Spoke-type non-pneumatic tire and its preparation method

Abstract

The present application provides a spoke-type non-pneumatic tire and a preparation method thereof, relating to the technical field of tires. The spoke-type non-pneumatic tire at least includes a tread and an adhesive layer. The adhesive layer is located on one side of the tread and is used for bonding with the tread. The adhesive layer includes an adhesive, and the tread includes a base rubber. The adhesive is used for crosslinking with the base rubber. The adhesive includes component A and component B, and the ratio range of component A to component B is 100:30 - 100:80. Component A includes, by weight parts: 80 - 100 parts of an olefin rubber, 3 - 6 parts of an anti-aging agent, 1 - 3 parts of a promoter, 1 - 3 parts of a crosslinking agent, 3 - 10 parts of an activator, 40 - 60 parts of a reinforcing agent, and 60 - 200 parts of a solvent A. Component B includes, by weight parts: 30 - 60 parts of an epoxy resin, 5 - 30 parts of an isocyanate, 1 - 3 parts of a fatty amine, 60 - 100 parts of a polyol, and 60 - 100 parts of a solvent B. Thus, the bonding strength requirements of the adhesive for the spoke-type non-pneumatic tire during high-speed operation and during sudden stops or sudden accelerations can be met.

Description

Technical Field

[0001] This application relates to the technical field of tires, and particularly to a spoke-type non-pneumatic tire and a preparation method thereof. Background Art

[0002] With the development of technology, spoke-type non-pneumatic tires, as tires for a new generation of electric vehicles, have received more and more extensive research and applications. A spoke-type non-pneumatic tire generally includes a tread, spokes, and a hub. The fitting method of the three will affect the performance of the entire spoke-type non-pneumatic tire.

[0003] Generally, an adhesive layer composed of an adhesive is used to bond the spokes and the tread in a spoke-type non-pneumatic tire. Most of the rubbers constituting the tread are natural rubber, styrene-butadiene rubber, cis-1,4-polybutadiene rubber, and isoprene rubber, etc. These rubbers are non-polar. After the currently commonly used adhesive bonds the spokes and the tread, the bonding strength is relatively low and cannot meet the bonding strength requirements of the adhesive during the high-speed operation, sudden stop, or sudden acceleration of the spoke-type non-pneumatic tire.

[0004] Therefore, there is an urgent need to develop a new type of adhesive for spoke-type non-pneumatic tires to solve the above problems. Summary of the Invention

[0005] Embodiments of this application provide a spoke-type non-pneumatic tire and a preparation method thereof, which can solve the problem that the adhesive in the adhesive layer for traditional spoke-type non-pneumatic tires has low bonding strength and cannot meet the bonding strength requirements of the adhesive during the high-speed operation, sudden stop, or sudden acceleration of the spoke-type non-pneumatic tire.

[0006] To achieve the above object, the embodiments of this application adopt the following technical solutions:

[0007] On the one hand, a spoke-type non-pneumatic tire is provided. The spoke-type non-pneumatic tire at least includes a tread and an adhesive layer. The adhesive layer is located on one side of the tread and is used for bonding with the tread. The adhesive layer includes an adhesive, and the tread includes a base rubber. The adhesive is used for crosslinking with the base rubber;

[0008] The adhesive includes component A and component B, and the ratio range of component A to component B is 100:30 - 100:80;

[0009] Component A includes, by weight parts:

[0010] olefin rubber, 80 - 100 parts;

[0011] anti-aging agent, 3 - 6 parts;

[0012] Accelerator, 1 - 3 parts;

[0013] Crosslinking agent, 1 - 3 parts;

[0014] Activator, 3 - 10 parts;

[0015] Reinforcing agent, 40 - 60 parts;

[0016] Solvent A, 60 - 200 parts;

[0017] The component B includes, by weight:

[0018] Epoxy resin, 30 - 60 parts;

[0019] Isocyanate, 5 - 30 parts;

[0020] Fatty amine, 1 - 3 parts;

[0021] Polyol, 60 - 100 parts;

[0022] Solvent B, 60 - 100 parts.

[0023] Furthermore, the peel strength of the adhesive layer ranges from 23 - 33 kN / m. Furthermore, the anti - aging agent includes secondary amine anti - aging agents;

[0024] The accelerator includes sulfenamide accelerators;

[0025] The crosslinking agent includes sulfur;

[0026] The activator includes metal inorganic activators;

[0027] The reinforcing agent includes carbon black;

[0028] The solvent A includes at least one of ketones and aromatic hydrocarbons. Furthermore, the epoxy resin includes bisphenol A epoxy resin;

[0029] The isocyanate includes diisocyanate;

[0030] The fatty amine includes fatty amines with double active groups;

[0031] The polyol includes polyols containing both olefinic bonds and multiple hydroxyl groups.

