Fire-fighting boots used in high-risk environment

Abstract

The invention discloses a fire-fighting boot used in a high-risk environment, and belongs to the technical field of fire-fighting equipment, the fire-fighting boot comprises a sole material and a vamp material, the sole material comprises butadiene rubber, polypropylene resin, mineral powder, carbon fiber, a modified flame retardant and the like, organic-inorganic materials are compounded, so that the puncture resistance of the sole is enhanced, and the service life of the sole is prolonged. The flame-retardant shoe sole can be worn in special environments such as earthquakes and fire disasters for a long time, particularly, in order to adapt to high-temperature and flammable environments in the fire disasters, the modified flame retardant enables the shoe sole to have a certain flame-retardant effect, flame-retardant factors P and N cooperate with each other, the effect is more obvious, the flame-retardant shoe sole is halogen-free, low in smoke amount and environmentally friendly, in addition, the vamp material is further improved, and the shoe sole is more environment-friendly. The glass fiber cloth has good mechanical properties, high strength, greatly enhanced impact resistance and high safety, and the modified coating is coated on the glass fiber cloth, so that the glass fiber cloth has ultraviolet resistance and improved aging resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of fire-fighting equipment and relates to a fire-fighting boot used in a high-risk environment. Background Art

[0002] Fire boots are essential equipment for firefighters. They have excellent protection against high temperatures, heat flow, flames and general chemicals, protecting firefighters from physical injury. They are also non-slip and suitable for walking on various surfaces, greatly improving the rescue efficiency of firefighters.

[0003] Reference is made to Chinese Patent CN105747364A, which discloses a fire boot comprising a boot sole comprising, from bottom to top, an elastic base layer, a steel plate layer, and a rubber inner layer. The elastic base layer comprises a PVC / NBR blend, dioctyl phthalate, carbon black, a plasticizer, an adhesive, titanium dioxide, paraffin wax, an activator, an accelerator, an antioxidant, and sulfur. The steel plate layer extends toward the rubber base layer with several anti-slip protrusions, which are exposed and in contact with the rubber base layer and the ground. Ceramic spacers are provided between the steel plate layer and the rubber inner layer. This invention reduces heat absorption by the steel plate and reduces damage to the rubber sole in high-temperature environments, thereby extending the service life of the boot and providing an anti-slip effect. However, due to the presence of a large amount of polymer in the raw materials, the boot is easily melted and burned when exposed to high temperatures, causing damage and loss of the boot's protective function. Therefore, it is necessary to develop a fire boot that is highly flame-retardant. Summary of the Invention

[0004] The purpose of the present invention is to provide a fire boot for use in high-risk environments to solve the problems involved in the background technology.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A fire boot for use in a high-risk environment, comprising a sole material and an upper material;

[0007] The sole material is prepared by the following steps:

[0008] Step A11: Mix 30-45 parts of butadiene rubber, 20-28 parts of polypropylene resin, 4-6 parts of hot melt adhesive, 4-6 parts of ore powder, 2-4 parts of sulfur, 3-5 parts of carbon fiber, and 1-3 parts of modified flame retardant to form a raw rubber sheet;

[0009] Step A12: Place the raw rubber sheet into a sole mold, apply 80-90 kg of pressure to the rubber sheet using a hydraulic press, and vulcanize it at a temperature of 100-115° C. for 8-12 minutes to obtain the sole.

[0010] Furthermore, the ore powder in step A11 is one or more of phosphotyrite, pyrite, lapis lazuli, copper ore, dolomite, and medical stone mixed in any proportion.

[0011] The shoe upper material is made by the following steps:

[0012] Step A21, coating the modified coating on a glass fiber cloth, and then applying polyethylene films to the upper and lower surfaces of the glass fiber cloth, respectively, and compacting them;

[0013] Step A22, drying the compacted glass fiber cloth to form a mat sheet;

[0014] Step A23, prepare a corresponding number of felt sheets according to the specifications of the plastic boots to be produced, cut the felt sheets, remove the polyethylene film on the felt sheets, stack and bond them in sequence, and then heat and pressurize them to produce the upper material.

[0015] The modified flame retardant is prepared by the following steps:

[0016] Step S11: anhydrous potassium carbonate, p-hydroxybenzaldehyde, and tetrahydrofuran are added to a dry three-necked flask, nitrogen is introduced, and the mixture is dissolved by stirring at room temperature. A tetrahydrofuran solution of hexachlorocyclotriphosphazene is added thereto, and the mixture is dripped over 1 hour. After reflux reaction for 0.5 hour, the temperature is raised to 65° C. and the reflux reaction is continued for 37-40 hours. The filtrate is filtered and concentrated to one-third of the original volume. Deionized water is added and stirred to precipitate. The precipitate is filtered and the filter cake is washed with deionized water 2-3 times, recrystallized with ethyl acetate 2-3 times, and then dried in a 50° C. oven for 8-10 hours to obtain intermediate 1.

