A high flame retardant and low resistance fire truck tire containing a detection chip and a preparation method thereof

Abstract

The present application discloses a high flame retardant and low resistance fire truck tire containing a detection chip and its preparation method, which belongs to the technical field of fire truck tires. The tire includes a tread, a buffer layer, a cord layer and a bead, and a chip assembly is encapsulated between the tread and the buffer layer. The tread is made by mixing and vulcanizing a tread rubber composition, and the tread rubber composition includes: 30-50 parts of natural rubber, 50-70 parts of chloroprene rubber, 40-60 parts of carbon black, 15-20 parts of modified conductive filler, 10-30 parts of modified silane, 3-6 parts of activator, 1-3 parts of vulcanizing agent, 1-3 parts of antioxidant, 1-2 parts of accelerator, and 1-2 parts of scorch retarder. The fire-fighting tire prepared using the above-mentioned tread rubber composition has high flame retardancy, low resistance, and high thermal conductivity, which improves the safety factor of tire use and can be applied to various harsh environments, thereby making firefighting and rescue work safer.

Description

Technical Field

[0001] The present application relates to a highly flame-retardant and low-resistance fire truck tire containing a built-in detection chip and a preparation method thereof, belonging to the technical field of fire truck tires. Background Art

[0002] In recent years, as the main equipment for fire protection and rescue, the safety protection of fire trucks is extremely important. Therefore, ensuring the safe operation of fire trucks is the primary prerequisite for the smooth implementation of rescue work.

[0003] Since the rescue environment of fire trucks is usually harsh, the tires of fire trucks constantly rub against uneven or high-temperature road surfaces during operation, causing static electricity to accumulate on the vehicle body and increase voltage, which can easily cause fires and electric shocks, hindering the rescue work and easily causing secondary injuries in accidents.

[0004] Existing fire truck tires are mainly focused on high flame retardancy and improving the fire resistance of tires, but do not focus on how to eliminate static electricity accumulation during vehicle driving. Therefore, the safety factor is low and cannot meet fire rescue needs. Summary of the Invention

[0005] In order to solve the above problems, a high-flame-retardant and low-resistance fire truck tire with a built-in detection chip and a preparation method thereof are provided. The fire-fighting-specific tire has high flame retardancy, low resistance, and high thermal conductivity properties, which improves the safety factor of tire use and can be used in various harsh environments, thereby making firefighting and rescue work safer.

[0006] According to one aspect of the present application, a highly flame-retardant and low-resistance fire truck tire containing a built-in detection chip is provided, comprising a tread, a buffer layer, a cord layer, and a bead, wherein the chip assembly is encapsulated between the tread and the buffer layer, and the tread is made by mixing and vulcanizing a tread rubber composition, wherein the tread rubber composition comprises:

[0007] 30-50 parts of natural rubber, 50-70 parts of chloroprene rubber, 40-60 parts of carbon black, 15-20 parts of modified conductive filler, 10-30 parts of modified silane, 3-6 parts of activator, 1-3 parts of vulcanizing agent, 1-3 parts of antioxidant, 1-2 parts of accelerator, 1-2 parts of scorch retarder;

[0008] The structural formula of the modified silane is:

[0009]

[0010] Wherein R1 is selected from vinyl or propenyl, R2 and R3 are independently selected from one of linear or branched C1-C3 alkyl groups, and R4 is selected from one of linear or branched C3-C8 alkyl groups.

[0011] The fire truck tire contains a chip assembly that can predict and transmit the tire's real-time status, facilitating prompting users to perform timely maintenance and improving driving safety. The tread, obtained by mixing and vulcanizing a tread rubber composition, is a crucial component of the fire truck tire and directly impacts its performance. The tread rubber composition uses natural rubber and chloroprene rubber as its base material, allowing their molecular chains to intersect during mixing, facilitating subsequent vulcanization and crosslinking of the tire. The chloroprene rubber itself contains chlorine atoms, which impart flame retardancy and corrosion resistance to the tire, significantly improving its resistance to oil, heat, flame, and chemical agents, and extending the tire's service life.

[0012] Carbon black and modified conductive fillers can increase the conductivity and wear resistance of tires, which is conducive to forming a conductive path inside the tire, reducing the resistance of the tire, thereby eliminating static electricity generated by the vehicle during driving and improving the safety performance of the tire; the double bonds contained in the modified silane can participate in the vulcanization process of the base rubber, so that the modified silane forms a cross-linked network with natural rubber and chloroprene rubber, improving the dispersibility of the modified silane in the tire, and the sulfonate group contained in the modified silane can increase the flame retardancy and conductivity of the tire.

[0013] Optionally, the chip assembly includes an RFID chip, a temperature collector connected to the RFID chip, a resistance sensor, and a data storage for storing data, wherein the data storage is connected to the temperature collector and the resistance sensor;

[0014] Optionally, the tread includes a crown, sidewalls and shoulders, a first electrostatic induction plate is arranged in the buffer layer corresponding to the crown position, and a second electrostatic induction plate is arranged between the buffer layer and the cord layer corresponding to the sidewall position, the first electrostatic induction plate and the second electrostatic induction plate are both connected to an electrostatic collector through a communication bus, and the electrostatic collector is connected to a data storage device.

[0015] Optionally, there are multiple first electrostatic induction sheets and multiple second electrostatic induction sheets, which are evenly distributed in the circumference of the tire.

[0016] Optionally, the buffer layer is at least two layers, the first electrostatic induction sheet is distributed between the two outermost buffer layers, and the second electrostatic induction sheet is arranged between the buffer layer and the cord layer and is arranged close to the cord layer.

