Composite tire and method for manufacturing the same

Abstract

The invention discloses a composite tire and a manufacturing method thereof. The method comprises surface pretreatment of a tire carcass, configuration of a tread treatment agent, and casting and molding the composite tire tread using a unique process. The method has the characteristics of simple manufacturing process and low cost. The manufactured composite tire has a series of outstanding advantages such as good elasticity, low rolling resistance, low fuel consumption, good tread wear resistance, etc., has high cost performance, and is easy to industrialize.

Description

Technical Field

[0001] The invention relates to the technical field of composite tire manufacturing, in particular to a composite tire and a manufacturing method thereof. Background Art

[0002] The so-called green tires refer to radial tires with low rolling resistance, low fuel consumption and low exhaust emissions. At the same time, in order to ensure the performance of the green tires, they must have both high anti-slip performance and good wear resistance. Compared with ordinary tires, green tires can reduce rolling resistance by 22-25% and save 3-8% fuel. Since Michelin of France announced in 1991 that it would vigorously develop green tires, major tire companies in Europe, the United States and Japan have successively accelerated the pace of research and development of green tires. At present, green tires have become a hot topic in the development of the tire industry.

[0003] Although many companies have conducted research on the application of polyurethane materials in tire manufacturing, the presence of relatively strong polar groups such as carbamate and polyurea in the polyurethane molecular chain leads to larger hydrogen bonds between and within the molecular chains, making the movement of the molecular chains more difficult, and generating a lot of internal heat under dynamic use conditions. In addition, polyurethane has the typical characteristics of poor thermal conductivity of polymer materials. The heat generated during long-term use is easily accumulated in the material, resulting in excessive temperature rise and ultimately overheating of the material, resulting in damage and failure. This has greatly restricted the application of polyurethane materials in tire manufacturing. Therefore, the polyurethane tires currently on the market are all low-speed tires. Summary of the invention

[0004] Based on this, the purpose of the present invention is to solve the shortcomings of cast polyurethane elastomer in the application of composite tire tread materials, and provide a composite tire and a method for manufacturing the same.

[0005] In a first aspect, an embodiment of the present invention provides a method for manufacturing a composite tire, comprising:

[0006] S1. Grinding the area where the tire carcass and the cast polyurethane elastomer are bonded, cleaning and drying the area for standby use, and completing the surface pretreatment of the tire carcass;

[0007] S2, preparing a mixed solution of trichloroisocyanuric acid and an acetone / butanone / ethyl acetate mixed solvent treated with anhydrous calcium chloride, and preparing a tread treatment agent using the mixed solution and a multi-graft adhesive solution;

[0008] S3, spraying or brushing the tread treatment agent on the prepared tire tread for surface modification;

[0009] S4. The surface-modified tire tread is casted with a modified polyurethane prepolymer or a linear polyurethane prepolymer to obtain a finished composite tire; wherein the preparation of the modified polyurethane prepolymer comprises: selecting a raw material of a casting polyurethane elastomer, preparing a polyurethane prepolymer with the selected raw material of the casting polyurethane elastomer, and modifying the polyurethane prepolymer to obtain a modified polyurethane prepolymer; the preparation of the linear polyurethane prepolymer comprises: preparing the linear polyurethane prepolymer with the selected raw material of the casting polyurethane elastomer and citing a supramolecular structure.

[0010] In the technical solution provided in the embodiment of the present invention, a composite tire tread is cast by adopting a unique process. This composite tire has a series of outstanding advantages such as good elasticity, low rolling resistance, low fuel consumption, and good tread wear resistance. In addition, the manufacturing process is simple, the cost is low, the composite tire has a high cost performance, and is easy to industrialize.

[0011] In a possible design, the multi-graft adhesive solution includes methyl methacrylate / acrylic acid / butyl acrylate / hydroxypropyl acrylate / chloroprene rubber;

[0012] A mixed solution of trichloroisocyanuric acid and an acetone / butanone / ethyl acetate mixed solvent treated with anhydrous calcium chloride is prepared, and a tread treatment agent is prepared using the mixed solution and a multi-graft adhesive solution, including:

[0013] Adding 3 to 15 parts by weight of the trichloroisocyanuric acid to 85 to 97 parts by weight of the acetone / butanone / ethyl acetate mixed solvent treated with anhydrous calcium chloride, and stirring rapidly to dissolve the mixture uniformly to obtain the mixed solution;

[0014] 10 to 30 parts by weight of the multi-graft adhesive solution is added to the mixed solution, and the mixture is stirred and mixed to obtain the tread treatment agent.