[0017] The reaction process is as follows:

[0018]

[0019] Step S12, adding ethyltriphenylphosphonium bromide to a three-necked flask, purging with nitrogen, adding anhydrous tetrahydrofuran, adding dropwise 1.3 mol / L n-butyllithium solution at -78°C, stirring at room temperature for 1 hour, then lowering the temperature to -78°C, adding dropwise a tetrahydrofuran solution of intermediate 1, continuing stirring at room temperature for 12 hours, pouring the reaction solution into n-hexane, letting it stand for 2 hours, filtering to remove the precipitate, and the filtrate being spin-dried and then recrystallized from n-propanol to obtain intermediate 2;

[0020] The reaction process is as follows:

[0021]

[0022] Step S13, adding a composite catalyst to a three-necked flask, introducing nitrogen, adding intermediate 2 and xylene, raising the temperature to 30° C., introducing hydrogen chloride, and reflux reaction for 4-5 hours to obtain intermediate 3;

[0023] The reaction process is as follows:

[0024]

[0025] Step S14, nitrogen is introduced into a three-necked flask, diethyl chlorophosphate and diethanolamine are added, and after stirring evenly, dibutyltin dilaurate is added thereto, the temperature is raised to 150° C., the mixture is refluxed for 6-7 hours, and distilled under reduced pressure to obtain intermediate 4;

[0026] The reaction process is as follows:

[0027]

[0028] Step S15, add intermediate 4, tetrahydrofuran and triethylamine to a three-necked flask, stir evenly, add the tetrahydrofuran solution of intermediate 3 thereto, control the dripping within 1 hour, introduce nitrogen, heat to 80°C and reflux for 20-22 hours, rotary evaporate the obtained product to remove the solvent, wash with deionized water 2-3 times, and then place in a 60°C oven to dry for 3-4 hours to obtain a modified flame retardant.

[0029] The reaction process is as follows:

[0030]

[0031] Furthermore, the amount ratio of anhydrous potassium carbonate, p-hydroxybenzaldehyde, tetrahydrofuran, and the tetrahydrofuran solution of hexachlorocyclotriphosphazene in step S11 is 35.3-35.8 g:19.8-20.1 g:198-203 mL:97-100 mL, and the amount ratio of hexachlorocyclotriphosphazene and tetrahydrofuran in the tetrahydrofuran solution of hexachlorocyclotriphosphazene is 8.2-8.5 g:100 mL.

[0032] Furthermore, the amount ratio of ethyltriphenylphosphonium bromide, anhydrous tetrahydrofuran, n-butyllithium solution, and tetrahydrofuran solution of intermediate 1 in step S12 is 10.2-10.5 mmol:40.2-40.8 mL:7.5-7.8 mL:19.8-20.5 mL, and the amount ratio of tetrahydrofuran and intermediate 1 in the tetrahydrofuran solution of intermediate 1 is 20 mL:7.1-7.4 mmol.

[0033] Furthermore, in step S13, the molar ratio of the intermediate 2, xylene, and hydrogen chloride is 1:10-13:1, the amount of the composite catalyst is 0.3-0.5% of the mass of the intermediate 2, and the composite catalyst is a mixture of ZnCl2 and FeCl3 in a molar ratio of 9:1.

[0034] Furthermore, in step S14, the molar ratio of diethyl chlorophosphate to diethanolamine is 1:1.3, and the amount of dibutyltin dilaurate is 0.5% of the total mass of diethyl chlorophosphate and diethanolamine.

[0035] Furthermore, in step S15, the amount ratio of intermediate 4, tetrahydrofuran, triethylamine, and tetrahydrofuran solution of intermediate 3 is 5.2-5.8 g:100-110 mL:11.5-12.2 mL:45.5-46.3 mL, and the amount ratio of tetrahydrofuran and intermediate 3 in the tetrahydrofuran solution of intermediate 3 is 5.2-5.3 g:50 mL.

[0036] The modified coating is prepared by the following steps:

[0037] Step S21, adding a 2.5% by mass sodium hydroxide solution to an acetone solution of 2,4-dihydroxybenzophenone, stirring evenly, then adding a cyanuric chloride acetone solution dropwise thereto, reflux at 2-5°C for 6 hours, adding ice water for hydrolysis, adding a 30% by mass hydrochloric acid solution to adjust the pH to 6.2-6.5, standing for 12-24 hours, filtering, washing the filter cake with acetone, and drying at 60-70°C for 4-5 hours to obtain intermediate 5;

[0038] The reaction process is as follows:

[0039]

[0040] Step S22: add intermediate 5 and dioxane to a three-necked flask, stir evenly, add half of the diaminodiphenylmethane, heat to 50°C and react for 6-7 hours, then add the other half of the diaminodiphenylmethane, heat to 100°C and react for 11-13 hours, filter, wash the filter cake with deionized water 2-3 times, and then dry in an oven at 60-65°C for 4-5 hours to obtain intermediate 6;

[0041] The reaction process is as follows:

[0042]

[0043] Step S23, adding intermediate 6, dimethylacetamide, and xylene to a three-necked flask, heating to 80-85° C., stirring evenly, adding 1,2,4-trimellitic anhydride chloride, heating to 120-140° C., and reacting for 5-6 hours to obtain a prepolymer;

[0044]

[0045] Step S24, dissolving the prepolymer in N-methylpyrrolidone, adding a mixed solvent thereto, adding dispersant BYK-163, MoS2, and graphite under high-speed stirring, dispersing at high speed for 30 minutes, adding it to a ball mill and grinding it for 5-6 hours, and passing it through a 300-mesh sieve to obtain a modified coating.

[0046] Furthermore, in step S21, the amount ratio of the acetone solution of 2,4-dihydroxybenzophenone, the sodium hydroxide solution, and the acetone solution of cyanuric chloride is 15.6-16.2 mL: 20.3-21.4 mL: 20.4-21.8 mL, the amount ratio of 2,4-dihydroxybenzophenone and acetone in the acetone solution of 2,4-dihydroxybenzophenone is 2.2-2.4 g: 15 mL, and the amount ratio of cyanuric chloride and acetone in the acetone solution of cyanuric chloride is 4.2-4.5 g: 20 mL.