[0017] Optionally, the temperature collector is a module whose impedance changes with temperature, and the RFID chip and the data collector are connected via a tuning circuit to obtain the real-time temperature value of the current tire according to the correction value of the impedance change.

[0018] Optionally, the temperature collector and the resistance sensor are connected to a data storage device wirelessly or electrically. The data storage device has the function of pre-storing original data and threshold values. The data storage device is connected to a reader wirelessly. The reader can read the real-time resistance value and real-time temperature value in the data storage device, and process the data in the data storage device to obtain the instantaneous resistance change rate, the instantaneous temperature rise rate and the instantaneous thermal conductivity rate.

[0019] Optionally, the chip assembly is also provided with a voltage conversion module, a microcontroller and an energy storage device. The piezoelectric film sensor is connected to the voltage conversion module, and the voltage conversion module is connected to the energy storage device and the microcontroller respectively. The energy storage device is used to store the charge generated by the piezoelectric film sensor and supply power to the remaining components. The microcontroller is connected to the temperature collector, the resistance sensor and the data storage device.

[0020] Optionally, the chip assembly further includes a tire pressure sensor, a noise sensor, and an acceleration sensor, and the tire pressure sensor, noise sensor, and acceleration sensor are all connected to the data storage device.

[0021] Optionally, the modified conductive filler is carbon nanotubes and alumina modified by (3-aminopropyl)-triethoxysilane and phosphorus oxychloride compounds, (3-aminopropyl)-triethoxysilane is first used to aminate the carbon nanotubes and alumina to obtain an amination product, and then the amination product is reacted with the phosphorus oxychloride compound to obtain the modified conductive filler.

[0022] Optionally, the preparation method of the modified conductive filler is:

[0023] placing carbon nanotubes and aluminum oxide in a first solution containing (3-aminopropyl)-triethoxysilane, performing amination at 100-120° C. for 15-20 hours, and obtaining an aminated product after centrifugal drying;

[0024] The aminated product and the phosphorus oxychloride compound are mixed in a second solution at a molar ratio of 1:(1-1.1), reacted at room temperature for 2-4 hours, and filtered and dried to obtain the modified conductive filler.

[0025] Optionally, the first solution is selected from toluene or xylene, and the second solution is selected from chloroform.

[0026] Using carbon nanotubes and alumina as conductive fillers can improve the coordination and dispersion effect with carbon black, and improve the dispersibility of carbon black and the modified conductive filler themselves, thereby reducing the loss factor and improving the conductivity of the tire. Using (3-aminopropyl)-triethoxysilane to aminate the carbon nanotubes and alumina can, firstly, allow the surfaces of the carbon nanotubes and alumina to contain amino groups, improving their compatibility with the modified silane and facilitating their uniform dispersion along the cross-linked network of the modified silane, thereby improving the uniformity of the conductive filler dispersion in the tire. Secondly, (3-aminopropyl)-triethoxysilane can increase the number of O-Si-O bonds and alkyl groups in the tire, promoting the movement of the tire's molecular chains, improving the migration resistance of the modified conductive filler, and broadening the tire's operating temperature range. The amination product reacts with phosphorus oxychloride compounds, resulting in the presence of -P=O bonds on the surface of the modified conductive filler. This makes the modified conductive filler self-flame retardant without the addition of flame retardants, and can also improve the tire's grip and wet skid resistance.

[0027] Optionally, the weight ratio of the carbon nanotubes to alumina is (4-9):1,

[0028] The particle size of the aluminum oxide is 500-800 nm.

[0029] The alumina particle size can reduce agglomeration in the tire and promote its uniform dispersion. Combined with the weight ratio of the carbon nanotubes to the alumina, the carbon nanotubes have a diameter between 500 and 800 nm, allowing the alumina to be evenly distributed between the carbon nanotubes, filling the gaps between the carbon nanotubes. This allows the alumina to form a dense conductive and flame-retardant layer, isolating oxygen and inhibiting tire combustion. It also reduces tire resistance, eliminates static electricity promptly, and prevents electric shock. If the alumina particle size is too small, it is prone to agglomeration, increasing the variability in the conductive and flame-retardant layer's conductivity, leading to excessive static electricity accumulation in the tire that cannot be effectively eliminated, increasing the tire's local resistance. If the alumina particle size is too large, the alumina cannot effectively fill the gaps between the carbon nanotubes, resulting in a discontinuous conductive path between the alumina and the carbon nanotubes, thereby reducing conductivity and flame retardancy, increasing the tire's resistance, and reducing the safety factor.

[0030] Optionally, the phosphorus oxychloride compound is selected from at least one of phenylphosphonyl dichloride, methyl dichlorophosphate, ethyl dichlorophosphate, 1-propylphosphonium dichloride, and tert-butylphosphonium dichloride.

[0031] The above-mentioned phosphorus oxychloride compounds all contain two phosphorus oxychloride groups. Firstly, they can increase their reaction activity with the amination product, making it easier to modify carbon nanotubes and alumina. Secondly, they can increase the number of phosphorus oxychloride groups on the surface of carbon nanotubes and alumina, further improving the flame retardancy, conductivity and corrosion resistance of the tire.

[0032] Optionally, the phosphorus oxychloride compound is phenylphosphonyl dichloride and 1-propylphosphonium dichloride in a weight ratio of 1:(4-5).

[0033] Phenylphosphonyl dichloride imparts benzene rings to the surface of the modified conductive filler, thereby improving the modified stability of the modified conductive filler. The propyl group in 1-propylphosphonium dichloride increases compatibility with the modified silane, facilitating uniform dispersion of the modified conductive filler along the cross-linked network of the modified silane. The weight ratio of the two substances maximizes the synergistic effects of the flame retardant and conductive properties of the modified conductive filler while also maintaining compatibility with the modified silane, thereby improving the dispersibility and stability of the modified conductive filler in the substrate.