[0015] In a possible design, the tread treatment agent is sprayed or brushed on the prepared tire tread for surface modification, including:

[0016] The tread treatment agent is evenly sprayed or brushed on the prepared tire tread, and the tire is left standing for 0.5 to 12 hours in an environment with a temperature of 60 to 80° C. and a humidity of 30 to 70%, thereby completing the surface modification treatment of the tire tread.

[0017] In one possible design, raw materials for the cast polyurethane elastomer are selected, including:

[0018] Selecting a material composed of a polyurethane prepolymer prepared from an oligomer polyol-isocyanate system and a small molecule diol / diamine as the raw material of the cast polyurethane elastomer;

[0019] Wherein, the oligomer polyol-isocyanate type system can be selected from system A or system B;

[0020] The system A is a prepolymer of polycaprolactone / tetrahydrofuran copolymer glycol / polycaprolactone glycol / polytetrahydrofuran glycol / polycarbonate glycol / hydroxy-terminated polybutadiene polyol-diphenylmethane diisocyanate system, wherein the molecular weight of the polyol / diol is between 600 and 5000; the chain extender is a low molecular weight diol / triol; and the chain extension coefficient is between 0.93 and 1.02;

[0021] The system B is a prepolymer of polycaprolactone / tetramethylene glycol / polycaprolactone glycol / polytetramethylene glycol / polycarbonate glycol / hydroxy-terminated polybutadiene polyol-p-phenylene diisocyanate system, wherein the molecular weight of the polyol / diol is between 600 and 5000; the chain extender is a low molecular weight diol / triol; and the chain extension coefficient is between 0.93 and 1.02.

[0022] In a possible design, a polyurethane prepolymer is prepared using selected raw materials of a cast polyurethane elastomer, including:

[0023] An oligomer polyol or a mixture of multiple oligomer diols is dehydrated at -0.095-0.098Mpa vacuum and 100-135°C for 14 hours; after cooling to below 40°C, isocyanate is slowly added in batches, stirred at a uniform speed for 0.5 hour, and slowly heated to 75-85°C after the temperature is stabilized, during which dry nitrogen is introduced, and the reaction conditions are kept stable for 2-3 hours. After stopping stirring, a prepolymer product is obtained, and the isocyanate content in the prepolymer is designed to be between 3 and 6.2.

[0024] In a possible design, the polyurethane prepolymer is modified, including:

[0025] After drying, 1414 para-aramid fibrid with a diameter of about 10 μm, a length of 0.5 to 2 mm and an aspect ratio of about 10 to 60 is slowly added to a mixed solution of γ-methacryloxypropyltrimethoxysilane / ethanol, and ultrasonic dispersion is adopted. After being uniformly dispersed, the mixture is filtered and placed in a vacuum drying oven, and dried for 3 to 5 hours at 230 to 250° C. under a vacuum state, and then taken out, cooled and crushed to obtain surface-modified aramid fibrid. The modified 1414 para-aramid fibrid is dispersed into a polyurethane prepolymer by a high-power ultrasonic disperser to obtain a polyurethane prepolymer modified by 1414 para-aramid fibrid. The weight of the 1414 para-aramid fibrid is 1 to 8% of the weight of the prepolymer. The amount of γ-methacryloxypropyltrimethoxysilane is 20 to 40% of the weight of the aramid fibrid, and the amount of ethanol is 3 to 10 times the weight of the coupling agent.

[0026] In a possible design, the modified polyurethane prepolymer is used to cast the surface-modified tire tread to obtain a composite tire product, including:

[0027] The modified polyurethane prepolymer is transferred to the A tank of the polyurethane elastomer casting machine, the material is heated to 75-85°C and filled with dry nitrogen for protection, the chain extender low molecular diol / triol is transferred to the B tank, the isocyanate content in the prepolymer is determined by the toluene di-n-butylamine method, and the amount of the prepolymer and the chain extender is calculated according to the set chain extension coefficient, and the parameters of the delivery metering pump of the casting machine A / B components are set according to the calculation;

[0028] The surface treated tire carcass is placed in a mold preheated to 110-130° C., and a pouring machine is started for pouring; after filling, the pressure is maintained at 0.2-0.3 MPa and the temperature is kept at 110-130° C. After 60-80 minutes, the mold is opened to take out the preformed composite tire and transferred to an oven or drying tunnel at 110-130° C., and post-treated for 12-24 hours to obtain the finished composite tire.