[0047] Furthermore, the molar ratio of the intermediate 5 and aminodiphenylmethane in step S22 is 1:1, and the amount of dioxane used is 324-356 mL of dioxane per mol of aminodiphenylmethane.

[0048] Furthermore, in step S23, the usage ratio of the intermediate 6, dimethylacetamide, xylene, and 1,2,4-trimellitic anhydride chloride is 36.5-40.7 g: 105-110 mL: 47.6-50.7 mL: 70.5-79.4 g.

[0049] Furthermore, in step S24, the usage ratio of the prepolymer, N-methylpyrrolidone, mixed solvent, dispersant BYK-163, MoS2, and graphite is 38.4-41.5 g: 104.3-106.5 mL: 138.3-146.8 mL: 0.6-0.7 g: 14.2-14.8 g: 6.4-6.8 g, and the mixed solvent is NMP, n-BA, DMF, and xylene mixed in a volume ratio of 4:4:1:1.

[0050] Beneficial effects of the present invention: The present invention aims to provide fire boots for use in high-risk environments. The fire boots include a sole and an upper. The raw materials of the sole material include butadiene rubber, polypropylene resin, mineral powder, carbon fiber, a modified flame retardant, etc. The composite of organic and inorganic materials enhances the puncture resistance of the sole, allowing long-term wear in special environments such as earthquakes and fires. In particular, the modified flame retardant provides a certain flame retardant effect to adapt to the high temperature and flammable environment of fires. First, p-hydroxybenzaldehyde reacts with hexachlorocyclotriphosphazene to remove HCl to generate intermediate 1. Intermediate 1 reacts with ethyltriphenylphosphonium bromide under the action of n-butyl lithium to generate intermediate 2. Intermediate 2 reacts with hydrogen chloride under the action of a composite catalyst to generate intermediate 3. Then, diethyl chlorophosphate and diethanolamine react through ester exchange to generate intermediate 4. Intermediate 4 reacts with intermediate 3 to remove HCl to generate a modified flame retardant. The modified flame retardant contains flame retardant factors P and N. P-based flame retardants are easy to decompose after absorbing heat, and the product has strong dehydration. At the same time, the water vapor generated absorbs heat and reduces the temperature of the material surface. The product can form a viscous liquid film to cover the carbon layer, further inhibiting the oxidation of the coke layer and playing a flame retardant role. N-based flame retardants are easy to decompose when heated, releasing non-combustible gases such as CO2, NH3, N2, H2O, etc., which dilute and dilute the concentration of combustible gases, and wrap the surface of the combustible material to reduce the temperature, thereby playing a flame retardant role. The synergistic effect of P and N series is more obvious, halogen-free, low in smoke, and environmentally friendly.

[0051] In addition, the upper material has also been further improved. The glass fiber cloth has good mechanical properties and high strength, which greatly enhances the impact resistance, effectively avoiding the phenomenon of kicking foreign objects or being crushed or hit by falling foreign objects during walking, and has high safety. The modified coating is coated on the glass fiber cloth to make it resistant to ultraviolet rays and add anti-aging properties. First, cyanuric chloride reacts with 2,4-dihydroxybenzophenone to generate intermediate 5, intermediate 5 reacts with diaminodiphenylmethane to generate intermediate 6, and intermediate 6 reacts with 1,2,4-trimellitic anhydride chloride to generate polyamide-amide acid prepolymer. The modified coating is prepared by mixing an amide-amic acid prepolymer with other additives. The presence of triazine rings and benzophenone structures in the polyamide-amic acid prepolymer enhances UV absorption. The oxygen atoms on the ketone group in the benzophenone form hydrogen bonds with the hydrogen atoms on the adjacent hydroxyl groups. These hydrogen bonds break and reconnect under the action of UV energy, achieving UV absorption. Simultaneously, the conjugation between the triazine ring and the benzene ring creates a large conjugated system, significantly red-shifting the compound's maximum absorption. This results in strong UV absorption across a wide range of 280-380nm, imparting aging resistance to the upper material. The fire boots prepared in this manner not only possess high safety, but also possess flame retardancy and aging resistance. DETAILED DESCRIPTION

[0052] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0053] Example 1

[0054] The modified flame retardant is prepared by the following steps:

[0055] Step S11: add 35.3 g of anhydrous potassium carbonate, 19.8 g of p-hydroxybenzaldehyde, and 198 mL of tetrahydrofuran to a dry three-necked flask, introduce nitrogen, and stir at room temperature to dissolve the mixture. Then, add 97 mL of a tetrahydrofuran solution of hexachlorocyclotriphosphazene and drip the mixture over a period of 1 hour. After reflux reaction for 0.5 hour, heat the mixture to 65° C. and continue reflux reaction for 37 hours. Filter the mixture with suction, concentrate the filtrate to one-third of its original volume, add deionized water, stir to separate out the precipitate, filter, wash the filter cake twice with deionized water, recrystallize the mixture twice with ethyl acetate, and dry the mixture in a 50° C. oven at 8 hours to obtain intermediate 1, wherein the ratio of hexachlorocyclotriphosphazene to tetrahydrofuran in the tetrahydrofuran solution of hexachlorocyclotriphosphazene is 8.2 g:100 mL.

