyl acetate each time is 8 times the mass of the hyperbranched composite), remove xylene and ethyl acetate by rotary evaporation at 65 °C, and finally vacuum dry at 60 °C for 6 h to obtain a reinforcing material; Among them, the preparation method of the silanized composite material includes the following steps: According to the mass ratio of the composite material, deionized water, and ethanol being 1.2:80:30, add the composite material to deionized water and ethanol, and stir at 55 °C for 35 min to obtain a dispersion. According to the mass ratio of 3-(triethoxysilyl)propyl succinic anhydride, ethanol, and the mixed solution of deionized water being 0.6:55, add 3-(triethoxysilyl)propyl succinic anhydride to the mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water is 9:1). After mixing evenly, obtain a silane solution. According to the mass ratio of the silane solution to the dispersion being 2:1, add the silane solution to the dispersion, then add acetic acid to adjust the pH value of the system to 3.2, raise the temperature to 95 °C, and maintain it for 24 h under a nitrogen atmosphere. After cooling to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 10 times the mass of the composite material), and finally vacuum dry at 80 °C for 24 h to obtain the silanized composite material; The preparation method of the composite material includes the following steps: According to the mass ratio of magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water being 2.2:2.2:1.2:4.2:320, mix magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water evenly to obtain a mixed solution. According to the mass ratio of the nanomaterial to the mixed solution being 3.2:7.5, add the nanomaterial to the mixed solution, and ultrasonically treat for 35 min (ultrasonic power is 100 W, ultrasonic frequency is 40 kHz), then heat to 85 °C, and then add 1 mol / L sodium hydroxide solution to adjust the pH value of the system to 10.5, continue to stir for 3 h, age at 85 °C for 12 h, filter through a 0.45 μm polyethersulfone membrane, wash with deionized water (the mass of deionized water is 5% of the mass of the above deionized water), and finally dry at 80 °C for 24 h to obtain the composite material, where the nanomaterial is composed of graphene oxide and molybdenum disulfide nanosheets mixed according to the mass ratio of 0.8:0.4; S3: Prepare the flame-retardant reinforced material, and the specific steps are as follows: A1: According to the mass ratio of the reinforcing material, formic acid, hydrogen peroxide aqueous solution, and dichloromethane being 2.2:0.8:1.8:50, mix the reinforcing material in step S2 with formic acid, then add it to 30 wt% hydrogen peroxide aqueous solution, and react at 65 °C for 7 h. After the reaction is completed, add it to dichloromethane, and wash 3 times with deionized water, saturated sodium bicarbonate aqueous solution, and saturated sodium chloride solution in sequence (the mass of deionized water each time is 30% of the mass of dichloromethane, the mass of saturated sodium bicarbonate aqueous solution each time is 20% of the mass of dichloromethane, and the mass of saturated sodium chloride solution each time is 20% of the mass of dichloromethane), dry with anhydrous sodium sulfate, filter, and finally vacuum dry at 65 °C for 24 h to obtain the epoxidized reinforcing material; A2: According to the mass ratio of the epoxy enhanced material, toluene, compound flame retardant, and triphenylphosphine being 2.6:4.1:0.9:0.01, mix the epoxy enhanced material and toluene evenly, then add the compound flame retardant and triphenylphosphine, and stir at 45°C for 1 h, then continue to stir at 80°C for 4 h. After the reaction ends, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 3 times the mass of toluene), then wash with 1 mol / L sodium hydroxide solution until the pH value of the system reaches 7, remove the residual moisture by rotary evaporation at 75°C, and finally vacuum dry at 60°C for 12 h to obtain the flame retardant enhanced material. Among them, the compound flame retardant is composed of 4-hydroxyphenyl(diphenyl)phosphate and 2,5-dihydroxyphenyl(diphenyl)phosphine oxide mixed according to the mass ratio of 0.9:0.6; S4: According to the mass ratio of polyvinyl chloride resin, sodium azide, N,N-dimethylformamide, water, and methanol mixed solution being 2.2:2.2:110:55, mix the polyvinyl chloride resin, sodium azide, and N,N-dimethylformamide, and stir at 35°C for 24 h, then precipitate into the water and methanol mixed solution (the volume ratio of water to methanol is 1:1), and vacuum dry at 50°C for 12 h to obtain component A. According to the mass ratio of component A, flame retardant enhanced material, cuprous bromide, 2,2-bipyridine, N,N-dimethylformamide, water, and methanol mixed solution being 1.2:0.4:0.02:0.03:50:30, add component A, the flame retardant enhanced material in step S3, cuprous bromide, and 2,2-bipyridine to N,N-dimethylformamide, and mix evenly, stir at 35°C for 24 h, filter, precipitate into the water and methanol mixed solution (the volume ratio of water to methanol is 1:1), and finally vacuum dry at 50°C for 12 h to obtain the modified polyvinyl chloride resin; A fire hose composite material with flame retardant and wear-resistant properties, comprising the following raw materials in parts by weight: 50 parts of modified polyvinyl chloride resin, 25 parts of chloroprene rubber, 6 parts of stabilizer YT-181, 1 part of antioxidant 1010, 0.6 part of calcium stearate, and 0.3 part of dicumyl peroxide; The preparation method comprises the following steps: Weigh the raw materials in parts by weight, mix the modified polyvinyl chloride resin, chloroprene rubber, stabilizer YT-181, antioxidant 1010, and calcium stearate, then put them into a kneader and knead for 5 min, then add dicumyl peroxide and continue to knead for 3 min. The kneading temperature is 115°C and the rotation speed is 50 rpm. After kneading and discharging, supplement the kneading on an open mill for 2 min. The temperature of the supplementary kneading is 100°C and the rotation speed is 20 rpm. Finally, after extrusion granulation and cooling to room temperature, a fire hose composite material with flame retardant and wear-resistant properties is obtained.

