Wear-resistant, heat-insulating and flame-retardant composite fire-fighting boot and preparation method thereof
By using composite materials and specific processes, the existing fire-fighting boots have been solved, and the problem of poor heat-resistant oxygen aging and wear resistance in high temperature environments is achieved, which has achieved higher flame retardant, heat insulation and wear resistance, and improved the protection ability of firefighters.
Patent Information
- Application Number
- CN202510037792.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-10
- Publication Date
- 2025-03-28
AI Technical Summary
The natural rubber materials of existing fire boots have poor thermal oxygen aging performance in high temperature environments and poor wear resistance, so they need to improve design to improve protection performance.
Fire boots are made of composite materials, including 3# smoke rubber, ethylene propylene ternary rubber, butyl rubber, carbon black, composite flame retardant and other components. Composite films are prepared through refining and vulcanization processes, and finally fire boots are made through adhesive, pressurization and sewing processes.
It improves the flame retardant, thermal insulation and wear resistance of fire boots, enhances the protection ability of firefighters in high temperature environments, and extends the service life of the boots.
Smart Images
Figure BDA0005236032130000091 
Figure BDA0005236032130000101
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of fire boots, and in particular to a wear-resistant, heat-insulating and flame-retardant composite fire boot and a preparation method thereof. Background Art
[0002] Fire boots are a kind of protective equipment specially designed for firefighters, mainly used to protect the feet and calves of firefighters from water immersion, external force damage, heat conduction and heat radiation, etc. Fire boots have multiple functions and technical features to ensure the safety of firefighters when performing their tasks.
[0003] At present, in the field of rubber film product manufacturing, composite materials are used to make rubber films to make fire boots, which play a strong protective role for firefighters in firefighting environments, earthquake rescue and disaster relief environments, etc.
[0004] Some fire boots in the prior art use natural rubber as the main component of the upper rubber material of fire-fighting protective boots, because natural rubber is a renewable natural green raw material with the advantages of low cost, high strength, high elasticity, high cold resistance, etc. However, there are a large number of irregular reactive double bonds on the main chain of natural rubber, which seriously affect its thermal oxygen stability, resulting in poor thermal oxygen aging resistance, and also affects its wear resistance. Therefore, it is necessary to improve the design of fire boots in the relevant technology. Summary of the invention
[0005] In view of the problems existing in the prior art, the present invention provides a wear-resistant, heat-insulating, flame-retardant composite firefighting boot and a preparation method thereof.
[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions:
[0007] A wear-resistant, heat-insulating and flame-retardant composite fire boot. The components of the fire boot include the following raw materials in parts by weight: 40-70 parts of 3# smoked sheet rubber, 15-35 parts of EPDM rubber, 10-30 parts of butadiene rubber, 10-20 parts of carbon black, 0.9-2.3 parts of accelerator, 5-8 parts of activator, 0.5-1.5 parts of stearic acid, 3.0-5.8 parts of antioxidant, 10-25 parts of white carbon black, 10-28 parts of filling material, 5-25 parts of white slip powder, 20-45 parts of composite flame retardant and 0.8-2.4 parts of sulfur.
[0008] Preferably, the components of the fire boots include the following raw materials in parts by weight: 55 parts of 3# smoke sheet glue, 25 parts of EPDM rubber, 20 parts of butadiene rubber, 15 parts of carbon black, 1.6 parts of accelerator, 6 parts of activator, 1 part of stearic acid, 4.5 parts of antioxidant, 17 parts of white carbon black, 20 parts of filling material, 15 parts of white slip, 30 parts of composite flame retardant, and 1.6 parts of sulfur.
[0009] Preferably, the accelerator is composed of accelerator M, accelerator DM and accelerator CZ, wherein: accelerator M is 0.2-0.8 parts, accelerator DM is 0.3-0.9 parts, and accelerator CZ is 0.4-0.6 parts.
[0010] Preferably, the antioxidant consists of antioxidant ODA, antioxidant D37, antioxidant 2246 and antioxidant MB, wherein: antioxidant ODA 0.8-1.4 parts, antioxidant D37 0.8-1.4 parts, antioxidant 2246 1.0-1.8 parts, antioxidant MB 0.4-1.2 parts.
[0011] Preferably, the composite flame retardant is composed of tribromophenol, aluminum tripolyphosphate and ammonium polyphosphate, wherein: tribromophenol is 7-16 parts, aluminum tripolyphosphate is 7-15 parts, and ammonium polyphosphate is 6-14 parts.
[0012] Preferably, the active agent is zinc oxide.
[0013] Preferably, the filling material is calcium carbonate particles.