[0029] In a possible design, the linear polyurethane prepolymer is prepared by using selected raw materials of a cast polyurethane elastomer and a supramolecular structure, including:

[0030] A supramolecular structure is introduced into the molecular chain of the cast polyurethane elastomer system for modification; wherein the supramolecular structure is a terminal hydroxyl hyperbranched monomer, and the synthesis method of the terminal hydroxyl hyperbranched monomer is as follows:

[0031] Trimethylolpropane and dimethylolpropionic acid in a molar ratio of 1:16-25 are added to a reactor, heated to 80-100° C., stirred and melted, butanediol in a molar ratio of 1-5 and oxalic acid in a molar ratio of 0.2-2.5 are added to the reactor, and under the catalytic effect of 0.5-1wt% trifluoromethanesulfonic acid as a reaction monomer, argon is passed at 100-120° C. in the early stage of the reaction to remove small molecular water, and the reaction process lasts for 1-3 hours; then the reaction temperature is raised to 1 25~145℃, pump the reaction system pressure to -0.095~0.098Mpa to vacuum out small molecules for 1~3 hours, then cool down for testing, the target value is the molecular weight of the terminal hydroxyl hyperbranched monomer is 1024g / mol~3500g / mol, and the degree of branching is 0.3~0.6; alternatively, directly use one or a mixture of Perstorp's terminal hydroxyl hyperbranched monomers BoltornH20, H30, H40 as the hyperbranched monomer;

[0032] The linear polyurethane prepolymer is prepared by: using an oligomer polyol or a mixture of multiple oligomer diols to dehydrate at -0.095-0.098Mpa vacuum and 100-135°C for 14 hours; after cooling to below 40°C, slowly adding isocyanate in batches, stirring at a uniform speed for 0.5 hour, slowly heating to 75-85°C after the temperature is stable, introducing dry nitrogen during the reaction, keeping the reaction conditions stable for 2-3 hours, stopping stirring to obtain a prepolymer product, and the isocyanate content in the prepolymer is designed to be between 3 and 6.2.

[0033] In a possible design, a linear polyurethane prepolymer is used to cast the surface-modified tire tread to obtain a composite tire product, including:

[0034] The linear polyurethane prepolymer is transferred to the A tank of the polyurethane elastomer casting machine, the material is heated to 75-85° C. and filled with dry nitrogen for protection, the chain extender low molecular diol / triol / terminal hydroxyl hyperbranched monomer is transferred to the B tank, the isocyanate content in the prepolymer is determined by the toluene di-n-butylamine method, and the amount of the prepolymer and the chain extender is calculated according to the set chain extension coefficient, and the parameters of the delivery metering pump of the casting machine A / B components are set according to the calculation;

[0035] The surface treated tire body is placed in a mold preheated to 110-130° C., and a pouring machine is started for pouring; after filling, the pressure is maintained at 0.2-0.3 MPa and the temperature is kept at 110-130° C. After 60-80 minutes, the mold is opened to take out the preformed composite tire and transferred to an oven or drying tunnel at 110-130° C., and post-treated for 12-24 hours to obtain the finished composite tire.

[0036] In a second aspect, an embodiment of the present invention provides a composite tire that can be manufactured by a method involved in any possible design of the first aspect.

[0037] For better understanding and implementation, the present invention is described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 A schematic flow chart of a method for manufacturing a composite tire provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0039] The directional terms such as up, down, left, right, front, back, front, back, top, bottom, etc. mentioned or may be mentioned in this specification are defined relative to their structure and are relative concepts. Therefore, they may change accordingly according to their different locations and different usage conditions. Therefore, these or other directional terms should not be interpreted as restrictive terms.

[0040] The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present disclosure. Instead, they are merely examples of embodiments consistent with some aspects of the present disclosure.

[0041] The terms used in this disclosure are only for the purpose of describing specific embodiments and are not intended to limit the disclosure. The singular forms of "a", "the" and "the" used in this disclosure are also intended to include plural forms, unless the context clearly indicates other meanings. It should also be understood that the term "and / or" used herein refers to and includes any or all possible combinations of one or more associated listed items.

[0042] Embodiment 1

[0043] This embodiment 1 provides a method for manufacturing a composite tire, such as Figure 1 As shown, the method may include the following steps:

[0044] S1. Grind the bonding area between the tire carcass and the cast polyurethane elastomer, clean and dry it for later use, and complete the surface pretreatment of the tire carcass.