[0034] Optionally, the modified silane is prepared by reacting monomer A and monomer B.

[0035] The monomer A is selected from at least one of dimethyl (dimethylamino) vinyl silane, allyl (diethylamino) dimethyl silane, and allyl (diisopropylamino) dimethyl silane;

[0036] The monomer B is selected from at least one of propane sultone, butane sultone, pentane sultone, hexane sultone, heptane sultone and octane sultone.

[0037] Monomer A and monomer B react to obtain a modified silane. The double bond in the modified silane participates in the vulcanization reaction of the rubber substrate, so that the modified silane molecular chain is distributed in the substrate in the form of a branched chain. The sulfonate group contained in the modified silane molecular chain can increase the flame retardancy and acid, alkali and salt corrosion resistance of the tire. The alkyl group contained can increase the mobility of the modified silane, facilitate the extension of the molecular chain, reduce the delayed heat generation of the tire, and improve the compatibility with the modified conductive filler, so as to facilitate the uniform dispersion of the modified conductive filler.

[0038] Optionally, the preparation method of the modified silane is:

[0039] The monomer A and monomer B in a molar ratio of 1:(1-1.1) are dissolved in the third solution, and stirred at 50-130° C. for 3-5 hours to obtain the product.

[0040] Optionally, the third solution is selected from ethanol, isopropanol or acetone.

[0041] Optionally, the activator is selected from at least one of zinc oxide, magnesium oxide, and quaternary ammonium salt;

[0042] The vulcanizing agent is at least one selected from dibenzoyl peroxide, tetramethylthiuram disulfide, barium peroxide, cadmium peroxide, magnesium peroxide, zinc peroxide, bis(2,4-dichloroformyl)peroxide, di-tert-butyl peroxide, 1,4-bis-tert-butylperoxyisopropylbenzene, diisopropylbenzene peroxide, tert-butyl perbenzoate, tert-butyl isopropyl peroxide, isochloropropyl peroxide, tert-butyl isopropyl carbonate, and tert-butyl peroxycarbonate;

[0043] The accelerator is selected from at least one of zinc dibutyldithiocarbamate, hexamethylenediaminecarbamate, ethylenediaminecarbamate, and N,N'-m-phenylenebismaleimide.

[0044] According to another aspect of the present application, a method for preparing a highly flame-retardant and low-resistance fire truck tire containing a detection chip as described above is provided, comprising the following steps:

[0045] (1) mixing the natural rubber, chloroprene rubber and modified silane in one step, then adding carbon black, modified conductive filler, activator, antioxidant and scorch retarder to perform two-step mixing and then discharge the rubber to obtain a mixed rubber;

[0046] (2) mixing the rubber compound, accelerator and vulcanizing agent in three steps, and then cooling the rubber compound to obtain the tread rubber composition;

[0047] (3) The cord layer, the buffer layer and the tire bead are assembled and formed, the chip assembly is pre-placed at the corresponding position of the buffer layer, and the tread rubber composition is attached to the buffer layer to form a tire blank, and then the tire blank is vulcanized to obtain the tire.

[0048] In step (1), the modified silane and the two rubber substrates are first mixed in one step to increase the mixing uniformity among the three, which is conducive to the uniform dispersion of the modified silane in the rubber substrate. On the basis of the uniform dispersion of the modified silane, carbon black and the modified conductive filler are added and mixed in a second step. The groups contained in the modified silane can improve the dispersion uniformity of the carbon black and the modified conductive filler, so that the molecular chains of the carbon black, the modified conductive filler and the modified silane form a dense conductive flame retardant layer.

[0049] Optionally, the temperature of the one-step mixing is 40-50° C. and the time is 5-15 min;

[0050] The temperature of the two-step mixing is 130-150°C and the time is 5-10 minutes;

[0051] The temperature of the three-step mixing is 50-70° C. and the time is 2-3 minutes.

[0052] The beneficial effects of this application include but are not limited to:

[0053] 1. According to the high flame retardant and low resistance fire truck tire containing a detection chip of the present application, through the synergistic cooperation of modified conductive filler and modified silane, the modified silane can form a cross-linked network with the rubber substrate, driving the modified conductive filler to be evenly dispersed in the rubber substrate, so that the modified conductive filler and modified silane form a dense conductive flame retardant layer, which can be in direct contact with the rim, can isolate oxygen and eliminate static electricity, thereby improving the flame retardancy, corrosion resistance, thermal conductivity, wear resistance and mechanical strength of the tire, and reducing the resistance of the tire, thereby making firefighting and fire rescue safer.

[0054] 2. According to the high flame retardant and low resistance fire truck tire containing a detection chip in the present application, modified conductive fillers are prepared using carbon nanotubes and alumina. The ratio and parameters of the two substances can synergistically affect the performance of the conductive flame retardant layer. Within the scope specified in the present application, on the basis of ensuring the conductive, flame retardant and anti-corrosion effects, it can also improve the mechanical properties of the tire, reduce rolling resistance and hysteresis heat generation.

[0055] 3. According to the highly flame-retardant and low-resistance fire truck tire containing a detection chip of the present application, the carbon nanotubes and alumina are first aminated and then reacted with phosphorus oxychloride compounds, which can increase the dispersion uniformity of the modified conductive filler and increase the compatibility with modified silane, thereby facilitating the improvement of the density of the conductive flame-retardant layer, thereby effectively eliminating static electricity and isolating oxygen.