[0056] Comparative Example 1 The difference between this comparative example and Example 3 is that when preparing the modified polyvinyl chloride resin, the bio-based plasticizer in step S1 is replaced with propargylated cashew phenol in equal mass, and the remaining steps and raw materials are the same as those in Example 3; S1: According to the mass ratio of propargylated cashew phenol to glycidyl of 4.6:7.8, mix propargylated cashew phenol and glycidyl evenly, and stir at a speed of 700 rpm for 15 min under a nitrogen atmosphere, then carry out a heating reaction. First, stir at 85 °C for 1.5 h, then stir at 105 °C for 3.5 h, and finally stir at 125 °C for 1.5 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 2 times the mass of glycidyl), and finally vacuum dry at 60 °C for 12 h to obtain a hyperbranched composite.

[0057] Comparative Example 2 The difference between this comparative example and Example 3 is that when preparing the modified polyvinyl chloride resin, the bio-based plasticizer in step S1 is replaced with castor oil in equal mass, and the remaining steps and raw materials are the same as those in Example 3; S1: According to the mass ratio of castor oil to glycidyl of 4.6:7.8, mix castor oil and glycidyl evenly, and stir at a speed of 700 rpm for 15 min under a nitrogen atmosphere, then carry out a heating reaction. First, stir at 85 °C for 1.5 h, then stir at 105 °C for 3.5 h, and finally stir at 125 °C for 1.5 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 2 times the mass of glycidyl), and finally vacuum dry at 60 °C for 12 h to obtain a hyperbranched composite.

[0058] Comparative Example 3 The difference between this comparative example and Example 3 is that when preparing the modified polyvinyl chloride resin, the bio-based plasticizer in step S1 is composed of a mixture of cashew phenol and castor oil, and the remaining steps and raw materials are the same as those in Example 3; S1: According to the mass ratio of the bio-based plasticizer to glycidyl of 4.6:7.8, mix the bio-based plasticizer and glycidyl evenly, and stir at a speed of 700 rpm for 15 min under a nitrogen atmosphere, then carry out a heating reaction. First, stir at 85 °C for 1.5 h, then stir at 105 °C for 3.5 h, and finally stir at 125 °C for 1.5 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 2 times the mass of glycidyl), and finally vacuum dry at 60 °C for 12 h to obtain a hyperbranched composite, where the bio-based plasticizer is composed of a mixture of cashew phenol and castor oil in a mass ratio of 1.2:0.6.