[0032] The solvent B includes at least one of ketones and aromatic hydrocarbons.

[0033] Furthermore, the base rubber of the tread surface includes natural rubber.

[0034] Furthermore, the spoke - type non - pneumatic tire further includes a spoke, the spoke is located on the side of the adhesive layer away from the tread surface, and the adhesive layer is also used for bonding with the spoke;

[0035] The material of the spoke includes any one of polyurethane and modified polyurethane.

[0036] On the other hand, a preparation method of the spoke-type non-pneumatic tire as described above is provided, including the following steps:

[0037] Clean the surface of the tread of the spoke-type non-pneumatic tire;

[0038] Prepare the adhesive;

[0039] Coat the adhesive on one side surface of the tread;

[0040] Bond the tread coated with the adhesive to the spoke to form a spoke-type non-pneumatic tire preform;

[0041] Inject the spoke-type non-pneumatic tire preform to obtain the spoke-type non-pneumatic tire; wherein, the injection temperature range is 130 - 260 °C, the heat preservation time after injection ranges from 1 - 30 min, the injection pressure range is 40 - 80 MPa, and the injection mold temperature range is 30 - 130 °C.

[0042] Further, the preparation of the adhesive includes:

[0043] Prepare the component A;

[0044] Prepare the component B;

[0045] Mix the component A and the component B evenly according to the ratio of 100:30 - 100:80 to obtain the adhesive.

[0046] Further, the preparation of the component A includes:

[0047] Mix the olefin rubber in a kneader at 50 - 60 °C for a period of time, then raise the temperature to 80 - 90 °C, add the anti-aging agent, the accelerator, the activator and the reinforcing agent, continue to knead and raise the temperature to 150 - 160 °C, and discharge the rubber to obtain the first rubber compound;

[0048] Let the first rubber compound stand at 20 - 25 °C for a period of time, then raise the temperature to 50 - 60 °C, add the cross-linking agent and open mill for a period of time, and then raise the temperature to 90 - 100 °C, and discharge the rubber to obtain the second rubber compound.

[0049] Mix the second rubber compound and the solvent A evenly to obtain the component A.

[0050] Further, the preparation of the component B includes:

[0051] The epoxy resin is dehydrated at 110 - 120 °C to obtain dehydrated epoxy resin;

[0052] After the dehydrated epoxy resin is cooled to 50 - 60 °C, the fatty amine is added to obtain modified epoxy resin;

[0053] After the modified epoxy resin is cooled to 20 - 30 °C, the solvent B is added and mixed evenly to obtain a homogeneous solution;

[0054] The polyol is dehydrated at 110 - 120 °C to obtain dehydrated polyol;

[0055] After the dehydrated polyol is cooled to 50 - 60 °C, the isocyanate is added to obtain a mixture with isocyanate groups at the ends and containing isocyanate;

[0056] The mixture with isocyanate groups at the ends and containing isocyanate is mixed evenly with the homogeneous solution, and after reacting at 30 - 40 °C for a period of time, the component B is obtained.

[0057] The embodiments of the present application provide a spoke - type non - pneumatic tire and its preparation method. Through the design of the self - molecular structure of the adhesive, the polyurethane - modified epoxy resin containing double bonds can achieve co - vulcanization with the rubber tread or the rubber in component A to form a network structure, so that the adhesive and the rubber tread are combined by chemical bonds, forming a chemical cross - linked structure as a whole, resulting in a relatively high bonding strength and good bonding performance. Therefore, it can meet the requirements for the bonding strength of the adhesive during the high - speed operation, sudden stop or sudden acceleration of the spoke - type non - pneumatic tire.

[0058] The above description is only an overview of the technical solution of the present application. In order to be able to understand the technical means of the present application more clearly, it can be implemented according to the content of the specification. And in order to make the above and other purposes, features and advantages of the present application more obvious and understandable, the following specifically gives the specific embodiments of the present application. Brief Description of the Drawings

[0059] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained according to these drawings.