[0056] 4. According to the highly flame-retardant and low-resistance fire truck tire containing a built-in detection chip of the present application, the modified silane participates in the vulcanization reaction of the rubber substrate, thereby introducing flame-retardant groups into the rubber molecular chain. The flame-retardant effect can be achieved without the need to add additional flame retardants. The modified silane has a large number of alkyl groups, which can increase the movement activity of the rubber molecular chain, thereby improving the elasticity of the tire and expanding the temperature range of the tire. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0058] Figure 1 Schematic diagram of the distribution of the first electrostatic induction sheet and the second electrostatic induction sheet involved in the embodiment of the present application.

[0059] List of parts and reference numerals:

[0060] 1. Fire truck tire; 2. Static collector; 3. First static induction plate; 4. Second static induction plate; 5. Communication bus. DETAILED DESCRIPTION

[0061] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0062] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0063] Example 1

[0064] This embodiment relates to a highly flame-retardant, low-resistance fire truck tire containing a built-in detection chip and a preparation method thereof. The tire includes a tread, a buffer layer, a cord layer, and a bead. The chip assembly is encapsulated between the tread and the buffer layer. The tread is made by mixing a tread rubber composition, which includes: 40 parts of natural rubber, 60 parts of chloroprene rubber, 50 parts of carbon black, 18 parts of modified conductive filler, 25 parts of modified silane, 4 parts of zinc oxide activator, 2 parts of tetramethylthiuram disulfide vulcanizing agent, 2 parts of antioxidant, 2 parts of N,N'-m-phenylene bismaleimide accelerator, and 2 parts of scorch retarder.

[0065] The modified silane is prepared by dissolving dimethyl(dimethylamino)vinylsilane in isopropanol, heating the mixture to 90°C under a nitrogen atmosphere, and then adding propane sultone dropwise in a molar ratio of dimethyl(dimethylamino)vinylsilane to propane sultone of 1:1.1. The mixture is stirred and reacted for 4 hours to obtain the modified silane.

[0066] The modified conductive filler is prepared by placing carbon nanotubes and alumina in a weight ratio of 6:1 in a xylene solution containing (3-aminopropyl)-triethoxysilane, with an alumina particle size of 600 nm, stirring at 100°C for 20 hours, centrifuging and drying to obtain an amination product, then placing the amination product in a chloroform solution, and dropwise adding phenylphosphonic dichloride and 1-propylphosphonic dichloride in a weight ratio of 1:4, the molar ratio of the amination product to the sum of phenylphosphonic dichloride and 1-propylphosphonic dichloride being 1:1, reacting under nitrogen at room temperature for 4 hours, and filtering and drying to obtain the result.

[0067] The tire preparation method comprises the following steps:

[0068] (1) Natural rubber, chloroprene rubber and modified silane are mixed in one step at 40°C for 10 minutes, and then carbon black, modified conductive filler, activator, antioxidant and scorch retarder are added and mixed in two steps at 140°C for 10 minutes, and then the rubber is discharged to obtain a mixed rubber;

[0069] (2) mixing the rubber compound, the accelerator, and the vulcanizing agent in three steps at 60° C. for 3 min, draining the rubber compound and cooling the compound to obtain a tread rubber composition;

[0070] (3) The cord layer, the buffer layer and the tire bead are assembled and formed, the chip assembly is pre-placed at the corresponding position of the buffer layer, and the tread rubber composition is attached to the buffer layer to form a tire blank, and then the tire blank is vulcanized to obtain tire 1#.

[0071] Example 2

[0072] This embodiment relates to a highly flame-retardant, low-resistance fire truck tire containing a built-in detection chip and a preparation method thereof. The tire includes a tread, a buffer layer, a cord layer, and a bead. The chip assembly is encapsulated between the tread and the buffer layer. The tread is made by mixing a tread rubber composition, which includes: 30 parts of natural rubber, 70 parts of chloroprene rubber, 40 parts of carbon black, 20 parts of modified conductive filler, 30 parts of modified silane, 3 parts of magnesium oxide activator, 1 part of dibenzoyl peroxide vulcanizing agent, 3 parts of antioxidant, 2 parts of zinc dibutyl dithiocarbamate accelerator, and 1 part of anti-scorch agent.

[0073] The modified silane is prepared by dissolving allyl (diethylamino) dimethyl silane in isopropanol, heating the mixture to 90°C under a nitrogen atmosphere, and then adding butane sultone dropwise in a molar ratio of allyl (diethylamino) dimethyl silane to butane sultone of 1:1. The mixture is stirred and reacted for 4 hours to obtain the modified silane.

[0074] The modified conductive filler is prepared by placing carbon nanotubes and alumina in a weight ratio of 4:1 in a xylene solution containing (3-aminopropyl)-triethoxysilane, with an alumina particle size of 800 nm, stirring at 120°C for 15 hours, centrifuging and drying to obtain an amination product, then placing the amination product in a chloroform solution, adding methyl dichlorophosphate dropwise, with a molar ratio of the amination product to methyl dichlorophosphate of 1:1.1, reacting under nitrogen at room temperature for 4 hours, and filtering and drying to obtain the result.

[0075] The tire preparation method comprises the following steps:

[0076] (1) Natural rubber, chloroprene rubber and modified silane are mixed in one step at 50°C for 5 minutes, and then carbon black, modified conductive filler, activator, antioxidant and scorch retarder are added and mixed in two steps at 130°C for 10 minutes, and then the rubber is discharged to obtain a mixed rubber;

[0077] (2) mixing the rubber compound, the accelerator, and the vulcanizing agent in three steps at 70° C. for 2 min, draining the rubber compound and cooling the compound to obtain a tread rubber composition;

[0078] (3) The cord layer, the buffer layer and the tire bead are assembled and formed, the chip assembly is pre-placed at the corresponding position of the buffer layer, and the tread rubber composition is attached to the buffer layer to form a tire blank, and then the tire blank is vulcanized to obtain tire 2#.