[0059] Comparative Example 4 The difference between this comparative example and Example 3 is that when preparing the modified polyvinyl chloride resin, in step S2, the composite material is directly composed of layered double hydroxide and nanomaterials, and the remaining steps and raw materials are the same as those in Example 3; The preparation method of the silanized composite material includes the following steps: According to the mass ratio of the composite material, deionized water, and ethanol being 1.2:80:30, add the composite material to deionized water and ethanol, and stir at 55 °C for 35 min to obtain a dispersion. According to the mass ratio of 3-(triethoxysilyl)propyl succinic anhydride, ethanol, and the mixed solution of deionized water being 0.6:55, add 3-(triethoxysilyl)propyl succinic anhydride to the mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water is 9:1), and after mixing evenly, obtain a silane solution. According to the mass ratio of the silane solution to the dispersion being 2:1, add the silane solution to the dispersion, then add acetic acid to adjust the pH value of the system to 3.2, raise the temperature to 95 °C, and maintain it for 24 h under a nitrogen atmosphere. After cooling to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 10 times the mass of the composite material), and finally dry in vacuum at 80 °C for 24 h to obtain the silanized composite material. Among them, the composite material is composed of layered double hydroxide and nanomaterials mixed in a mass ratio of 1:1, and the nanomaterials are composed of graphene oxide and molybdenum disulfide nanosheets mixed in a mass ratio of 0.8:0.4; The preparation method of the layered double hydroxide includes the following steps: According to the mass ratio of magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water being 2.2:2.2:1.2:4.2:320, mix magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water evenly, and stir at room temperature for 3 h. After filtration, wash with deionized water (the mass of deionized water is 5% of the mass of the above deionized water), and finally dry at 80 °C for 24 h to obtain the layered double hydroxide.

[0060] Comparative Example 5 The difference between this comparative example and Example 3 is that when preparing the modified polyvinyl chloride resin, the nanomaterials in step S2 are replaced with graphene oxide in equal mass, and the remaining steps and raw materials are the same as those in Example 3; The preparation method of the composite material includes the following steps: Mix magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water in a mass ratio of 2.2:2.2:1.2:4.2:320 to obtain a homogeneous mixed solution. Add graphene oxide to the mixed solution in a mass ratio of 3.2:7.5, and ultrasonically treat for 35 min (ultrasonic power is 100 W, ultrasonic frequency is 40 kHz). Then heat to 85 °C, add 1 mol / L sodium hydroxide solution to adjust the pH value of the system to 10.5, continue stirring for 3 h, age at 85 °C for 12 h, filter through a 0.45 μm polyethersulfone membrane, wash with deionized water (the mass of deionized water is 5% of the mass of the above-mentioned deionized water), and finally dry at 80 °C for 24 h to obtain the composite material.

[0061] Comparative Example 6 The difference between this comparative example and Example 3 is that when preparing the modified polyvinyl chloride resin, the nanomaterials in step S2 are replaced with molybdenum disulfide nanosheets in equal mass, and the remaining steps and raw materials are the same as those in Example 3; The preparation method of the composite material includes the following steps: Mix magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water in a mass ratio of 2.2:2.2:1.2:4.2:320 to obtain a homogeneous mixed solution. Add molybdenum disulfide nanosheets to the mixed solution in a mass ratio of 3.2:7.5, and ultrasonically treat for 35 min (ultrasonic power is 100 W, ultrasonic frequency is 40 kHz). Then heat to 85 °C, add 1 mol / L sodium hydroxide solution to adjust the pH value of the system to 10.5, continue stirring for 3 h, age at 85 °C for 12 h, filter through a 0.45 μm polyethersulfone membrane, wash with deionized water (the mass of deionized water is 5% of the mass of the above-mentioned deionized water), and finally dry at 80 °C for 24 h to obtain the composite material.

[0062] Comparative Example 7 The difference between this comparative example and Example 3 is that when preparing the modified polyvinyl chloride resin, the reinforcing material in step S3 is not epoxidized and directly combined with the compounded flame retardant, and the remaining steps and raw materials are the same as those in Example 3; S3: Mix the reinforcing material and toluene evenly according to the mass ratio of the reinforcing material, toluene, compound flame retardant, and triphenylphosphine of 2.6:4.1:0.9:0.01. Then add the compound flame retardant and triphenylphosphine, and stir at 45 °C for 1 h, and then continue to stir at 80 °C for 4 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 3 times the mass of toluene), then wash with 1 mol / L sodium hydroxide solution until the pH value of the system reaches 7, remove the residual water by rotary evaporation at 75 °C, and finally vacuum dry at 60 °C for 12 h to obtain the flame-retardant reinforcing material. Among them, the compound flame retardant is composed of diphenyl (4-hydroxyphenyl) phosphate and diphenyl (2,5-dihydroxyphenyl) phosphine oxide mixed according to the mass ratio of 0.9:0.6.