[0056] Step S12, adding 10.2 mmol of ethyltriphenylphosphonium bromide to a three-necked flask, passing nitrogen, adding 40.2 mL of anhydrous tetrahydrofuran, adding dropwise 7.5 mL of 1.3 mol / L n-butyllithium solution at -78 ° C., stirring at room temperature for 1 hour, then lowering the temperature to -78 ° C., adding dropwise 19.8 mL of a tetrahydrofuran solution of intermediate 1, continuing to stir at room temperature for 12 hours, pouring the reaction solution into n-hexane, letting it stand for 2 hours, filtering to remove the precipitate, and the filtrate was spin-dried and recrystallized from n-propanol to obtain intermediate 2, wherein the amount ratio of tetrahydrofuran to intermediate 1 in the tetrahydrofuran solution of intermediate 1 is 20 mL:7.1 mmol;

[0057] Step S13, adding a composite catalyst to a three-necked flask, passing nitrogen, adding intermediate 2 and xylene, raising the temperature to 30°C, passing hydrogen chloride, and reflux reaction for 4 hours to obtain intermediate 3, wherein the molar ratio of intermediate 2, xylene, and hydrogen chloride is 1:10:1, the amount of the composite catalyst is 0.3% of the mass of intermediate 2, and the composite catalyst is a mixture of ZnCl2 and FeCl3 in a molar ratio of 9:1;

[0058] Step S14, nitrogen is introduced into a three-necked flask, diethyl chlorophosphate and diethanolamine are added, and after stirring evenly, dibutyltin dilaurate is added thereto, and the temperature is raised to 150° C. and refluxed for 6 hours, followed by distillation under reduced pressure to obtain intermediate 4, wherein the molar ratio of diethyl chlorophosphate to diethanolamine is 1:1.3, and the amount of dibutyltin dilaurate is 0.5% of the total mass of diethyl chlorophosphate and diethanolamine;

[0059] Step S15, 5.2 g of intermediate 4, 100 mL of tetrahydrofuran and 11.5 mL of triethylamine were added to a three-necked flask, and after stirring evenly, 45.5 mL of tetrahydrofuran solution of intermediate 3 was added thereto, and the mixture was dripped within 1 hour. Nitrogen was introduced, and the temperature was raised to 80° C. and refluxed for 20 hours. The obtained product was rotary evaporated to remove the solvent, washed twice with deionized water, and then placed in a 60° C. oven to dry for 3 hours to obtain a modified flame retardant, wherein the amount ratio of tetrahydrofuran to intermediate 3 in the tetrahydrofuran solution of intermediate 3 is 5.2 g:50 mL.

[0060] Example 2

[0061] The modified flame retardant is prepared by the following steps:

[0062] Step S11: add 35.5 g of anhydrous potassium carbonate, 19.9 g of p-hydroxybenzaldehyde, and 201 mL of tetrahydrofuran to a dry three-necked flask, introduce nitrogen, and stir at room temperature to dissolve the mixture. Then, add 98 mL of a tetrahydrofuran solution of hexachlorocyclotriphosphazene and drip the mixture over a period of 1 hour. After reflux reaction for 0.5 hour, heat the mixture to 65° C. and continue reflux reaction for 38 hours. Filter the mixture with suction, concentrate the filtrate to one-third of its original volume, add deionized water, stir to precipitate, filter, wash the filter cake twice with deionized water, recrystallize the mixture twice with ethyl acetate, and dry the mixture in a 50° C. oven at 9 hours to obtain intermediate 1, wherein the ratio of hexachlorocyclotriphosphazene to tetrahydrofuran in the tetrahydrofuran solution of hexachlorocyclotriphosphazene is 8.3 g:100 mL.

[0063] Step S12, adding 10.3 mmol of ethyltriphenylphosphonium bromide to a three-necked flask, passing nitrogen, adding 40.6 mL of anhydrous tetrahydrofuran, adding dropwise 7.6 mL of 1.3 mol / L n-butyllithium solution at -78 ° C., stirring at room temperature for 1 hour, then lowering the temperature to -78 ° C., adding dropwise 20.3 mL of a tetrahydrofuran solution of intermediate 1, continuing to stir at room temperature for 12 hours, pouring the reaction solution into n-hexane, letting it stand for 2 hours, filtering to remove the precipitate, and the filtrate was spin-dried and recrystallized from n-propanol to obtain intermediate 2, wherein the amount ratio of tetrahydrofuran to intermediate 1 in the tetrahydrofuran solution of intermediate 1 is 20 mL:7.3 mmol;

[0064] Step S13, adding a composite catalyst to a three-necked flask, passing nitrogen, adding intermediate 2 and xylene, raising the temperature to 30°C, passing hydrogen chloride, and reflux reaction for 4 hours to obtain intermediate 3, wherein the molar ratio of intermediate 2, xylene, and hydrogen chloride is 1:12:1, the amount of the composite catalyst is 0.4% of the mass of intermediate 2, and the composite catalyst is a mixture of ZnCl2 and FeCl3 in a molar ratio of 9:1;

[0065] Step S14, nitrogen is introduced into a three-necked flask, diethyl chlorophosphate and diethanolamine are added, and after stirring evenly, dibutyltin dilaurate is added thereto, and the temperature is raised to 150° C. and refluxed for 6 hours, followed by distillation under reduced pressure to obtain intermediate 4, wherein the molar ratio of diethyl chlorophosphate to diethanolamine is 1:1.3, and the amount of dibutyltin dilaurate is 0.5% of the total mass of diethyl chlorophosphate and diethanolamine;

[0066] Step S15, 5.5 g of intermediate 4, 105 mL of tetrahydrofuran and 11.8 mL of triethylamine were added to a three-necked flask, and after stirring evenly, 45.9 mL of tetrahydrofuran solution of intermediate 3 was added thereto, and the mixture was dripped within 1 hour. Nitrogen was introduced, and the temperature was raised to 80° C. and refluxed for 21 hours. The obtained product was rotary evaporated to remove the solvent, washed twice with deionized water, and then placed in a 60° C. oven to dry for 3 hours to obtain a modified flame retardant, wherein the amount ratio of tetrahydrofuran to intermediate 3 in the tetrahydrofuran solution of intermediate 3 is 5.2 g:50 mL.