[0014] The present invention also discloses a method for preparing a wear-resistant, heat-insulating and flame-retardant composite firefighting boot, which comprises the following steps:
[0015] S1. Weigh 3# cigarette sheet rubber, EPDM rubber and cis-1,4-butadiene rubber in proportion, use an open mill to plasticate, pass through 8 times and leave for 8 hours to obtain a mixed rubber material;
[0016] S2, put the mixed rubber obtained in S1 into an internal mixer, weigh carbon black, activator, stearic acid, antioxidant, white carbon black, filler, white slip and composite flame retardant according to proportion, adjust the rotor speed to 50r / min, internal mixer for 3-4min, the discharge temperature is 135°C, unload the mill, cool, park for 8 hours, and set aside;
[0017] S3, adding accelerator and sulfur to the material obtained in step S2, the rotor speed of the internal mixer is 50r / min, the internal mixer is kneaded for 3-4min, the discharge temperature is 135°C, the sheet is removed from the mixer, and the sheet is cooled for 8 hours to obtain a composite film for making fire boots, which is left at room temperature for 24h for standby use;
[0018] S4. Vulcanize the composite material film on a flat vulcanizer to prepare a sample, use a rubber boot making mold to make the sole and upper, and make fire boots through gluing, pressurizing and sewing processes.
[0019] Preferably, in step S4, the vulcanization conditions are 138-143°C×15MPa×(t90+2min).
[0020] The beneficial effects of the present invention are:
[0021] The composite flame retardant composed of tribromophenol, aluminum tripolyphosphate and ammonium polyphosphate has good flame retardant properties and enhances the fire protection effect of fire boots. In the fire boots produced, the fire boots use high temperature resistant felt as the shoe lining, which has low high temperature shrinkage and poor heat conduction, and plays a good heat insulation and protection effect.
[0022] The composite film obtained in this application has good flame retardancy. After contacting the flame, if combustion occurs, the continuous burning time is no more than 5 seconds. The fire boots sole is protected by steel plates, with a puncture resistance of 1100N, and the steel head protects the toes, with an impact resistance of 200 joules. The bonding strength between the fire boots sole and the upper is ≥4N / mm, the upper folding resistance: continuous flexion 125,000 times, no cracks, the sole wear resistance: the relative volume wear is no more than 250mm 3 .
[0023] The fire boots are equipped with double handles near the wearing opening, which is convenient for firefighters to quickly put on the equipment. The upper of the fire boots is equipped with high-temperature resistant fluorescent cloth strips, which can serve as a warning. In the harsh environment of the search and rescue site, the reflective strips are eye-catching and easy to search and rescue.
[0024] Stearic acid has good compatibility with EPDM rubber, which can promote the uniform dispersion of white carbon black, zinc oxide, white slip and calcium carbonate particles in rubber, which is beneficial to improve the dynamic mechanical properties and cross-linking density of composite film, and thus improve the tensile strength of fire boots. There is physical adsorption between the active groups on the surface of white slip and the molecules of 3# smoke sheet rubber, EPDM rubber and butadiene rubber, as well as chemical bonding, to form a strong composite material. When the rubber molecules are subjected to external forces, the inhomogeneous network structure disperses the stress to other molecular chains, improving the overall mechanical properties of the rubber. DETAILED DESCRIPTION
[0025] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are 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 creative work are within the scope of protection of the present invention.
[0026] Embodiment 1:
[0027] The present embodiment discloses a wear-resistant, heat-insulating, flame-retardant composite fire boot, the components of which include the following raw materials in parts by weight: 40 parts of 3# smoke sheet rubber, 15 parts of EPDM rubber, 10 parts of butadiene rubber, 10 parts of carbon black, 0.9 parts of accelerator, 5 parts of zinc oxide, 0.5 parts of stearic acid, 3.0 parts of antioxidant, 10 parts of white carbon black, 10 parts of calcium carbonate particles, 5 parts of white slip, 20 parts of composite flame retardant, and 0.8 parts of sulfur.
[0028] The accelerator is composed of accelerator M, accelerator DM and accelerator CZ, wherein: accelerator M is 0.2 parts, accelerator DM is 0.3 parts, and accelerator CZ is 0.4 parts.
[0029] The antioxidant consists of antioxidant ODA, antioxidant D37, antioxidant 2246 and antioxidant MB, wherein: antioxidant ODA 0.8 part, antioxidant D37 0.8 part, antioxidant 2246 1.0 part, antioxidant MB 0.4 part.
[0030] The composite flame retardant is composed of tribromophenol, aluminum tripolyphosphate and ammonium polyphosphate, wherein: tribromophenol is 7 parts, aluminum tripolyphosphate is 7 parts, and ammonium polyphosphate is 6 parts.