[0079] Example 3

[0080] This embodiment relates to a highly flame-retardant, low-resistance fire truck tire containing a built-in detection chip and a preparation method thereof. The tire includes a tread, a buffer layer, a cord layer, and a bead. The chip assembly is encapsulated between the tread and the buffer layer. The tread is made by mixing a tread rubber composition, which includes: 50 parts of natural rubber, 50 parts of chloroprene rubber, 60 parts of carbon black, 15 parts of modified conductive filler, 10 parts of modified silane, 6 parts of a quaternary ammonium salt activator, 3 parts of a tetramethylthiuram disulfide vulcanizing agent, 1 part of an antioxidant, 1 part of a hexamethylenediamine carbamate accelerator, and 1 part of a scorch retarder.

[0081] The modified silane is prepared by dissolving allyl (diisopropylamino) dimethylsilane in isopropanol, heating the mixture to 90°C under a nitrogen atmosphere, and then adding hexasultone dropwise in a molar ratio of allyl (diisopropylamino) dimethylsilane to hexasultone of 1:1.1. The mixture is stirred and reacted for 5 hours to obtain the obtained product.

[0082] The modified conductive filler is prepared by placing carbon nanotubes and alumina in a weight ratio of 9:1 in a xylene solution containing (3-aminopropyl)-triethoxysilane, with an alumina particle size of 500 nm, stirring at 100°C for 20 hours, centrifuging and drying to obtain an amination product, then placing the amination product in a chloroform solution, adding tert-butyl dichlorophosphinoyl dropwise, with a molar ratio of the amination product to tert-butyl dichlorophosphinoyl of 1:1, reacting under nitrogen at room temperature for 4 hours, and filtering and drying to obtain the result.

[0083] The tire preparation method comprises the following steps:

[0084] (1) Natural rubber, chloroprene rubber and modified silane are mixed in one step at 40°C for 15 minutes, and then carbon black, modified conductive filler, activator, antioxidant and scorch retarder are added and mixed in two steps at 150°C for 5 minutes, and then the rubber is discharged to obtain a mixed rubber;

[0085] (2) mixing the rubber compound, accelerator and vulcanizing agent in three steps at 50° C. for 3 min, draining and cooling the rubber compound to obtain a tread rubber composition;

[0086] (3) The cord layer, the buffer layer and the tire bead are assembled and formed, the chip assembly is pre-placed at the corresponding position of the buffer layer, and the tread rubber composition is attached to the buffer layer to form a tire blank, and then the tire blank is vulcanized to obtain tire 3#.

[0087] Example 4

[0088] The difference between this embodiment and embodiment 1 is that the modified conductive filler is only modified carbon nanotubes and does not contain aluminum oxide. The modification steps of the modified conductive filler, the number of other components and the tire preparation method are the same as those in embodiment 1, and tire 4# is obtained.

[0089] Example 5

[0090] The difference between this embodiment and embodiment 1 is that the modified conductive filler is obtained by modifying carbon nanotubes and aluminum oxide in a weight ratio of 1:6. The modification steps of the modified conductive filler, the number of other components and the tire preparation method are the same as those in embodiment 1, and tire 5# is obtained.

[0091] Example 6

[0092] This example differs from Example 1 in that the modified conductive filler is modified using a different procedure. Specifically, carbon nanotubes and aluminum oxide (alumina) in a weight ratio of 6:1 are placed in a xylene solution containing (3-aminopropyl)-triethoxysilane, with an alumina particle size of 600 nm. The mixture is stirred at 100°C for 20 hours for amination, followed by centrifugation and drying. No phosphorus oxychloride compound is used for modification. The remaining component quantities and tire preparation method are the same as in Example 1, resulting in tire #6.

[0093] Example 7

[0094] The difference between this embodiment and embodiment 1 is that glutaryl dichloride is used instead of phenylphosphonyl dichloride and 1-propylphosphonium dichloride. The modification steps of the remaining modified conductive filler, the number of components and the tire preparation method are the same as those in embodiment 1, and tire 7# is obtained.

[0095] Example 8

[0096] The difference between this embodiment and embodiment 1 is that the alumina particle size is 1 μm, and the proportions of the other components and the tire preparation method are the same as those in embodiment 1, thus obtaining tire 8#.

[0097] Example 9

[0098] The difference between this embodiment and embodiment 1 is that the weight ratio of phenylphosphonic dichloride to 1-propylphosphonium dichloride is 4:1, and the modification steps of the remaining modified conductive fillers, the number of components, and the tire preparation method are the same as those in embodiment 1, thus obtaining tire 9#.

[0099] Example 10

[0100] The difference between this embodiment and embodiment 1 is that the modified silane is 10 parts, and the parts of the other components and the tire preparation method are the same as those in embodiment 1, so as to obtain tire 10#.

[0101] Example 11

[0102] The difference between this embodiment and embodiment 1 is that octane sultone is used instead of propane sultone, and the parts of the other components and the tire preparation method are the same as those in embodiment 1, so as to obtain tire 11#.

[0103] Comparative Example 1

[0104] The difference between this comparative example and Example 1 is that unmodified dimethyl (dimethylamino) vinyl silane is used instead of modified silane, and the parts of the remaining components and the tire preparation method are the same as those in Example 1, thus obtaining comparative tire D1#.

[0105] Comparative Example 2

[0106] This comparative example differs from Example 1 in the modification steps for the modified silane: Specifically, dimethyl(dimethylamino)vinylsilane was dissolved in isopropyl alcohol, heated to 70°C under a nitrogen atmosphere, and then dichlorobutane was added dropwise at a molar ratio of 1:1.1. The reaction was stirred for 4 hours to yield the modified silane. The remaining component quantities and tire preparation method were the same as in Example 1, yielding comparative tire D2#.