[0045] In the specific implementation process, a transition layer film with good adhesion to rubber and polyurethane can be prepared first. When the rubber carcass is formed, the transition layer film is attached to the rubber carcass. After vulcanization, the bonding area between the rubber carcass and the cast polyurethane elastomer is polished and cleaned, dried and set aside, thereby completing the surface pretreatment of the tire carcass.

[0046] S2. Prepare a mixed solution of trichloroisocyanuric acid and an acetone / butanone / ethyl acetate mixed solvent treated with anhydrous calcium chloride, and prepare a tread treatment agent using the mixed solution and a multi-graft adhesive solution.

[0047] In a specific implementation, the multi-graft adhesive solution may include methyl methacrylate / acrylic acid / butyl acrylate / hydroxypropyl acrylate / chloroprene rubber.

[0048] In a specific implementation process, 3 to 15 parts by weight of the trichloroisocyanuric acid can be added to 85 to 97 parts by weight of the acetone / butanone / ethyl acetate mixed solvent treated with anhydrous calcium chloride, and the mixed solution can be obtained after rapid stirring and dissolution. 10 to 30 parts by weight of the multi-graft adhesive solution can be added to the mixed solution, and the tread treatment agent can be obtained after stirring and mixing.

[0049] S3, spraying or brushing the tread treatment agent on the prepared tire tread for surface modification.

[0050] In the specific implementation process, the tread treatment agent is evenly sprayed or brushed on the tire tread prepared in step S1, and after being parked for 0.5 to 12 hours in an environment with a temperature of 60 to 80°C and a humidity of 30 to 70%, the surface modification treatment of the tread of the tire carcass is completed, and the process of pouring the polyurethane tread material can be carried out.

[0051] S4. The modified polyurethane prepolymer or linear polyurethane prepolymer is used to cast the surface-modified tire tread to obtain a finished composite tire.

[0052] In a specific implementation process, the preparation of the modified polyurethane prepolymer may include: selecting raw materials of a cast polyurethane elastomer, using the selected raw materials of the cast polyurethane elastomer to prepare a polyurethane prepolymer, and modifying the polyurethane prepolymer to obtain a modified polyurethane prepolymer; the preparation of the linear polyurethane prepolymer may include: using the selected raw materials of the cast polyurethane elastomer and citing a supramolecular structure to prepare the linear polyurethane prepolymer.

[0053] In the specific implementation process, a polyurethane prepolymer prepared from an oligomer polyol-isocyanate system and a material composed of a small molecule diol / diamine can be selected as the raw material of the cast polyurethane elastomer. The oligomer polyol-isocyanate system can be selected from system A or system B.

[0054] The system A can be a prepolymer of polycaprolactone / tetrahydrofuran copolymer glycol / polycaprolactone glycol / polytetrahydrofuran glycol / polycarbonate glycol / hydroxy-terminated polybutadiene polyol-diphenylmethane diisocyanate system, wherein the molecular weight of the polyol / diol is between 600 and 5000; the chain extender is a low molecular weight diol / triol; and the chain extension coefficient is between 0.93 and 1.02;

[0055] The system B can be a polycaprolactone / tetramethylene glycol copolymer / polycaprolactone glycol / polytetramethylene glycol / polycarbonate glycol / hydroxy-terminated polybutadiene polyol-p-phenylene diisocyanate system prepolymer, wherein the molecular weight of the polyol / diol is between 600 and 5000; the chain extender is a low molecular weight diol / triol; and the chain extension coefficient is between 0.93 and 1.02.

[0056] In the specific implementation process, after selecting the raw materials of the cast polyurethane elastomer, the modification of the cast polyurethane elastomer prepolymer in step S4 may include two methods:

[0057] Method 1

[0058] (1) First prepare the polyurethane prepolymer:

[0059] One oligomer polyol or a mixture of multiple oligomer diols can be dehydrated at -0.095-0.098Mpa vacuum and 100-135°C for 14 hours; after cooling to below 40°C, isocyanate is slowly added in batches, stirred at a uniform speed for 0.5 hour, and slowly heated to 75-85°C after the temperature stabilizes, during which dry nitrogen is introduced, and the reaction conditions are kept stable for 2-3 hours. After stopping stirring, a prepolymer product is obtained, and the isocyanate content in the prepolymer is designed to be between 3 and 6.2.