[0031] This embodiment also discloses a method for preparing a wear-resistant, heat-insulating, flame-retardant composite firefighting boot, comprising the following steps:
[0032] S1. Weigh 3# cigarette sheet rubber, EPDM rubber and cis-1,4-butadiene rubber in proportion, use an open mill to plasticate, pass through 8 times and leave for 8 hours to obtain a mixed rubber material;
[0033] S2, put the mixed rubber material obtained in S1 into an internal mixer, weigh carbon black, activator, stearic acid, antioxidant, white carbon black, filler, white slip and composite flame retardant according to proportion, adjust the rotor speed to 50r / min, internal mixer for 3min, the discharge temperature to 135°C, unload the mill, cool, park for 8 hours, and set aside;
[0034] S3, adding accelerator and sulfur to the material obtained in step S2, the rotor speed of the internal mixer is 50r / min, the internal mixer is kneaded for 3min, the discharge temperature is 135°C, the sheet is removed from the mixer, and the sheet is cooled for 8 hours to obtain a composite film for making fire boots, which is left at room temperature for 24h for standby use;
[0035] S4. Vulcanize the composite film on a flat vulcanizer to prepare samples. The vulcanization conditions are 138°C×15MPa×(t90+2min). Use a rubber boots making mold to make the sole and upper. Use gluing, pressurizing and sewing processes to make fire boots.
[0036] Embodiment 2:
[0037] The present embodiment discloses a wear-resistant, heat-insulating, flame-retardant composite fire boot, the components of which include the following raw materials in parts by weight: 70 parts of 3# smoke sheet rubber, 35 parts of EPDM rubber, 30 parts of butadiene rubber, 20 parts of carbon black, 2.3 parts of accelerator, 8 parts of zinc oxide, 1.5 parts of stearic acid, 5.8 parts of antioxidant, 25 parts of white carbon black, 28 parts of calcium carbonate particles, 25 parts of white slip, 45 parts of composite flame retardant, and 2.4 parts of sulfur.
[0038] The accelerator is composed of accelerator M, accelerator DM and accelerator CZ, wherein: accelerator M is 0.8 parts, accelerator DM is 0.9 parts, and accelerator CZ is 0.6 parts.
[0039] The antioxidant consists of antioxidant ODA, antioxidant D37, antioxidant 2246 and antioxidant MB, wherein: antioxidant ODA 1.4 parts, antioxidant D37 1.4 parts, antioxidant 2246 1.8 parts, antioxidant MB 1.2 parts.
[0040] The composite flame retardant is composed of tribromophenol, aluminum tripolyphosphate and ammonium polyphosphate, wherein the tribromophenol is 16 parts, the aluminum tripolyphosphate is 15 parts and the ammonium polyphosphate is 14 parts.
[0041] This embodiment also discloses a method for preparing a wear-resistant, heat-insulating, flame-retardant composite firefighting boot, comprising the following steps:
[0042] S1. Weigh 3# cigarette sheet rubber, EPDM rubber and cis-1,4-butadiene rubber in proportion, use an open mill to plasticate, pass through 8 times and leave for 8 hours to obtain a mixed rubber material;
[0043] S2, put the mixed rubber obtained in S1 into an internal mixer, weigh carbon black, activator, stearic acid, antioxidant, white carbon black, filler, white slip and composite flame retardant according to proportion, adjust the rotor speed to 50r / min, internal mixer for 4min, the discharge temperature to 135°C, unload the mill, cool, park for 8 hours, and set aside;
[0044] S3, adding accelerator and sulfur to the material obtained in step S2, the rotor speed of the internal mixer is 50r / min, the internal mixer is kneaded for 4min, the discharge temperature is 135°C, the sheet is removed from the mixer, and the sheet is cooled for 8 hours to obtain a composite film for making fire boots, which is left at room temperature for 24h for standby use;
[0045] S4. Vulcanize the composite film on a flat vulcanizer to prepare samples. The vulcanization conditions are 143℃×15MPa×(t90+2min). Use a rubber boots making mold to make the sole and upper. Use gluing, pressurizing and sewing processes to make fire boots.
[0046] Embodiment 3:
[0047] The present embodiment discloses a wear-resistant, heat-insulating, flame-retardant composite fire boot, the components of which include the following raw materials in parts by weight: 55 parts of 3# smoke sheet rubber, 25 parts of EPDM rubber, 20 parts of butadiene rubber, 15 parts of carbon black, 1.5 parts of accelerator, 7 parts of zinc oxide, 1.0 parts of stearic acid, 4.5 parts of antioxidant, 17 parts of white carbon black, 19 parts of calcium carbonate particles, 15 parts of white slip, 30 parts of composite flame retardant, and 1.6 parts of sulfur.