[0060] Figure 1 It is a schematic structural diagram of a spoke - type non - pneumatic tire provided by the embodiment of the present application;

[0061] Figure 2Schematic diagram of the bonding of an adhesive to a rubber tread surface provided by an embodiment of the present application;

[0062] Figure 3 Process flow chart for the preparation of a spoke-type non-pneumatic tire provided by an embodiment of the present application;

[0063] Figure 4 Process flow chart for the preparation of an adhesive provided by an embodiment of the present application;

[0064] Figure 5 Process flow chart for the preparation of another adhesive provided by an embodiment of the present application;

[0065] Figure 6 Process flow chart for the preparation of yet another adhesive provided by an embodiment of the present application. Detailed implementation manners

[0066] In order to make the technical problems to be solved, technical solutions and beneficial effects of the present application clearer and more understandable, the present application will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0067] In the present application, the term "and / or" describes the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B may represent: A exists alone, A and B exist simultaneously, and B exists alone. Where A and B may be singular or plural. The character " / " generally represents an "or" relationship between the front and back associated objects.

[0068] In the present application, "at least one" means one or more, and "a plurality" means two or more. "At least one (item)" or its similar expression means any combination of these items, including any combination of single item (item) or plural items (items). For example, "at least one (item) of a, b or c", or, "at least one (item) of a, b and c" can both represent: a, b, c, a-b (i.e., a and b), a-c, b-c or a-b-c, where a, b, c can be single or plural respectively.

[0069] It should be understood that in various embodiments of the present application, the magnitudes of the sequence numbers of the above processes do not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.

[0070] The terms used in the embodiments of the present application are for the purpose of describing specific embodiments only and are not intended to limit the present application. The singular forms "a", "the" and "said" used in the embodiments of the present application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0071] The weight of the relevant components mentioned in the specification of the embodiments of the present application not only can refer to the specific content of each component, but also can represent the proportional relationship of the weights between the components. Therefore, as long as the content of the relevant components in the specification of the embodiments of the present application is enlarged or reduced in proportion, it is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass mentioned in the specification of the embodiments of the present application can be mass units well-known in the chemical industry such as μg, mg, g, kg, etc.

[0072] The terms "first" and "second" are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX can also be referred to as the second XX, and similarly, the second XX can also be referred to as the first XX. Thus, the features defined with "first" and "second" can explicitly or implicitly include one or more of such features.

[0073] In a first aspect, the embodiments of the present application provide a spoke-type non-pneumatic tire. The spoke-type non-pneumatic tire at least includes a tread and an adhesive layer. The adhesive layer is located on one side of the tread and is used for bonding with the tread. The adhesive layer includes an adhesive. The tread includes a base rubber. The adhesive is used for crosslinking with the base rubber. The adhesive includes component A and component B. The ratio range of component A to component B is 100:30 - 100:80.

[0074] Among them, component A includes, by weight parts: olefin rubber, 80 - 100 parts; antioxidant, 3 - 6 parts; accelerator, 1 - 3 parts; crosslinking agent, 1 - 3 parts; activator, 3 - 10 parts; reinforcing agent, 40 - 60 parts; solvent A, 60 - 200 parts.

[0075] Among them, component B includes, by weight parts: epoxy resin, 30 - 60 parts; isocyanate, 5 - 30 parts; fatty amine, 1 - 3 parts; polyol, 60 - 100 parts; solvent B, 60 - 100 parts.

[0076] In practical applications, when the ratio of component A to component B is too high or too low, the strength of the adhesive is low. Therefore, the ratio range of component A to component B can be set to 100:30 - 100:80, which can make the strength of the adhesive better. Exemplarily, the ratio of component A to component B can be 100:30, 100:40, 100:50, 100:60, 100:70, or 100:80, etc.

[0077] It should be understood that the above spoke-type non-pneumatic tire including at least a tread and an adhesive layer means that: as Figure 1 shown, in addition to including a tread and an adhesive layer, the spoke-type non-pneumatic tire further includes a spoke and a hub. The spoke is located on the side of the adhesive layer away from the tread. The spoke includes a plurality of spokes. One end of each spoke is used to be connected to the tread after being bonded through the adhesive layer, and the other end of each spoke is connected to the hub. Of course, the spoke-type non-pneumatic tire also has other structures. Only the content related to the invention point is described here, and other content can be obtained through related technologies.

[0078] In practical applications, the above-mentioned olefin rubber in component A refers to a rubber containing double bonds in the molecular chain. For example, cis-1,4-polybutadiene rubber (abbreviated as cis-butadiene rubber), etc. Exemplarily, the olefin rubber can be 80 parts, 85 parts, 90 parts, 95 parts, 98 parts, or 100 parts, etc. by weight.