[0060] (2) modifying the polyurethane prepolymer:

[0061] The 1414 para-aramid fibrid with a diameter of about 10 μm, a length of 0.5 to 2 mm and an aspect ratio of about 10 to 60 can be dried and slowly added into a mixed solution of γ-methacryloxypropyltrimethoxysilane / ethanol, dispersed by ultrasonic wave, filtered after being evenly dispersed and placed in a vacuum drying oven, dried for 3 to 5 hours at 230 to 250° C. under vacuum, taken out, cooled and crushed to obtain surface-modified aramid fibrid; the modified 1414 para-aramid fibrid is dispersed into a polyurethane prepolymer by a high-power ultrasonic disperser to obtain a polyurethane prepolymer modified by 1414 para-aramid fibrid; wherein the weight of the 1414 para-aramid fibrid is 1 to 8% of the weight of the prepolymer; the amount of γ-methacryloxypropyltrimethoxysilane is 20 to 40% of the weight of the aramid fibrid, and the amount of ethanol is 3 to 10 times the weight of the coupling agent.

[0062] In the specific implementation process, it is possible to consider using isocyanate monomers to synthesize trimers, such as TDI, IPDI or HDI, HMDI trimers, as fiber treatment agents to replace coupling agents.

[0063] Method 2

[0064] (i) Modifying the molecular chain of the cast polyurethane elastomer system by introducing a supramolecular structure, wherein the supramolecular structure is a terminal hydroxyl hyperbranched monomer, and the synthesis method of the terminal hydroxyl hyperbranched monomer is as follows:

[0065] Trimethylolpropane and dimethylolpropionic acid in a molar ratio of 1:16-25 are added to a reactor, heated to 80-100° C., stirred and melted, butanediol in a molar ratio of 1-5 and oxalic acid in a molar ratio of 0.2-2.5 are added to the reactor, and under the catalytic effect of 0.5-1wt% trifluoromethanesulfonic acid as a reaction monomer, argon is passed at 100-120° C. in the early stage of the reaction to remove small molecular water, and the reaction process lasts for 1-3 hours; then the reaction temperature is raised to 1 25~145℃, pump the reaction system pressure to -0.095~0.098Mpa, vacuum out small molecules for 1~3 hours, then cool down for testing, the target value is the molecular weight of the terminal hydroxyl hyperbranched monomer is 1024g / mol~3500g / mol, and the degree of branching is 0.3~0.6; alternatively, directly use one or a mixture of Perstorp's terminal hydroxyl hyperbranched monomers BoltornH20, H30, H40 as the hyperbranched monomer.

[0066] In the specific implementation process, in addition to the above-mentioned trifluoromethanesulfonic acid, one of p-toluenesulfonic acid, stannous octoate, n-butyl titanate, and thionyl chloride can also be used as a catalyst, and the dosage can be set to a concentration between 1 / 10,000 and 1 / 1,000 in the reaction system.

[0067] (2) Preparation of the linear polyurethane prepolymer: an oligomer polyol or a mixture of oligomer diols can be used to dehydrate at -0.095 to 0.098 MPa vacuum and 100 to 135° C. for 14 hours; after cooling to below 40° C., isocyanate is slowly added in batches and stirred at a constant speed for 0.5 hour. After the temperature stabilizes, the temperature is slowly raised to 75 to 85° C., during which dry nitrogen is introduced, and the reaction conditions are kept stable for 2 to 3 hours. After stopping stirring, a prepolymer product is obtained, and the isocyanate content in the prepolymer is designed to be between 3 and 6.2.

[0068] In the first embodiment of the present invention, a hyperbranched structure is introduced into a group of formulas, wherein a terminal hydroxyl hyperbranched monomer is synthesized, and a linear polyurethane prepolymer is combined for chain extension, and a hyperbranched structure is introduced into the system, taking into account the advantages of polyurethane and hyperbranched polymers, and the heat resistance of the material can be effectively improved. For example, by introducing a terminal hydroxyl hyperbranched monomer into a polyurethane elastomer system, the purpose is to form a tighter network structure by introducing a multi-hydroxyl hyperbranched monomer, and at the same time, because the terminal hydroxyl hyperbranched monomer can form a better interpenetrating network structure with the polyurethane macromolecule, the effect of improving the tensile strength and heat resistance of the material can be achieved.

[0069] In the specific implementation process, if the modification of the cast polyurethane elastomer prepolymer is carried out by adopting the above-mentioned method 1, the specific implementation steps of the casting molding of the composite tire can be as follows:

[0070] The modified polyurethane prepolymer is transferred to the A tank of the polyurethane elastomer casting machine, the material is heated to 75-85°C and filled with dry nitrogen for protection, the chain extender low molecular diol / triol is transferred to the B tank, the isocyanate content in the prepolymer is determined by the toluene di-n-butylamine method, and the amount of the prepolymer and the chain extender is calculated according to the set chain extension coefficient, and the parameters of the delivery metering pump of the casting machine A / B components are set according to the calculation.