[0063] Comparative Example 8 The difference between this comparative example and Example 3 is that when preparing the modified polyvinyl chloride resin, the compound flame retardant in step S3 is replaced with diphenyl (4-hydroxyphenyl) phosphate in equal mass, and the remaining steps and raw materials are the same as those in Example 3; A2: Mix the epoxy reinforcing material and toluene evenly according to the mass ratio of the epoxy reinforcing material, toluene, diphenyl (4-hydroxyphenyl) phosphate, and triphenylphosphine of 2.6:4.1:0.9:0.01. Then add diphenyl (4-hydroxyphenyl) phosphate and triphenylphosphine, and stir at 45 °C for 1 h, and then continue to stir at 80 °C for 4 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 3 times the mass of toluene), then wash with 1 mol / L sodium hydroxide solution until the pH value of the system reaches 7, remove the residual water by rotary evaporation at 75 °C, and finally vacuum dry at 60 °C for 12 h to obtain the flame-retardant reinforcing material.

[0064] Comparative Example 9 The difference between this comparative example and Example 3 is that when preparing the modified polyvinyl chloride resin, the compound flame retardant in step S3 is replaced with diphenyl (2,5-dihydroxyphenyl) phosphine oxide in equal mass, and the remaining steps and raw materials are the same as those in Example 3; A2: According to the mass ratio of the epoxy enhanced material, toluene, 2,5-dihydroxyphenyl(diphenyl)phosphine oxide, and triphenylphosphine being 2.6:4.1:0.9:0.01, mix the epoxy enhanced material and toluene evenly, then add 2,5-dihydroxyphenyl(diphenyl)phosphine oxide and triphenylphosphine, and stir at 45°C for 1 h, then continue to stir at 80°C for 4 h. After the reaction ends, cool to room temperature, filter, wash with deionized water 3 times (the mass of deionized water each time is 3 times the mass of toluene), then wash with 1 mol / L sodium hydroxide solution until the pH value of the system reaches 7, remove the residual moisture by rotary evaporation at 75°C, and finally vacuum dry at 60°C for 12 h to obtain the flame-retardant enhanced material.

[0065] Comparative Example 10 The difference between this comparative example and Example 3 is that when preparing the modified polyvinyl chloride resin, the polyvinyl chloride resin in step S4 is directly mixed with the flame-retardant enhanced material, and the remaining steps and raw materials are the same as those in Example 3; S4: According to the mass ratio of polyvinyl chloride resin, flame-retardant enhanced material, and N,N-dimethylformamide being 1.2:0.4:50, add the polyvinyl chloride resin and the flame-retardant enhanced material in step S3 to N,N-dimethylformamide and mix evenly, stir at 35°C for 24 h, filter, wash with deionized water (the mass of deionized water is 60% of the mass of N,N-dimethylformamide), and finally vacuum dry at 50°C for 12 h to obtain the modified polyvinyl chloride resin.

[0066] Now, conduct flame retardancy, abrasion resistance, and mechanical property tests on the fire hose composite materials with flame retardancy and abrasion resistance prepared in Examples 1-3 and Comparative Examples 1-10; conduct flame retardancy tests according to the UL 94 fire test standard; conduct abrasion resistance tests according to GB / T 9867-2008 "Determination of Abrasion Resistance of Vulcanized Rubber or Thermoplastic Rubber (Rotary Drum Abrasion Machine Method)"; conduct tensile strength and elongation at break tests according to GB / T 528-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber", and characterize the mechanical properties by tensile strength and elongation at break.

[0067] The test results are shown in Table 1 below: Table 1 Performance Parameters of Fire Hose Composite Materials with Flame Retardancy and Abrasion Resistance Prepared in Examples 1-3 and Comparative Examples 1-10