[0079] The above-mentioned antioxidant can be a secondary amine antioxidant. The antioxidant can be used as a stabilizer and has good protection efficiency against aging caused by light, heat, ozone, etc. during the synthesis process. The secondary amine antioxidant can include RD445, etc. RD445 is a low-pollution aryl secondary amine antioxidant with good antioxidant efficiency. Exemplarily, the antioxidant can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or 6 parts, etc. by weight.

[0080] The above-mentioned accelerator can be a sulfenamide accelerator. The sulfenamide accelerator is a benzothiazole sulfenamide compound used as a vulcanization accelerator, which can accelerate the chemical reaction rate and promote the curing during the adhesive processing or the generation of the physical properties of the cured product. The sulfenamide accelerator can include N-cyclohexyl-2-benzothiazole sulfenamide (CZ), N-tert-butyl-2-benzothiazole sulfenamide (NS), N,N-2-dicyclohexyl-2,2-dibenzothiazole sulfenamide (DZ), N-oxydiethylene-2-benzothiazole sulfenamide (NOBS), etc. Exemplarily, the accelerator can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 2.8 parts, or 3 parts, etc. by weight.

[0081] The above crosslinking agent can be sulfur, and the crosslinking agent here is also the vulcanizing agent. Exemplarily, the crosslinking agent can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 2.8 parts or 3 parts, etc. by weight.

[0082] The above activator can be a metal-based inorganic activator. For example, zinc oxide (ZnO), etc. The activator can be used to promote the vulcanization reaction, and at the same time can also promote the blending and dispersion of the filler. Using a very small amount of activator can significantly improve the vulcanization reaction. Exemplarily, the activator can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts or 10 parts, etc. by weight.

[0083] The above reinforcing agent can be carbon black, etc. The activity on the surface of carbon black particles is not uniform, with a small number of strong active sites and a large number of adsorption sites with different energies. Therefore, carbon black has different binding energies for the rubber chains on its surface, which can be mostly adsorption caused by van der Waals forces and a small number of chemical bonds. Exemplarily, the reinforcing agent can be 40 parts, 45 parts, 50 parts, 55 parts, 58 parts or 60 parts, etc. by weight.

[0084] The above solvent A can be at least one of ketones and aromatic hydrocarbons. For example, methyl ethyl ketone, acetone, toluene, xylene, etc. Exemplarily, the solvent A can be 60 parts, 80 parts, 10 parts, 140 parts, 190 parts or 200 parts, etc. by weight.

[0085] Thus, the finally generated component A is a rubber compound containing olefin bonds and sulfur and is dissolved in the solvent A.

[0086] In practical applications, the above epoxy resin in component B can be bisphenol A type epoxy resin. For example, E51, etc. Exemplarily, the epoxy resin can be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or 60 parts, etc. by weight.

[0087] The above isocyanate can be diisocyanate. For example, liquefied diphenylmethane diisocyanate (liquefied MDI), toluene diisocyanate and 1,5-naphthalene diisocyanate, etc. Exemplarily, the epoxy resin can be 5 parts, 8 parts, 10 parts, 15 parts, 20 parts or 30 parts, etc. by weight.

[0088] The above fatty amine can be a fatty amine with double active groups. For example, diethylenetriamine, etc. Exemplarily, the fatty amine can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 2.8 parts or 3 parts, etc. by weight.

[0089] The above polyol can be a molecule containing both an olefin bond and a hydroxyl group, and the number of hydroxyl groups is greater than or equal to 2, such as, for example, hydroxyl-terminated polybutadiene. Exemplarily, the polyol can be 60 parts, 70 parts, 80 parts, 85 parts, 90 parts, or 100 parts by weight, etc.

[0090] The above B solvent can be at least one of ketones and aromatic hydrocarbons, such as, for example, methyl ethyl ketone, acetone, toluene, and xylene. Exemplarily, the B solvent can be 60 parts, 70 parts, 80 parts, 85 parts, 90 parts, or 100 parts by weight, etc.

[0091] Thus, since the B component is a modified product with an isocyanate group at the end, its modified epoxy resin and polyol have two subsequent reactions: 1. The molecule of the modified B component contains both a double bond and an isocyanate group at the same time. The double bond can further crosslink the sulfur in the A component with the base rubber on the molecule of the base rubber; and, 2. The isocyanate in the B component can undergo a polycondensation reaction with the polyol to form polyurethane. The polyurethane can modify the epoxy resin, making the B component a modified epoxy resin, and at the same time introducing a double bond, an amide group, and an amino group into its molecule. Then, the isocyanate group of the B component can further react with the amide group on the polyurethane molecule to achieve chemical linkage of the two molecules.