[0071] The surface treated tire carcass is placed in a mold preheated to 110-130° C., and a pouring machine is started for pouring; after filling, the pressure is maintained at 0.2-0.3 MPa and the temperature is kept at 110-130° C. After 60-80 minutes, the mold is opened to take out the preformed composite tire and transferred to an oven or drying tunnel at 110-130° C., and post-treated for 12-24 hours to obtain the finished composite tire.

[0072] In the specific implementation process, if the modification of the cast polyurethane elastomer prepolymer is carried out by the above-mentioned method 2, the specific implementation steps of the casting molding of the composite tire can be as follows:

[0073] The linear polyurethane prepolymer is transferred to the A tank of the polyurethane elastomer casting machine, the material is heated to 75-85° C. and filled with dry nitrogen for protection, the chain extender low molecular diol / triol / terminal hydroxyl hyperbranched monomer is transferred to the B tank, the isocyanate content in the prepolymer is determined by the toluene di-n-butylamine method, and the amount of the prepolymer and the chain extender is calculated according to the set chain extension coefficient, and the parameters of the delivery metering pump of the casting machine A / B components are set according to the calculation.

[0074] The surface treated tire body is placed in a mold preheated to 110-130° C., and a pouring machine is started for pouring; after filling, the pressure is maintained at 0.2-0.3 MPa and the temperature is kept at 110-130° C. After 60-80 minutes, the mold is opened to take out the preformed composite tire and transferred to an oven or drying tunnel at 110-130° C., and post-treated for 12-24 hours to obtain the finished composite tire.

[0075] It can be seen from the above description that the technical solution provided by the embodiment of the present invention has the following advantages compared with the prior art:

[0076] A. The composite tire manufactured by the technical solution provided in the first embodiment can combine the advantages of low rolling resistance, safety, high comfort of the radial tire body and wear resistance and pollution-free of the polyurethane elastomer, and is a new type of green and environmentally friendly tire.

[0077] B. By utilizing the small deformation of radial tire body and the wear resistance of polyurethane elastomer, on the one hand, the amount of natural rubber used in the tread can be reduced, the tire can be lightweight and the rolling resistance can be reduced. On the other hand, the tire cost can be greatly reduced while ensuring performance, thus meeting market demand.

[0078] C. By using a special transition layer between the rubber carcass and the polyurethane tread, the transition layer can produce chemical cross-linking with the rubber and the polyurethane elastomer. In addition, with the help of a compounded surface treatment agent, the rubber surface is chlorinated and the grafted chloroprene adhesive is introduced, which can produce very high bonding strength, good bonding effect and simple process.

[0079] D. By modifying the polyurethane elastomer with modified carbon nanotubes, the performance at high temperature and thermal aging performance are improved, and the thermal conductivity of the material is effectively improved, eliminating heat accumulation inside the material during dynamic use.

[0080] E. The polyurethane elastomer is modified by using 1414 para-aramid fiber which has high specific strength, specific stiffness and good impact resistance, thereby improving the strength of the material and its performance at high temperature.

[0081] F. The cast polyurethane elastomer with the characteristics of "integrated polyurethane elastomer" is designed by referring to the molecular structure of rubber. It has high elasticity at an appropriate hardness (75-85A). On the basis of maintaining high wear resistance, it shows excellent dynamic performance, low heat generation, low hysteresis, and lower fuel consumption. At the same time, it has relatively good grip performance and anti-skid performance, ensuring the safety performance of the composite tire.

[0082] Embodiment 2

[0083] The second embodiment provides a composite tire, which can be manufactured by any possible implementation method of the first embodiment.