[0067] Example 3

[0068] The modified flame retardant is prepared by the following steps:

[0069] Step S11: add 35.8 g of anhydrous potassium carbonate, 20.1 g of p-hydroxybenzaldehyde, and 203 mL of tetrahydrofuran to a dry three-necked flask, introduce nitrogen, and stir at room temperature to dissolve the mixture. Then, add 100 mL of a tetrahydrofuran solution of hexachlorocyclotriphosphazene and drip the mixture over a period of 1 hour. After reflux reaction for 0.5 hour, heat the mixture to 65° C. and continue reflux reaction for 40 hours. Filter the mixture with suction, concentrate the filtrate to one-third of its original volume, add deionized water, stir to precipitate, filter, wash the filter cake with deionized water three times, recrystallize the mixture with ethyl acetate three times, and dry it in a 50° C. oven at 10 hours to obtain intermediate 1, wherein the ratio of hexachlorocyclotriphosphazene to tetrahydrofuran in the tetrahydrofuran solution of hexachlorocyclotriphosphazene is 8.5 g:100 mL.

[0070] Step S12, adding 10.5 mmol of ethyltriphenylphosphonium bromide to a three-necked flask, passing nitrogen, adding 40.8 mL of anhydrous tetrahydrofuran, adding dropwise 7.8 mL of 1.3 mol / L n-butyllithium solution at -78 ° C., stirring at room temperature for 1 hour, then lowering the temperature to -78 ° C., adding dropwise 20.5 mL of a tetrahydrofuran solution of intermediate 1, continuing to stir at room temperature for 12 hours, pouring the reaction solution into n-hexane, letting it stand for 2 hours, filtering to remove the precipitate, and the filtrate was spin-dried and recrystallized from n-propanol to obtain intermediate 2, wherein the amount ratio of tetrahydrofuran to intermediate 1 in the tetrahydrofuran solution of intermediate 1 is 20 mL:7.4 mmol;

[0071] Step S13, adding a composite catalyst to a three-necked flask, passing nitrogen, adding intermediate 2 and xylene, raising the temperature to 30°C, passing hydrogen chloride, and reflux reaction for 5 hours to obtain intermediate 3, wherein the molar ratio of intermediate 2, xylene, and hydrogen chloride is 1:13:1, the amount of the composite catalyst is 0.5% of the mass of intermediate 2, and the composite catalyst is a mixture of ZnCl2 and FeCl3 in a molar ratio of 9:1;

[0072] Step S14, nitrogen is introduced into a three-necked flask, diethyl chlorophosphate and diethanolamine are added, and after stirring, dibutyltin dilaurate is added thereto, and the temperature is raised to 150° C. and refluxed for 7 hours, and distilled under reduced pressure to obtain intermediate 4, wherein the molar ratio of diethyl chlorophosphate to diethanolamine is 1:1.3, and the amount of dibutyltin dilaurate is 0.5% of the total mass of diethyl chlorophosphate and diethanolamine;

[0073] Step S15, 5.8 g of intermediate 4, 110 mL of tetrahydrofuran and 12.2 mL of triethylamine were added to a three-necked flask, and after stirring evenly, 46.3 mL of tetrahydrofuran solution of intermediate 3 was added thereto, and the mixture was dripped within 1 hour. Nitrogen was introduced, and the temperature was raised to 80° C. and refluxed for 22 hours. The obtained product was rotary evaporated to remove the solvent, washed with deionized water 3 times, and then placed in a 60° C. oven to dry for 4 hours to obtain a modified flame retardant, wherein the amount ratio of tetrahydrofuran to intermediate 3 in the tetrahydrofuran solution of intermediate 3 is 5.3 g:50 mL.

[0074] Example 4

[0075] The modified coating is prepared by the following steps:

[0076] Step S21, adding 20.3 mL of 2.5% sodium hydroxide solution by mass to 15.6 mL of 2,4-dihydroxybenzophenone in acetone solution, stirring evenly, and then adding 20.4 mL of cyanuric chloride in acetone solution dropwise thereto, reflux at 2°C for 6 hours, adding ice water for hydrolysis, adding 30% hydrochloric acid solution by mass to adjust the pH to 6.2, standing for 12 hours, filtering, washing the filter cake with acetone, and drying at 60°C for 4 hours to obtain intermediate 5, wherein the amount ratio of 2,4-dihydroxybenzophenone to acetone in the acetone solution of 2,4-dihydroxybenzophenone is 2.2 g:15 mL, and the amount ratio of cyanuric chloride to acetone in the acetone solution of cyanuric chloride is 4.2 g:20 mL;