[0092] In summary, the adhesive of the embodiment of the present application can be synthesized from the A component and the B component. The peel strength range of the adhesive is 23 - 33 KN / m. Exemplarily, the peel strength of the adhesive can be 23 KN / m, 25 KN / m, 28 KN / m, 29 KN / m, 30 KN / m, or 33 KN / m, etc.

[0093] In practical applications, the base rubber on the above-mentioned wheel surface can include natural rubber. Any natural rubber can be used for conventional natural rubber, as long as it is known as natural rubber, and the place of origin, etc. are not restricted. For example, natural rubber can contain cis-1,4-polyisoprene as the main agent, and can also contain trans-1,4-polyisoprene according to the required properties. Therefore, the above natural rubber can include natural rubber containing trans-1,4-isoprene as the main agent in addition to natural rubber containing cis-1,4-polyisoprene as the main agent.

[0094] Thus, during the process of coating the adhesive prepared in the embodiment of the present application on the base rubber of the wheel surface and curing it, the adhesive can bond with the base rubber, and its bonding method is as Figure 2 shown.

[0095] The embodiment of the present application provides an adhesive. Through the design of the molecular structure of the adhesive itself, the polyurethane-modified epoxy resin containing double bonds can be co-vulcanized with the rubber tread or the rubber in component A to form a network structure, so that the adhesive and the rubber tread are combined by chemical bonds, and a chemical cross-linked structure is formed as a whole, resulting in a relatively high bonding strength and good bonding performance. Therefore, it can meet the requirements for the bonding strength of the adhesive during the high-speed operation, sudden stop or sudden acceleration of the spoke-type non-pneumatic tire.

[0096] Further, the material of the spoke includes any one of polyurethane and modified polyurethane.

[0097] It should be noted that the main molding process of the spoke-type non-pneumatic tire is that the tread is first vulcanized and molded, the surface of the hub is molded and treated, and the spoke is injection-molded. The spoke and the tread are bonded through an adhesive layer composed of an adhesive.

[0098] The embodiment of the present application provides an adhesive. Through the design of the molecular structure of the adhesive itself, the polyurethane-modified epoxy resin containing double bonds can be co-vulcanized with the rubber tread or the rubber in component A to form a network structure. At the same time, the isocyanate group can react with the urethane group in the spoke to form a covalent bond, that is, covalently bond with its molecule. In this way, the spoke, the adhesive, and the rubber tread can be combined by chemical bonds, and a chemical cross-linked structure is formed as a whole, resulting in a relatively high bonding strength and good bonding performance. Therefore, it can meet the requirements for the bonding strength of the adhesive during the high-speed operation, sudden stop or sudden acceleration of the spoke-type non-pneumatic tire.

[0099] In the second aspect, the embodiment of the present application provides a preparation method of the above-mentioned spoke-type non-pneumatic tire.

[0100] As Figure 3 shown, the preparation method of the spoke-type non-pneumatic tire includes the following steps:

[0101] S1. Clean the surface of the tread of the spoke-type non-pneumatic tire.

[0102] S2. Prepare the adhesive.

[0103] S3. Coat the adhesive on one side surface of the tread.

[0104] S4. Bond the tread coated with the adhesive to the spoke to form a spoke-type non-pneumatic tire preform.

[0105] S5. Inject the spoke-type non-pneumatic tire preform to obtain the spoke-type non-pneumatic tire.

[0106] Among them, the injection molding temperature range is 130 - 260 °C, the heat preservation time after injection molding is 1 - 30 min, the injection molding pressure range is 40 - 80 MPa, and the injection mold temperature range is 30 - 130 °C.

[0107] It should be noted that the order of the above steps S1 and S2 is not specifically limited. Step S1 can be carried out first and then step S2, or step S2 can be carried out first and then step S1, or steps S1 and S2 can be carried out simultaneously.

[0108] In practical applications, the spoke-type non-pneumatic tire preform can be injection molded in an injection molding machine.

[0109] Exemplarily, the injection molding temperature can be 130 °C, 160 °C, 200 °C, 220 °C, 240 °C or 260 °C, etc., the heat preservation time after injection molding can be 1 min, 5 min, 10 min, 15 min, 20 min or 30 min, etc., the injection molding pressure can be 40 MPa, 50 MPa, 60 MPa, 65 MPa, 60 MPa or 80 MPa, etc., and the injection mold temperature can be 30 °C, 40 °C, 50 °C, 80 °C, 100 °C or 130 °C, etc.