[0068] As can be seen from the data in Table 1 above, by comparing Comparative Examples 1-6 with Example 3, it can be known that when the bio-based plasticizer in Step S1 is replaced with propargylated cashew phenol or castor oil in equal mass, or the bio-based plasticizer in Step S1 is composed of a mixture of cashew phenol and castor oil, or the composite material in Step S2 is directly composed of a layered double hydroxide and a nanomaterial, or the nanomaterial in Step S2 is replaced with graphene oxide or molybdenum disulfide nanosheets in equal mass to prepare a composite material for fire hoses with flame retardant and wear-resistant properties, the test results are worse than those of Example 3. This shows that the bio-based plasticizer composed of a mixture of propargylated cashew phenol and castor oil has a synergistic effect, can better improve the flexibility of polyvinyl chloride resin, and can increase the binding force between the bio-based plasticizer and the silanized composite material; combining the nanomaterial with the layered double hydroxide first and then with the silane coupling agent can enhance its dispersibility, prevent its agglomeration, and effectively improve the wear-resistant and mechanical properties of polyvinyl chloride resin; the nanomaterial composed of a mixture of graphene oxide and molybdenum disulfide nanosheets has a synergistic effect, has good wear-resistant properties, and has a certain flame retardancy, which can further improve the wear-resistant, flame retardant, and mechanical properties of the composite material for fire hoses. As can be seen from the comparison between Comparative Examples 7-10 and Example 3, when the reinforcing material in Step S3 is not epoxidized and directly combined with the compound flame retardant, or the compound flame retardant in Step S3 is replaced with 4-hydroxyphenyl diphenyl phosphate or 2,5-dihydroxyphenyl diphenyl phosphine oxide in equal mass, or the polyvinyl chloride resin in Step S4 is directly mixed with the flame retardant reinforcing material to prepare a composite material for fire hoses with flame retardant and wear-resistant properties, the test results are worse than those of Example 3. This shows that epoxidizing the reinforcing material first can improve the binding force between the reinforcing material and the compound flame retardant; the compound flame retardant composed of 4-hydroxyphenyl diphenyl phosphate and 2,5-dihydroxyphenyl diphenyl phosphine oxide has a synergistic flame retardant effect, can effectively improve the flame retardant and mechanical properties of polyvinyl chloride resin; chemically combining the polyvinyl chloride resin with the flame retardant reinforcing material increases the binding force between the two, improves the compatibility between the flame retardant reinforcing material and the polyvinyl chloride resin, and further improves the wear-resistant, flame retardant, and mechanical properties of the composite material for fire hoses.

[0069] As can be seen from Table 1 above, compared with the fire hose composite materials with flame retardant and wear resistance prepared in Comparative Examples 1-10, the fire hose composite materials with flame retardant and wear resistance prepared in Examples 1-3 are obtained by combining a bio-based plasticizer with glycidyl, then combining with a silanized composite material, epoxidizing and modifying, then combining with a compound flame retardant, and finally combining with polyvinyl chloride resin to obtain a modified polyvinyl chloride resin. The modified polyvinyl chloride resin, chloroprene rubber, stabilizer, antioxidant, lubricant and vulcanizing agent are mixed and extruded into pellets to obtain a fire hose composite material with flame retardant and wear resistance, meeting the requirements of the test performance. However, the fire hose composite materials with flame retardant and wear resistance prepared in Comparative Examples 1-10 do not meet the standard of the performance requirements, indicating that the fire hose composite material prepared by the present invention has good flame retardant performance, wear resistance, thermal stability and mechanical properties, and a long service life, with good comprehensive performance.

[0070] In the description of the specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0071] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the invention or exceed the scope defined by the present invention, they should fall within the protection scope of the present invention.

Claims

1. A composite material for fire hose with flame retardant and wear resistant properties, characterized in that: The method comprises the following raw materials in parts by weight: 40-50 parts of modified polyvinyl chloride resin, 20-25 parts of chloroprene rubber, 3-6 parts of stabilizer, 0.5-1 parts of antioxidant, 0.4-0.6 parts of lubricant and 0.1-0.3 parts of vulcanizing agent; The preparation method of the modified polyvinyl chloride resin comprises the following steps: S1: hyperbranched composites were obtained by combining bio-based plasticizers with glycidol; S2: combining the hyperbranched composite with the silanized composite to obtain a reinforced material; S3: After the reinforcing material is modified by epoxidation, it is combined with a compound flame retardant to obtain a flame retardant reinforcing material; S4: Modified polyvinyl chloride resin is obtained by combining flame retardant reinforcing materials with polyvinyl chloride resin.

2. The composite material for fire hose with flame retardant and wear resistant properties according to claim 1, characterized in that: Step S1 is specifically as follows: The bio-based plasticizer and glycidol are mixed evenly, stirred for 15-25 minutes under a nitrogen atmosphere, and then heated for reaction. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed with deionized water, and finally vacuum dried at 50-60° C. to obtain a hyperbranched composite.

3. The composite material for fire hose with flame retardant and wear resistant properties according to claim 2, characterized in that: The bio-based plasticizer is composed of propargyl cardanol and castor oil mixed in a mass ratio of 1-1.2:0.5-0.

6.