[0077] Step S22: add intermediate 5 and dioxane to a three-necked flask, stir evenly, add half of the diaminodiphenylmethane, heat to 50° C. and react for 6 h, then add the other half of the diaminodiphenylmethane, heat to 100° C. and react for 11 h, filter, wash the filter cake twice with deionized water, and then dry in a 60° C. oven for 4 h to obtain intermediate 6, wherein the molar ratio of intermediate 5 to aminodiphenylmethane is 1:1, and the amount of dioxane is 324 mL per mol of aminodiphenylmethane;

[0078] Step S23, 36.5 g of intermediate 6, 105 mL of dimethylacetamide, and 47.6 mL of xylene were added to a three-necked flask, the temperature was raised to 80° C., and after stirring evenly, 70.5 g of 1,2,4-trimellitic anhydride chloride was added thereto, and the temperature was raised to 120° C. and reacted for 5 h to obtain a prepolymer;

[0079] Step S24, 38.4 g of the prepolymer was dissolved in 104.3 mL of N-methylpyrrolidone, 138.3 mL of a mixed solvent was added thereto, 0.6 g of a dispersant BYK-163, 14.2 g of MoS2, and 6.4 g of graphite were added under high-speed stirring, and after high-speed dispersion for 30 minutes, the mixture was added to a ball mill and ground for 5 hours, and passed through a 300-mesh sieve to obtain a modified coating, wherein the mixed solvent was NMP, n-BA, DMF, and xylene mixed in a volume ratio of 4:4:1:1.

[0080] Example 5

[0081] The modified coating is prepared by the following steps:

[0082] Step S21, adding 20.9 mL of a 2.5% sodium hydroxide solution by mass to 15.8 mL of an acetone solution of 2,4-dihydroxybenzophenone, stirring evenly, and then adding dropwise 20.9 mL of an acetone solution of cyanuric chloride. After reflux reaction at 4°C for 6 hours, ice water is added for hydrolysis, and a 30% hydrochloric acid solution by mass is added to adjust the pH to 6.3. The mixture is allowed to stand for 18 hours, filtered, and the filter cake is washed with acetone and dried at 65°C for 4 hours to obtain intermediate 5, wherein the amount ratio of 2,4-dihydroxybenzophenone to acetone in the acetone solution of 2,4-dihydroxybenzophenone is 2.3 g:15 mL, and the amount ratio of cyanuric chloride to acetone in the acetone solution of cyanuric chloride is 4.3 g:20 mL;

[0083] Step S22: add intermediate 5 and dioxane to a three-necked flask, stir evenly, add half of the diaminodiphenylmethane, heat to 50° C. and react for 6 h, then add the other half of the diaminodiphenylmethane, heat to 100° C. and react for 12 h, filter, wash the filter cake twice with deionized water, and then dry in a 63° C. oven for 4 h to obtain intermediate 6, wherein the molar ratio of intermediate 5 to aminodiphenylmethane is 1:1, and the amount of dioxane is 335 mL of dioxane per mol of aminodiphenylmethane;

[0084] Step S23, 38.7 g of intermediate 6, 107 mL of dimethylacetamide, and 49.5 mL of xylene were added to a three-necked flask, the temperature was raised to 83° C., and after stirring evenly, 75.3 g of 1,2,4-trimellitic anhydride chloride was added thereto, and the temperature was raised to 130° C. and reacted for 5 h to obtain a prepolymer;

[0085] Step S24, 39.6 g of the prepolymer was dissolved in 105.2 mL of N-methylpyrrolidone, 142.5 mL of a mixed solvent was added thereto, 0.6 g of a dispersant BYK-163, 14.5 g of MoS2, and 6.7 g of graphite were added under high-speed stirring, and after high-speed dispersion for 30 minutes, the mixture was added to a ball mill and ground for 5 hours, and passed through a 300-mesh sieve to obtain a modified coating, wherein the mixed solvent was NMP, n-BA, DMF, and xylene mixed in a volume ratio of 4:4:1:1.

[0086] Example 6

[0087] The modified coating is prepared by the following steps:

[0088] Step S21, adding 21.4 mL of a 2.5% sodium hydroxide solution by mass to 16.2 mL of an acetone solution of 2,4-dihydroxybenzophenone, stirring evenly, and then adding dropwise 21.8 mL of an acetone solution of cyanuric chloride thereto. After reflux reaction at 5° C. for 6 h, ice water is added for hydrolysis, and a 30% hydrochloric acid solution by mass is added to adjust the pH to 6.5. The mixture is allowed to stand for 24 h, filtered, and the filter cake is washed with acetone and dried at 70° C. for 5 h to obtain intermediate 5, wherein the ratio of 2,4-dihydroxybenzophenone to acetone in the acetone solution of 2,4-dihydroxybenzophenone is 2.4 g:15 mL, and the ratio of cyanuric chloride to acetone in the acetone solution of cyanuric chloride is 4.5 g:20 mL;

[0089] Step S22: add intermediate 5 and dioxane to a three-necked flask, stir evenly, add half of the diaminodiphenylmethane, heat to 50° C. and react for 7 h, then add the other half of the diaminodiphenylmethane, heat to 100° C. and react for 13 h, filter, wash the filter cake three times with deionized water, and then dry in a 65° C. oven for 5 h to obtain intermediate 6, wherein the molar ratio of intermediate 5 to aminodiphenylmethane is 1:1, and the amount of dioxane is 356 mL of dioxane per mol of aminodiphenylmethane;

[0090] Step S23, 40.7 g of intermediate 6, 110 mL of dimethylacetamide, and 50.7 mL of xylene were added to a three-necked flask, the temperature was raised to 85° C., and after stirring evenly, 79.4 g of 1,2,4-trimellitic anhydride chloride was added thereto, and the temperature was raised to 140° C. and reacted for 6 h to obtain a prepolymer;

[0091] Step S24, 41.5 g of the prepolymer was dissolved in 106.5 mL of N-methylpyrrolidone, 146.8 mL of a mixed solvent was added thereto, 0.7 g of a dispersant BYK-163, 14.8 g of MoS2, and 6.8 g of graphite were added under high-speed stirring, and after high-speed dispersion for 30 minutes, the mixture was added to a ball mill and ground for 6 hours, and passed through a 300-mesh sieve to obtain a modified coating, wherein the mixed solvent was NMP, n-BA, DMF, and xylene mixed in a volume ratio of 4:4:1:1.