[0107] Comparative Example 3

[0108] The difference between this comparative example and Example 1 is that trimethylsilyldiethylamine is used instead of dimethyl(dimethylamino)vinylsilane, and the parts of the other components and the tire preparation method are the same as those in Example 1, so as to obtain comparative tire D3#.

[0109] Comparative Example 4

[0110] The difference between this comparative example and Example 1 is that the modified conductive filler is 10 parts, and the parts of the other components and the tire preparation method are the same as those in Example 1, so as to obtain comparative tire D4#.

[0111] Comparative Example 5

[0112] The difference between this comparative example and Example 1 is that the tire preparation method is different, specifically:

[0113] (1) Natural rubber and chloroprene rubber are mixed in one step at 40°C for 10 minutes, and then modified silane, carbon black, modified conductive filler, activator, antioxidant and scorch retarder are added and mixed in two steps at 140°C for 10 minutes, and then the rubber is discharged to obtain a mixed rubber;

[0114] (2)(3) Same as Example 1, that is, comparison tire D5# is obtained.

[0115] Test Example 1 Flame retardant performance test

[0116] 1. Oxygen Index: Tested in accordance with GB / T 10707-2008 Method A. Cut the tire into strips measuring 108mm x 6.5mm x 3.25mm. Tested at 23±2°C, 50±55°C relative humidity.

[0117] 2. Vertical combustion: The test is conducted using the GB / T 10707-2008 vertical combustion method. The tire is cut into strips measuring 130mm*13mm*3mm. The tire is exposed to the heat for at least 16 hours at a temperature of 23±2°C and a humidity of 50±10%.

[0118] The tread rubber compositions obtained in the examples and comparative examples were vulcanized separately to obtain tread samples. The tread samples were subjected to the above-mentioned test. Ten parallel experiments were performed for each group, and the average value was taken. The results are shown in Table 1 below, where t1 refers to the flaming combustion time of the sample after the flame is applied for the first time, t2 refers to the flaming combustion time of the sample after the flame is applied for the second time, and tg refers to the flameless combustion time of the sample after the flame is applied for the second time.

[0119] Table 1

[0120]

[0121]

[0122] Test Example 2 Mechanical, Electrical and Thermal Conductivity Tests

[0123] The tread rubber compositions obtained in the examples and comparative examples were vulcanized separately to obtain tread samples, and the tread samples were tested for tensile stress, strength, rebound, wear index, hardness, electrical resistance, and thermal conductivity in accordance with national standards. The dynamic viscoelastic properties of the vulcanized rubber were tested using DMA, and the DMA testing conditions were: 60°C strain sweep (static 10%, dynamic 0.1% to 5%, f = 10 Hz). The tire samples were measured using a high resistance meter in accordance with GB / T1692-2008. The results are shown in Tables 2 and 3.

[0124] Table 2

[0125]

[0126]

[0127] Table 3

[0128]

[0129] According to the data obtained from the above-mentioned Test Example 1 and Test Example 2, the fire truck tire prepared by the tread rubber composition adopted in this application can improve the flame retardancy, corrosion resistance, thermal conductivity, wear resistance and mechanical strength of the tire, reduce the resistance of the tire, and promptly eliminate the static electricity accumulation generated by the tire during use, thereby avoiding electric shock, meeting the rescue needs of the fire, and improving the safety during the rescue process.

[0130] Example 12

[0131] This embodiment relates to the specific structure of a highly flame-retardant, low-resistance fire truck tire containing a built-in detection chip. The fire truck tire encapsulates a chip component between the tread and the buffer layer, and can promptly obtain parameters such as the temperature, tire pressure, and resistance of the fire truck tire, thereby determining whether the fire truck tire is in a safe driving state and reminding firefighters to take appropriate actions in a timely manner based on the tire status.

[0132] For example, when a fire truck stops at a fire scene, if the ground temperature is high, the heat from the ground will be transferred to the fire truck tires, causing changes in the fire truck's tire temperature, tire pressure, and resistance. The chip component will wirelessly transmit real-time tire temperature, tire pressure, resistance, and other information to the fire truck's reader. The reader can read and write the information in the chip component through application software, thereby presenting the information to firefighters, who can take corresponding actions after seeing the information.

[0133] Specifically, the chip assembly is pre-placed in the tire blank during the preparation of the fire truck tire, and can be integrally formed into the tire as the tire blank is vulcanized. The vulcanization process will not cause damage to the chip assembly and detection sensitivity.

[0134] As an embodiment, the chip assembly includes an RFID chip, a temperature collector connected to the RFID chip, a resistance sensor, and a data storage for storing data, wherein the data storage is connected to the temperature collector and the resistance sensor.

[0135] During actual use, fire trucks may encounter road conditions with high road temperatures or those with spreading fires. These conditions increase tire temperature and generate static electricity, which triggers the transmission of real-time tire temperature and resistance values ​​to a data storage device via a temperature collector and resistance sensor. The data storage device pre-stores raw data and thresholds. Once connected to a reader, the reader can read the real-time resistance and temperature values ​​stored in the data storage device. This data allows for real-time monitoring of tire changes, providing safety warnings for tire blowouts, fires, or electric shocks. For example, if the fire truck's tire temperature or resistance is detected to be about to exceed a threshold, it can be determined that the fire truck is no longer suitable for that location, allowing firefighters to move the vehicle to a safe location before continuing with rescue operations.