4. The composite material for fire hose with flame retardant and wear resistant properties according to claim 1, characterized in that: Step S2 is specifically as follows: The hyperbranched composite in step S1 is heated to 65-70°C, and then the silanized composite material is added and mixed evenly, and then p-toluenesulfonic acid is added, and the reaction is stirred at 70-75°C for 2-3h. After the reaction is completed, it is cooled to room temperature, washed with xylene and ethyl acetate, and xylene and ethyl acetate are removed by rotary evaporation. Finally, it is vacuum dried at 50-60°C to obtain a reinforced material.

5. The composite material for fire hose with flame retardant and wear resistant properties according to claim 4, characterized in that: The preparation method of the silanized composite material comprises the following steps: The composite material is added to deionized water and ethanol, and stirred at 45-55° C. for 25-35 minutes to obtain a dispersion, a silane coupling agent is added to the mixed solution of ethanol and deionized water, and the mixture is evenly mixed to obtain a silane solution, the silane solution is added to the dispersion, acetic acid is added to adjust the pH value of the system, the temperature is increased to 85-95° C., and maintained under a nitrogen atmosphere for 22-24 hours, filtered, washed with deionized water, and finally vacuum dried at 75-80° C. to obtain a silanized composite material.

6. The composite material for fire hose with flame retardant and wear resistant properties according to claim 5, characterized in that: The preparation method of the composite material comprises the following steps: Magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride and deionized water are mixed uniformly to obtain a mixed solution, the nanomaterial is added to the mixed solution, and ultrasonic treatment is performed for 25-35 minutes, and then the solution is heated to 75-85°C, and then a sodium hydroxide solution is added to adjust the pH value of the system, and stirring is continued for 2-3 hours, and the solution is aged at 75-85°C for 10-12 hours, filtered through a filter membrane, washed with deionized water, and finally dried at 75-80°C to obtain a composite material.

7. The composite material for fire hose with flame retardant and wear resistant properties according to claim 1, characterized in that: Step S3 is specifically as follows: A1: The reinforcing material in step S2 is mixed with formic acid, then added into a hydrogen peroxide aqueous solution, and reacted at 55-65° C. for 5-7 hours. After the reaction is completed, it is added into dichloromethane, washed with deionized water, a saturated sodium bicarbonate aqueous solution and a saturated sodium chloride solution, dried with anhydrous sodium sulfate, filtered, and finally dried in vacuum at 55-65° C. to obtain an epoxidized reinforcing material; A2: Mix the epoxidized reinforcing material and toluene evenly, then add the compound flame retardant and triphenylphosphine, and stir at 35-45°C for 0.5-1h, and then continue stirring at 70-80°C for 3.5-4h. After the reaction is completed, cool to room temperature, filter, wash with deionized water, then wash with sodium hydroxide solution, remove residual moisture by rotary evaporation, and finally vacuum dry at 50-60°C to obtain a flame retardant reinforcing material.

8. The composite material for fire hose with flame retardant and wear resistant properties according to claim 7, characterized in that: In step A2, the composite flame retardant is composed of 4-hydroxyphenyl (diphenyl) phosphate and 2,5-dihydroxyphenyl (diphenyl) phosphine oxide mixed in a mass ratio of 0.8-0.9:0.5-0.

6.

9. The composite material for fire hose with flame retardant and wear resistant properties according to claim 1, characterized in that: Step S4 is specifically as follows: The polyvinyl chloride resin, sodium azide and N,N-dimethylformamide are mixed, stirred at 25-35°C for 22-24h, then precipitated into a mixed solution of water and methanol, and vacuum dried at 40-50°C to obtain component A. Component A, the flame retardant reinforcing material in step S3, cuprous bromide and 2,2-bipyridine are added to N,N-dimethylformamide, and mixed evenly, stirred at 25-35°C for 22-24h, cooled to room temperature, filtered, precipitated into a mixed solution of water and methanol, and finally vacuum dried at 40-50°C to obtain a modified polyvinyl chloride resin.

10. A method for preparing a composite material for fire hose having flame retardant and wear resistant properties according to any one of claims 1 to 9, characterized in that: The following steps are involved: Weigh the raw materials by mass, mix the modified polyvinyl chloride resin, chloroprene rubber, stabilizer, antioxidant and lubricant, then put them into an internal mixer and mix them for 3-5 minutes, then add the vulcanizer and continue mixing for 2-3 minutes, and after the internal mixer is discharged, mix them on an open mixer for 1-2 minutes, and finally extrude and granulate and cool to room temperature to obtain a composite material for fire hoses with flame retardant and wear resistant properties.

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