[0092] Example 7

[0093] A fire boot for use in a high-risk environment, comprising a sole material and an upper material;

[0094] The sole material is prepared by the following steps:

[0095] Step A11: 30 parts of butadiene rubber, 20 parts of polypropylene resin, 4 parts of hot melt adhesive, 4 parts of phosphite, 2 parts of sulfur, 3 parts of carbon fiber, and 1 part of the modified flame retardant prepared in Example 1 are mixed and kneaded to form a raw rubber sheet;

[0096] Step A12: Place the raw rubber sheet into a sole mold, apply 80 kg of pressure to the rubber sheet using a hydraulic press, and vulcanize it at 100° C. for 8 minutes to obtain the sole.

[0097] The shoe upper material is made by the following steps:

[0098] Step A21, coating the modified coating prepared in Example 4 on a glass fiber cloth, and then affixing polyethylene films to the upper and lower surfaces of the glass fiber cloth, respectively, and compacting them;

[0099] Step A22, drying the compacted glass fiber cloth to form a mat sheet;

[0100] Step A23, prepare a corresponding number of felt sheets according to the specifications of the plastic boots to be produced, cut the felt sheets, remove the polyethylene film on the felt sheets, stack and bond them in sequence, and then heat and pressurize them to produce the upper material.

[0101] Example 8

[0102] A fire boot for use in a high-risk environment, comprising a sole material and an upper material;

[0103] The sole material is prepared by the following steps:

[0104] Step A11: 38 parts of butadiene rubber, 24 parts of polypropylene resin, 5 parts of hot melt adhesive, 5 parts of pyrite, 3 parts of sulfur, 4 parts of carbon fiber, and 2 parts of the modified flame retardant prepared in Example 2 are mixed in parts by weight to form a raw rubber sheet;

[0105] Step A12: Load the raw rubber sheet into the sole mold, apply 85 kg of pressure to the rubber sheet using a hydraulic press, and vulcanize it at a temperature of 110° C. for 10 minutes to obtain the sole.

[0106] The shoe upper material is made by the following steps:

[0107] Step A21, coating the modified coating prepared in Example 5 on a glass fiber cloth, and then affixing polyethylene films to the upper and lower surfaces of the glass fiber cloth, respectively, and compacting them;

[0108] Step A22, drying the compacted glass fiber cloth to form a mat sheet;

[0109] Step A23, prepare a corresponding number of felt sheets according to the specifications of the plastic boots to be produced, cut the felt sheets, remove the polyethylene film on the felt sheets, stack and bond them in sequence, and then heat and pressurize them to produce the upper material.

[0110] Example 9

[0111] A fire boot for use in a high-risk environment, comprising a sole material and an upper material;

[0112] The sole material is prepared by the following steps:

[0113] Step A11: 45 parts of butadiene rubber, 28 parts of polypropylene resin, 6 parts of hot melt adhesive, 6 parts of medical stone, 4 parts of sulfur, 5 parts of carbon fiber, and 3 parts of the modified flame retardant prepared in Example 3 are mixed and kneaded to form a raw rubber sheet.

[0114] Step A12: Place the raw rubber sheet into a sole mold, apply 90 kg of pressure to the rubber sheet using a hydraulic press, and vulcanize it at a temperature of 115° C. for 12 minutes to obtain the sole.

[0115] The shoe upper material is made by the following steps:

[0116] Step A21, coating the modified coating prepared in Example 6 on a glass fiber cloth, and then affixing polyethylene films to the upper and lower surfaces of the glass fiber cloth, respectively, and compacting them;

[0117] Step A22, drying the compacted glass fiber cloth to form a mat sheet;

[0118] Step A23, prepare a corresponding number of felt sheets according to the specifications of the plastic boots to be produced, cut the felt sheets, remove the polyethylene film on the felt sheets, stack and bond them in sequence, and then heat and pressurize them to produce the upper material.

[0119] Comparative Example 1

[0120] Fire boots produced by Huangshan Qiyun Fire Equipment Co., Ltd.

[0121] Comparative Example 2

[0122] The fire boots of Comparative Example 2 refer to Example 7, except that no modified flame retardant is added.

[0123] Comparative Example 3

[0124] The fire boots of Comparative Example 3 refer to Example 7, except that the modified coating is not applied.