[0136] The data collected by the resistance sensor can firstly represent the real-time resistance value and instantaneous resistance change rate of the fire truck tire, judge whether there is static electricity accumulation in the fire truck tire during rescue work, and reduce the probability of fire or electric shock caused by static electricity accumulation in the fire truck tire; secondly, with the long-term use of the fire truck tire, the overall resistivity of the tire changes. The resistivity of the fire truck tire can be compared with the original factory data pre-stored in the data storage to judge the degree of tire wear, thereby judging whether the fire truck tire can continue to be used and statistically calculating the remaining useful time of the fire truck tire, so as to remind firefighters to replace the fire truck tire in time.

[0137] Specifically, the connection method between the temperature collector and the resistance sensor and the data storage device can adopt the existing methods in the prior art, such as wireless connection or electrical connection. And the power supply method of the above-mentioned chip assembly can adopt the existing methods, such as obtaining the energy required for work by the magnetic field generated by the reader or setting a piezoelectric film sensor in the tire, and generating charge by the deformation of the piezoelectric film sensor. In this way, the chip assembly is also provided with a voltage conversion module, a microcontroller and an energy storage device. The piezoelectric film sensor is connected to the voltage conversion module, and the voltage conversion module is respectively connected to the energy storage device and the microcontroller. The energy storage device is used to store the charge generated by the piezoelectric film sensor and supply power to the remaining components. The microcontroller is connected to the temperature collector, the resistance sensor and the data storage device. Through the above-mentioned different methods, the normal operation of the chip assembly of the present application can be achieved, thereby realizing the safe monitoring of the fire truck tires and improving the safety of the fire truck during use.

[0138] In a preferred embodiment, the temperature collector is a temperature-measuring material whose impedance changes with temperature. The RFID chip and the temperature collector are connected via a tuned circuit to obtain the current tire temperature based on the correction value of the impedance change. The RFID chip can select an electronic tag with a specific frequency band as needed. When the temperature collector and the RFID chip are connected, the current tire temperature can be corrected based on the RFID chip's impedance value, thereby improving the accuracy of tire temperature detection. Furthermore, under the above-mentioned configuration, the data collected by the temperature collector is transmitted to a data storage device. A reader reads the data from the data storage device and, after processing by application software, calculates the instantaneous temperature rise rate and instantaneous thermal conductivity of the fire truck tire. When the instantaneous data exceeds a certain value, even if the real-time tire temperature has not yet exceeded the threshold, an alarm is issued to the firefighters, allowing sufficient time for rescue operations and adjustments.

[0139] Similarly, after the data collected by the resistance sensor is transmitted to the data storage device, the reader and application software process the data in the data storage device to obtain the instantaneous resistance change rate to determine the resistance development trend inside the fire truck tire and the static electricity accumulation inside the tire. Based on the real-time resistance data and the instantaneous resistance change rate, a comprehensive assessment of the fire truck tire is conducted to remind firefighters to take corresponding measures as soon as possible.

[0140] As an embodiment, the chip assembly also includes a tire pressure sensor, a noise sensor and an acceleration sensor. The tire pressure sensor, noise sensor and acceleration sensor are all connected to the data storage device. Through the above settings, the tire pressure value, noise value and acceleration value of the fire truck tire can be obtained in time, thereby increasing the basis for judging the safety of the fire truck tire.

[0141] refer to Figure 1 As an embodiment, the tread includes a crown, a sidewall and a shoulder. A first electrostatic induction sheet 3 is provided in the buffer layer at the corresponding crown position, and a second electrostatic induction sheet 4 is provided between the buffer layer and the cord layer at the corresponding sidewall position. The first electrostatic induction sheet 3 and the second electrostatic induction sheet 4 are both connected to the electrostatic collector 2 through a communication bus 5, and the electrostatic collector 2 is connected to the data storage.

[0142] The first electrostatic induction sheet 3 and the second electrostatic induction sheet 4 can detect the analog signal of the fire truck tire 1 and transmit the signal to the digital electrostatic collector 2 through the signal amplifier and the data processor, so as to know the static electricity accumulation at different positions of the fire truck tire 1, and cooperate with the resistance sensor to obtain the real-time conductivity of the fire truck tire 1. When the static electricity value transmitted by the electrostatic collector 2 received by the reader exceeds the threshold, the reader also reads the real-time resistance value and instantaneous resistance change rate transmitted by the resistance sensor. After comprehensive judgment, if it is found that the value exceeds the standard, an early warning will be issued to the firefighters to remind them to perform safe static electricity handling operations.

[0143] As a preferred embodiment, the first electrostatic induction sheet 3 and the second electrostatic induction sheet 4 can be provided in multiple numbers and evenly distributed in the circumferential direction of the tire. Figure 1 Taking the first electrostatic induction sheet 3 and the second electrostatic induction sheet 4 as an example, four first electrostatic induction sheets 3 can be set at corresponding positions of the tire crown, and one second electrostatic induction sheet 4 can be set at corresponding positions of the tire sidewall and on both sides of the first electrostatic induction sheet 3. The first electrostatic induction sheet 3 and the second electrostatic induction sheet 4 are connected through a communication bus 5. Figure 1The first and second electrostatic induction plates 3 and 4 form a closed loop via a communication bus 5, enabling circumferential static data detection of the fire truck tire 1. The multiple distributed first and second electrostatic induction plates 3 and 4 ensure that damage to one does not affect the normal operation of the remaining plates, thereby extending the detection time of the fire truck tire 1. The data collected from multiple plates can also be compared with each other, increasing the accuracy of the fire truck tire 1 detection.

[0144] As a specific embodiment, the first electrostatic induction sheet 3 is distributed between the two outermost buffer layers, and the second electrostatic induction sheet 4 is arranged between the buffer layer and the carcass layer, and is arranged close to the carcass layer. During the molding process of the above-mentioned fire truck tire 1, the first electrostatic induction sheet 3 and the second electrostatic induction sheet 4 can be installed in the corresponding positions.