[0048] The accelerator is composed of accelerator M, accelerator DM and accelerator CZ, wherein: accelerator M is 0.5 parts, accelerator DM is 0.6 parts, and accelerator CZ is 0.4 parts.
[0049] The antioxidant consists of antioxidant ODA, antioxidant D37, antioxidant 2246 and antioxidant MB, wherein: antioxidant ODA 1.0 part, antioxidant D37 1.0 part, antioxidant 2246 1.5 parts, antioxidant MB 1.0 part.
[0050] The composite flame retardant is composed of tribromophenol, aluminum tripolyphosphate and ammonium polyphosphate, wherein: tribromophenol is 9 parts, aluminum tripolyphosphate is 10 parts, and ammonium polyphosphate is 11 parts.
[0051] This embodiment also discloses a method for preparing a wear-resistant, heat-insulating, flame-retardant composite firefighting boot, comprising the following steps:
[0052] S1. Weigh 3# cigarette sheet rubber, EPDM rubber and cis-1,4-butadiene rubber in proportion, use an open mill to plasticate, pass through 8 times and leave for 8 hours to obtain a mixed rubber material;
[0053] S2, put the mixed rubber material obtained in S1 into an internal mixer, weigh carbon black, activator, stearic acid, antioxidant, white carbon black, filler, white slip and composite flame retardant according to proportion, adjust the rotor speed to 50r / min, internal mixer for 3min, the discharge temperature to 135°C, unload the mill, cool, park for 8 hours, and set aside;
[0054] S3, adding accelerator and sulfur to the material obtained in step S2, the rotor speed of the internal mixer is 50r / min, the internal mixer is kneaded for 3min, the discharge temperature is 135°C, the sheet is removed from the mixer, and the sheet is cooled for 8 hours to obtain a composite film for making fire boots, which is left at room temperature for 24h for standby use;
[0055] S4. Vulcanize the composite film on a flat vulcanizer to prepare samples. The vulcanization conditions are 140℃×15MPa×(t90+2min). Use a rubber boots making mold to make the sole and upper. Use gluing, pressurizing and sewing processes to make fire boots.
[0056] Comparative Example 1:
[0057] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The difference between the fire boot and Example 3 is that no 3# smoke sheet glue is added.
[0058] Comparative Example 2:
[0059] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The difference between the fire boot and Example 3 is that no EPDM rubber is added.
[0060] Comparative Example 3:
[0061] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The difference between the fire boot and Example 3 is that no butadiene rubber is added.
[0062] Comparative Example 4:
[0063] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The difference between the fire boot and Example 3 is that no carbon black is added.
[0064] Comparative Example 5:
[0065] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The wear-resistant, heat-insulating, flame-retardant composite fire boot is different from Example 3 only in that no accelerant is added.
[0066] Comparative Example 6:
[0067] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The difference between the fire boot and Example 3 is that zinc oxide is not added.
[0068] Comparative Example 7:
[0069] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The fire boot is different from Example 3 only in that stearic acid is not added.
[0070] Comparative Example 8:
[0071] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The difference between the fire boot and Example 3 is that no antioxidant is added.
[0072] Comparative Example 9:
[0073] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The fire boot is different from Example 3 only in that no white carbon black is added.
[0074] Comparative Example 10:
[0075] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The fire boot is different from Example 3 only in that no calcium carbonate particles are added.
[0076] Comparative Example 11:
[0077] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The difference between the fire boot and Example 3 is that no white slip powder is added.
[0078] Comparative Example 12:
[0079] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The difference between the fire boot and Example 3 is that no composite flame retardant is added.
[0080] Comparative Example 13:
[0081] A wear-resistant, heat-insulating, flame-retardant composite fire boot. The difference between the fire boot and Example 3 is that no sulfur is added.
[0082] The fire boots obtained in the above-mentioned Examples 1-3 and Comparative Examples 1-13 were subjected to performance tests to measure the comprehensive performance of the fire boots. The results are shown in Table 1.
[0083] Table 1 Performance parameters of fire boots obtained in Examples 1-3 and Comparative Examples 1-13
[0084]
[0085]
[0086] From Table 1, we can see that:
[0087] The film of composite rubber material is flame retardant. If it burns after contacting the flame, the continuous burning time shall not exceed 5 seconds. The sole of the fire boots is protected by steel plate, which is puncture resistant to 1100N. The steel head protects the toes and has an impact resistance of 200 joules. The bonding strength between the sole and the upper of the fire boots is ≥4N / mm. The folding resistance of the upper: there should be no cracks after continuous bending for 125,000 times; the wear resistance of the sole: the relative volume wear is not more than 250mm 3 The composite flame retardant composed of tribromophenol, aluminum tripolyphosphate and ammonium polyphosphate has good flame retardant properties and enhances the fire protection effect of fire boots.