[0084] The above-mentioned embodiments only express several implementation methods of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A method for manufacturing a composite tire, characterized in that: include: S1. Grinding the area where the tire carcass and the cast polyurethane elastomer are bonded, cleaning and drying the area for standby use, and completing the surface pretreatment of the tire carcass; S2, preparing a mixed solution of trichloroisocyanuric acid and a mixed solvent of acetone, butanone and ethyl acetate treated with anhydrous calcium chloride, and preparing a tread treatment agent using the mixed solution and a multi-graft adhesive solution; S3, spraying or brushing the tread treatment agent on the prepared tire tread for surface modification; S4, using the modified polyurethane prepolymer or the linear polyurethane prepolymer to cast the tire tread after surface modification to obtain a finished composite tire; wherein the preparation of the modified polyurethane prepolymer includes: selecting a raw material of a casting polyurethane elastomer, using the selected raw material of the casting polyurethane elastomer to prepare a polyurethane prepolymer, and modifying the polyurethane prepolymer to obtain the modified polyurethane prepolymer; the preparation of the linear polyurethane prepolymer includes: using the selected raw material of the casting polyurethane elastomer and citing a supramolecular structure to prepare the linear polyurethane prepolymer; Wherein, the polyurethane prepolymer is subjected to modification treatment, comprising: After drying, 1414 para-aramid fibrids with a diameter of 10 μm, a length of 0.5 to 2 mm, and an aspect ratio of 10 to 60 are slowly added to a mixed solution of γ-methacryloxypropyltrimethoxysilane and ethanol, and ultrasonic dispersion is used. After being evenly dispersed, the mixture is filtered and placed in a vacuum drying oven, and dried at 230 to 250° C. for 3 to 5 hours under vacuum, taken out, cooled, and crushed to obtain surface-modified aramid fibrids; the modified 1414 para-aramid fibrids are dispersed into a polyurethane prepolymer using a high-power ultrasonic disperser to obtain a polyurethane prepolymer modified with 1414 para-aramid fibrids; wherein the weight of the 1414 para-aramid fibrids is 1 to 8% of the weight of the prepolymer; the amount of γ-methacryloxypropyltrimethoxysilane is 20 to 40% of the weight of the aramid fibrids, and the amount of ethanol is 3 to 10 times the weight of the coupling agent; The linear polyurethane prepolymer is prepared by using selected raw materials of cast polyurethane elastomer and citing supramolecular structure, including: A supramolecular structure is introduced into the molecular chain of the cast polyurethane elastomer system for modification; wherein the supramolecular structure is a terminal hydroxyl hyperbranched monomer, and the synthesis method of the terminal hydroxyl hyperbranched monomer is as follows: Trimethylolpropane and dimethylolpropionic acid in a molar ratio of 1:16-25 are added to a reactor, heated to 80-100°C, stirred and melted, butanediol in a molar ratio of 1-5 and oxalic acid in a molar ratio of 0.2-2.5 are added to the reactor, and under the catalytic effect of 0.5-1wt% trifluoromethanesulfonic acid as a reaction monomer, argon is passed at 100-120°C in the early stage of the reaction to remove small molecular water, and the reaction process lasts for 1-3 hours; then the reaction temperature is raised to 1 25~145℃, pump the reaction system pressure to -0.095~0.098Mpa to vacuum out small molecules for 1~3 hours, then cool down for testing, the target value is the molecular weight of the terminal hydroxyl hyperbranched monomer is 1024g / mol~3500g / mol, and the degree of branching is 0.3~0.6; alternatively, directly use one or a mixture of Perstorp's terminal hydroxyl hyperbranched monomers BoltornH20, H30, H40 as the hyperbranched monomer; The linear polyurethane prepolymer is prepared by: using an oligomer polyol or a mixture of multiple oligomer diols to dehydrate at -0.095-0.098Mpa vacuum and 100-135°C for 14 hours; after cooling to below 40°C, slowly adding isocyanate in batches, stirring at a uniform speed for 0.5 hour, slowly heating to 75-85°C after the temperature stabilizes, during which dry nitrogen is introduced, keeping the reaction conditions stable for 2-3 hours, stopping stirring to obtain a prepolymer product, and the isocyanate content in the prepolymer is designed to be between 3 and 6.

2.

2. The method according to claim 1, characterized in that The multi-graft adhesive solution includes methyl methacrylate, acrylic acid, butyl acrylate, hydroxypropyl acrylate, and chloroprene rubber; A mixed solution of trichloroisocyanuric acid and a mixed solvent of acetone, butanone and ethyl acetate treated with anhydrous calcium chloride is prepared, and a tread treatment agent is prepared by using the mixed solution and a multi-graft adhesive solution, including: Adding 3 to 15 parts by weight of the trichloroisocyanuric acid to 85 to 97 parts by weight of the mixed solvent of acetone, butanone and ethyl acetate treated with anhydrous calcium chloride, and stirring rapidly to dissolve uniformly to obtain the mixed solution; 10 to 30 parts by weight of the multi-graft adhesive solution is added to the mixed solution, and the mixture is stirred and mixed to obtain the tread treatment agent.