[0145] Specifically, the chip component can be installed at any position in the circumference of the tire as needed, which is well known to those skilled in the art. For example, the chip component is installed at the corresponding position of the sidewall, and the chip component is wrapped by the tread rubber composition at the sidewall position. For another example, the chip component is installed at the corresponding position of the crown, and the chip component is wrapped by the tread rubber composition at the crown position. Chip components can also be set at the corresponding positions of the sidewall and the crown to detect information at different positions of the tire, and the reader and application processing software can also compare and process the tire information at different positions to make a comprehensive judgment. The processing of the above-mentioned setting positions, readers and application processing software can all adopt existing methods in the prior art and will not be repeated here.

[0146] The foregoing is merely an embodiment of the present application, and the scope of protection of the present application is not limited by these specific embodiments, but is determined by the claims of the present application. For those skilled in the art, the present application may have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc. made within the technical ideas and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A high flame retardant and low resistance fire truck tire containing a detection chip, comprising a tread, a buffer layer, a cord layer and a bead, wherein a chip component is encapsulated between the tread and the buffer layer, characterized in that: The tread is made by mixing and vulcanizing a tread rubber composition, wherein the tread rubber composition comprises: 30-50 parts of natural rubber, 50-70 parts of chloroprene rubber, 40-60 parts of carbon black, 15-20 parts of modified conductive filler, 10-30 parts of modified silane, 3-6 parts of activator, 1-3 parts of vulcanizing agent, 1-3 parts of antioxidant, 1-2 parts of accelerator and 1-2 parts of scorch retarder; The structural formula of the modified silane is: ， Wherein R1 is selected from vinyl or propenyl, R2 and R3 are independently selected from one of linear or branched C1-C3 alkyl groups, and R4 is selected from one of linear or branched C3-C8 alkyl groups.

2. The high flame retardant and low resistance fire truck tire with a built-in detection chip according to claim 1, characterized in that: The chip assembly includes an RFID chip, a temperature collector connected to the RFID chip, a resistance sensor, and a data storage for storing data. The data storage is connected to the temperature collector and the resistance sensor.

3. The high flame retardant and low resistance fire truck tire with a built-in detection chip according to claim 1, characterized in that: The modified conductive filler is carbon nanotubes and aluminum oxide modified by (3-aminopropyl)-triethoxysilane and phosphorus oxychloride compounds. (3-aminopropyl)-triethoxysilane is first used to aminate the carbon nanotubes and aluminum oxide to obtain an amination product, and then the amination product is reacted with the phosphorus oxychloride compound to obtain the modified conductive filler.

4. The high flame retardant and low resistance fire truck tire with a built-in detection chip according to claim 3, characterized in that: The preparation method of the modified conductive filler is: placing carbon nanotubes and aluminum oxide in a first solution containing (3-aminopropyl)-triethoxysilane, performing amination at 100-120° C. for 15-20 hours, and obtaining an aminated product after centrifugal drying; The aminated product and the phosphorus oxychloride compound are mixed in a second solution at a molar ratio of 1:(1-1.1), reacted at room temperature for 2-4 hours, and filtered and dried to obtain the modified conductive filler.

5. The high flame retardant and low resistance fire truck tire with a built-in detection chip according to claim 3, characterized in that: The phosphorus oxychloride compound is at least one selected from phenylphosphonyl dichloride, methyl dichlorophosphate, ethyl dichlorophosphate, 1-propylphosphonium dichloride and tert-butylphosphonium dichloride.

6. The high flame retardant and low resistance fire truck tire with built-in detection chip according to claim 5, characterized in that: The phosphorus oxychloride compound is phenylphosphonic dichloride and 1-propylphosphonium dichloride in a weight ratio of 1:(4-5).

7. The high flame retardant and low resistance fire truck tire with a built-in detection chip according to claim 1, characterized in that: The modified silane is prepared by reacting monomer A and monomer B, wherein monomer A is selected from at least one of dimethyl (dimethylamino) vinyl silane, allyl (diethylamino) dimethyl silane and allyl (diisopropylamino) dimethyl silane; The monomer B is selected from at least one of propane sultone, butane sultone, pentane sultone, hexane sultone, heptane sultone and octane sultone.

8. The high flame retardant and low resistance fire truck tire with built-in detection chip according to claim 7, characterized in that: The preparation method of the modified silane is: The monomer A and monomer B in a molar ratio of 1: (1-1.1) are dissolved in the third solution, and stirred at 50-130° C. for 3-5 hours to obtain the product.

9. A method for preparing a high flame retardant and low resistance fire truck tire containing a detection chip, for preparing the high flame retardant and low resistance fire truck tire containing a detection chip according to any one of claims 1 to 8, characterized in that: The steps include: (1) mixing the natural rubber, chloroprene rubber and modified silane in one step, then adding carbon black, modified conductive filler, activator, antioxidant and anti-scorch agent to mix in two steps and then discharge the rubber to obtain a mixed rubber; (2) mixing the rubber compound, accelerator and vulcanizing agent in three steps, and then cooling the rubber compound to obtain the tread rubber composition; (3) The cord layer, the buffer layer and the tire bead are assembled and formed, the chip assembly is pre-placed at the corresponding position of the buffer layer, and the tread rubber composition is attached to the buffer layer to form a tire blank, and then the tire blank is vulcanized to obtain the tire.

10. The method for preparing a highly flame-retardant and low-resistance fire truck tire containing a detection chip according to claim 9, characterized in that: The temperature of the one-step mixing is 40-50°C and the time is 5-15 minutes; The temperature of the two-step mixing is 130-150°C and the time is 5-10 minutes; The temperature of the three-step mixing is 50-70° C. and the time is 2-3 minutes.

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