[0088] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A wear-resistant, heat-insulating, flame-retardant composite fire boot, characterized in that: The components of the fire boots include the following raw materials in parts by weight: 40-70 parts of 3# smoked rubber, 15-35 parts of EPDM rubber, 10-30 parts of butadiene rubber, 10-20 parts of carbon black, 0.9-2.3 parts of accelerator, 5-8 parts of activator, 0.5-1.5 parts of stearic acid, 3.0-5.8 parts of antioxidant, 10-25 parts of white carbon black, 10-28 parts of filling material, 5-25 parts of white slip powder, 20-45 parts of composite flame retardant and 0.8-2.4 parts of sulfur.
2. The wear-resistant, heat-insulating, flame-retardant composite firefighting boots according to claim 1 are characterized in that: The components of the fire boots include the following raw materials in parts by weight: 55 parts of 3# smoked rubber, 25 parts of EPDM rubber, 20 parts of butadiene rubber, 15 parts of carbon black, 1.6 parts of accelerator, 6 parts of activator, 1 part of stearic acid, 4.5 parts of antioxidant, 17 parts of white carbon black, 20 parts of filling material, 15 parts of white slip, 30 parts of composite flame retardant, and 1.6 parts of sulfur.
3. The wear-resistant, heat-insulating, flame-retardant composite firefighting boots according to claim 2 are characterized in that: The accelerator is composed of accelerator M, accelerator DM and accelerator CZ, wherein: accelerator M accounts for 0.2-0.8 parts, accelerator DM accounts for 0.3-0.9 parts, and accelerator CZ accounts for 0.4-0.6 parts.
4. The wear-resistant, heat-insulating, flame-retardant composite firefighting boots according to claim 2 are characterized in that: The antioxidant consists of antioxidant ODA, antioxidant D37, antioxidant 2246 and antioxidant MB, wherein: antioxidant ODA accounts for 0.8-1.4 parts, antioxidant D37 accounts for 0.8-1.4 parts, antioxidant 2246 accounts for 1.0-1.8 parts, and antioxidant MB accounts for 0.4-1.2 parts.
5. The wear-resistant, heat-insulating, flame-retardant composite firefighting boots according to claim 2 are characterized in that: The composite flame retardant is composed of tribromophenol, aluminum tripolyphosphate and ammonium polyphosphate, wherein the tribromophenol is 7-16 parts, the aluminum tripolyphosphate is 7-15 parts and the ammonium polyphosphate is 6-14 parts.
6. The wear-resistant, heat-insulating, flame-retardant composite firefighting boots according to claim 2 are characterized in that: The active agent is zinc oxide.
7. The wear-resistant, heat-insulating, flame-retardant composite firefighting boots according to claim 2 are characterized in that: The filling material is calcium carbonate particles.
8. A method for preparing the wear-resistant, heat-insulating, flame-retardant composite firefighting boots according to any one of claims 1 to 7, characterized in that: The steps include: S1. Weigh 3# cigarette sheet rubber, EPDM rubber and cis-1,4-butadiene rubber in proportion, use an open mill to plasticate, pass through 8 times and leave for 8 hours to obtain a mixed rubber material; S2, put the mixed rubber obtained in S1 into an internal mixer, weigh carbon black, activator, stearic acid, antioxidant, white carbon black, filler, white slip and composite flame retardant according to proportion, adjust the rotor speed to 50r / min, internal mixer for 3-4min, the discharge temperature is 135°C, unload the mill, cool, park for 8 hours, and set aside; S3, adding accelerator and sulfur to the material obtained in step S2, the rotor speed of the internal mixer is 50r / min, the internal mixer is kneaded for 3-4min, the discharge temperature is 135°C, the sheet is removed from the mixer, and the sheet is cooled for 8 hours to obtain a composite film for making fire boots, which is left at room temperature for 24h for standby use; S4. Vulcanize the composite material film on a flat vulcanizer to prepare a sample, use a rubber boot making mold to make the sole and upper, and make fire boots through gluing, pressurizing and sewing processes.
9. The method for preparing the wear-resistant, heat-insulating and flame-retardant composite firefighting boots according to claim 8, characterized in that: In step S4, the vulcanization conditions are 138-143°C×15MPa×(t90+2min).