[0125] The following performance tests were conducted on Examples 7-9 and Comparative Examples 1-3: (1) Anti-smashing performance: GB16756-5.4.3 (An1 type: impact hammer mass 23 kg, drop height 900 mm, after the test, the deformation gap in the toe is greater than 15 mm, which is qualified) was used to test the anti-smashing performance of the sole and upper; (2) Flame retardant performance: oxygen index test: according to national standard GT2406.2-2009, vertical burning test: according to national standard GT2408-1996; (3) Anti-aging performance: artificial accelerated aging test was conducted in accordance with GB / T 16422.2-1999 using a xenon arc lamp aging test chamber, with a relative spectral irradiance of 0.5 W / (m2·nm) at 340 nm, a test time of 1200 h, a black standard thermometer temperature of 65°C, a chamber temperature of 40°C, a relative humidity of 50%, and a spray cycle of 18 min spray and 102 min rest. The test data are shown in Table 1:

[0126] Table 1

[0127]

[0128]

[0129] It can be seen from Table 1 that, compared with Comparative Examples 1-3, the firefighting boots of Examples 7-9 not only have anti-smashing and anti-puncture properties and high safety, but also have flame retardant and anti-aging properties.

[0130] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0131] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A fire boot for use in high-risk environments, comprising a sole material and an upper material, characterized in that: The sole material comprises the following raw materials in parts by weight: 30-45 parts of butadiene rubber, 20-28 parts of polypropylene resin, 4-6 parts of hot melt adhesive, 4-6 parts of ore powder, 2-4 parts of sulfur, 3-5 parts of carbon fiber, and 1-3 parts of modified flame retardant; The modified flame retardant is prepared by the following steps: Step S11, anhydrous potassium carbonate, p-hydroxybenzaldehyde, and tetrahydrofuran are added to a dry three-necked flask, nitrogen is introduced, and the mixture is stirred at room temperature to dissolve. A tetrahydrofuran solution of hexachlorocyclotriphosphazene is added thereto, and the mixture is refluxed for 0.5 h, then heated to 65° C. and reacted for 37-40 h. The mixture is filtered and the filtrate is concentrated to one-third of the original volume. Deionized water is added and stirred to precipitate, which is filtered. The filter cake is washed, recrystallized, and dried to obtain Intermediate 1; Step S12, adding ethyltriphenylphosphonium bromide to a three-necked flask, purging with nitrogen, adding anhydrous tetrahydrofuran, adding n-butyllithium solution dropwise at -78°C, stirring at room temperature for 1 hour, then lowering the temperature to -78°C, adding a tetrahydrofuran solution of intermediate 1 dropwise, continuing to stir at room temperature for 12 hours, pouring the reaction solution into n-hexane, letting it stand for 2 hours, filtering, and the filtrate is spin-dried and recrystallized to obtain intermediate 2; Step S13, adding a composite catalyst to a three-necked flask, introducing nitrogen, adding intermediate 2 and xylene, raising the temperature to 30° C., introducing hydrogen chloride, and reflux reaction for 4-5 hours to obtain intermediate 3; Step S14, nitrogen is introduced into a three-necked flask, diethyl chlorophosphate and diethanolamine are added, and after stirring evenly, dibutyltin dilaurate is added thereto, the temperature is raised to 150° C., the mixture is refluxed for 6-7 hours, and distilled under reduced pressure to obtain intermediate 4; Step S15: After the intermediate 4, tetrahydrofuran and triethylamine are stirred evenly, a tetrahydrofuran solution of the intermediate 3 is added thereto, nitrogen is introduced, the temperature is raised to 80° C. and refluxed for 20-22 hours, the obtained product is subjected to rotary evaporation to remove the solvent, and the product is washed and dried to obtain a modified flame retardant.

2. The fire boots for use in high-risk environments according to claim 1, characterized in that: In step S11, the dosage ratio of anhydrous potassium carbonate, p-hydroxybenzaldehyde, tetrahydrofuran, and the tetrahydrofuran solution of hexachlorocyclotriphosphazene is 35.3-35.8 g:19.8-20.1 g:198-203 mL:97-100 mL, and the dosage ratio of hexachlorocyclotriphosphazene and tetrahydrofuran in the tetrahydrofuran solution of hexachlorocyclotriphosphazene is 8.2-8.5 g:100 mL.

3. The fire boots for use in high-risk environments according to claim 1, characterized in that: The amount ratio of ethyltriphenylphosphonium bromide, anhydrous tetrahydrofuran, n-butyllithium solution, and tetrahydrofuran solution of intermediate 1 in step S12 is 10.2-10.5 mmol:40.2-40.8 mL:7.5-7.8 mL:19.8-20.5 mL, and the amount ratio of tetrahydrofuran and intermediate 1 in the tetrahydrofuran solution of intermediate 1 is 20 mL:7.1-7.4 mmol.

4. The fire boots for use in high-risk environments according to claim 1, characterized in that: In step S13, the molar ratio of the intermediate 2, xylene, and hydrogen chloride is 1:10-13:1, and the amount of the composite catalyst is 0.3-0.5% of the mass of the intermediate 2. The composite catalyst is a mixture of ZnCl2 and FeCl3 in a molar ratio of 9:

1.

5. The fire boots for use in high-risk environments according to claim 1, characterized in that: In step S14, the molar ratio of diethyl chlorophosphate to diethanolamine is 1:1.3, and the amount of dibutyltin dilaurate is 0.5% of the total mass of diethyl chlorophosphate and diethanolamine.

6. The fire boots for use in high-risk environments according to claim 1, characterized in that: In step S15, the usage ratio of intermediate 4, tetrahydrofuran, triethylamine, and tetrahydrofuran solution of intermediate 3 is 5.2-5.8 g:100-110 mL:11.5-12.2 mL:45.5-46.3 mL, and the usage ratio of tetrahydrofuran and intermediate 3 in the tetrahydrofuran solution of intermediate 3 is 5.2-5.3 g:50 mL.

Images