3. The method according to claim 1, characterized in that The tread treatment agent is sprayed or brushed on the prepared tire tread for surface modification, including: The tread treatment agent is evenly sprayed or brushed on the prepared tire tread, and the tire is left standing for 0.5 to 12 hours in an environment with a temperature of 60 to 80° C. and a humidity of 30 to 70%, thereby completing the surface modification treatment of the tire tread.

4. The method according to any one of claims 1 to 3, characterized in that: Select raw materials for cast polyurethane elastomers, including: Selecting a material composed of a polyurethane prepolymer prepared from an oligomer polyol-isocyanate system and a small molecule diol and a diamine as the raw material of the cast polyurethane elastomer; Wherein, the oligomer polyol-isocyanate type system can be selected from system A or system B; The system A is a prepolymer of polycaprolactone, tetrahydrofuran copolymer glycol, polycaprolactone glycol, polytetrahydrofuran glycol, polycarbonate glycol, hydroxy-terminated polybutadiene polyol-diphenylmethane diisocyanate system, wherein the molecular weight of the polyol and diol is between 600 and 5000; the chain extender is a low molecular weight diol and triol; and the chain extension coefficient is between 0.93 and 1.02; The system B is a prepolymer of polycaprolactone, tetrahydrofuran copolymer glycol, polycaprolactone glycol, polytetrahydrofuran glycol, polycarbonate glycol, terminal hydroxyl polybutadiene polyol-p-phenylene diisocyanate system, wherein the molecular weight of the polyol and diol is between 600 and 5000; the chain extender is a low molecular weight diol and triol; and the chain extension coefficient is between 0.93 and 1.

02.

5. The method according to claim 4, characterized in that The polyurethane prepolymer is prepared by using selected raw materials of the casting polyurethane elastomer, including: A kind of oligomer polyol or a mixture of multiple oligomer diols is dehydrated at -0.095-0.098Mpa vacuum and 100-135°C for 14 hours; after cooling to below 40°C, isocyanate is slowly added in batches, stirred at a uniform speed for 0.5 hour, and slowly heated to 75-85°C after the temperature is stabilized, during which dry nitrogen is introduced, and the reaction conditions are kept stable for 2-3 hours. After stopping stirring, a prepolymer product is obtained, and the isocyanate content in the prepolymer is designed to be between 3 and 6.

2.

6. The method according to claim 1, characterized in that The modified polyurethane prepolymer is used to cast the surface-modified tire tread to obtain a composite tire product, including: The modified polyurethane prepolymer is transferred to the A tank of the polyurethane elastomer casting machine, the material is heated to 75-85°C and filled with dry nitrogen for protection, the chain extender low molecular diol and triol are transferred to the B tank, the isocyanate content in the prepolymer is determined by the toluene di-n-butylamine method, and the amount of the prepolymer and the chain extender is calculated according to the set chain extension coefficient, and the parameters of the delivery metering pump of the casting machine A / B components are set according to the calculation; The surface treated tire carcass is placed in a mold preheated to 110-130° C., and a pouring machine is started for pouring; after filling, the pressure is maintained at 0.2-0.3 MPa and the temperature is kept at 110-130° C. After 60-80 minutes, the mold is opened to take out the preformed composite tire and transferred to an oven or drying tunnel at 110-130° C., and post-treated for 12-24 hours to obtain the finished composite tire.

7. The method according to claim 1, characterized in that The tire tread after surface modification is poured with linear polyurethane prepolymer to obtain a composite tire product, including: The linear polyurethane prepolymer is transferred to the A tank of the polyurethane elastomer casting machine, the material is heated to 75-85° C. and filled with dry nitrogen for protection, the chain extender low molecular weight diol, triol, and terminal hydroxyl hyperbranched monomer are transferred to the B tank, the isocyanate content in the prepolymer is determined by the toluene di-n-butylamine method, and the amount of the prepolymer and the chain extender is calculated according to the set chain extension coefficient, and the parameters of the delivery metering pump of the casting machine A / B components are set according to the calculation; The surface treated tire body is placed in a mold preheated to 110-130° C., and a pouring machine is started for pouring; after filling, the pressure is maintained at 0.2-0.3 MPa and the temperature is kept at 110-130° C. After 60-80 minutes, the mold is opened to take out the preformed composite tire and transferred to an oven or drying tunnel at 110-130° C., and post-treated for 12-24 hours to obtain the finished composite tire.

8. A composite tire, characterized in that: The method is manufactured by any one of claims 1 to 7.

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