[0110] Through the injection molding process, the co-vulcanization reaction between the adhesive and the rubber tread can be promoted, realizing the chemical bonding of the molecular chains of the rubber part of the adhesive and the rubber tread; moreover, the isocyanate-modified epoxy resin containing double bonds can co-vulcanize with the rubber tread or the rubber in component A to form a network structure. At the same time, the isocyanate group can react with the urethane group in the spoke to form a covalent bond, that is, covalently combine with its molecule, so that the spoke, the adhesive, and the rubber tread are combined by chemical bonds, ensuring good bonding strength, and thus meeting the requirements for the bonding strength of the adhesive during the high-speed operation, sudden stop or sudden acceleration of the spoke-type non-pneumatic tire.

[0111] Furthermore, as Figure 4 shown, the above step S2. Preparing the adhesive includes:

[0112] S21. Preparing component A.

[0113] S22. Preparing component B.

[0114] S23. After uniformly mixing component A and component B in a ratio of 100:30 - 100:80, the adhesive is prepared.

[0115] Even further, as Figure 5 shown, the above step S21. Preparing component A includes:

[0116] S211. After kneading the olefin rubber at 50 - 60 °C for a period of time, raise the temperature to 80 - 90 °C, add antioxidant, accelerator, activator and reinforcing agent, continue to knead and raise the temperature to 150 - 160 °C, then discharge the rubber to obtain the first stock.

[0117] In practical applications, the olefin rubber can be placed in a kneader for kneading. Kneading is to mix the raw rubber and various auxiliary materials together.

[0118] It should be understood that kneading the olefin rubber at 50 - 60 °C can reduce the subsequent plasticizing difficulty.

[0119] The above-mentioned temperature rise to 80 - 90 °C is to disperse the raw rubber.

[0120] The above-mentioned temperature rise to 150 - 160 °C is for mixing.

[0121] S212. After storing the first stock at 20 - 25 °C for a period of time, raise the temperature to 50 - 60 °C, add crosslinking agent and open mill for a period of time, then raise the temperature to 90 - 100 °C, and discharge the rubber to obtain the second stock.

[0122] In practical applications, the first stock can be placed in an open mill for open milling. Open milling is to add vulcanization to the kneaded rubber stock and further mix it to prepare for mold pressing vulcanization.

[0123] It should be understood that storing the first stock at 20 - 25 °C for a period of time is to make the additives disperse better.

[0124] The above-mentioned temperature rise to 90 - 100 °C is because at this temperature, the basic rubber stock mixing is completed.

[0125] S213. After mixing the second stock with solvent A evenly, component A is prepared.

[0126] In practical applications, the second stock and solvent A are placed in a reaction kettle for mixing. The purpose of mixing with solvent A is to form a homogeneous solution, which is convenient for subsequent mixing, dispersion, coating and infiltration.

[0127] Furthermore, as Figure 6 shown, the above-mentioned step S22. Preparing component B includes:

[0128] S221. Dehydrate the epoxy resin at 110 - 120 °C to obtain dehydrated epoxy resin.

[0129] Since the reaction rate of water and isocyanate is very fast, in order to avoid consuming the reactive groups and ensure the strength of the final adhesive layer, the epoxy resin is dehydrated in advance, and high-temperature dehydration is to prevent solvent volatilization.

[0130] After cooling the dehydrated epoxy resin to 50 - 60 °C, add fatty amine to obtain the modified epoxy resin.

[0131] It should be understood that the above cooling to 50 - 60 °C is to prevent explosive polymerization during the subsequent reaction process due to excessive temperature, and at the same time can promote the reaction.

[0132] After cooling the modified epoxy resin to 20 - 30 °C, add solvent B and mix evenly to obtain a homogeneous solution.

[0133] Dehydrate the polyol at 110 - 120 °C to obtain the dehydrated polyol.

[0134] Since the reaction rate of water and isocyanate is very fast, in order to avoid consuming the reactive groups and ensure the strength of the final adhesive layer, the polyol is dehydrated in advance, and high-temperature dehydration is to prevent solvent volatilization.

[0135] After cooling the dehydrated polyol to 50 - 60 °C, add isocyanate to obtain a mixture containing isocyanate groups at the end and isocyanate.

[0136] Mix the mixture containing isocyanate groups at the end and isocyanate with the homogeneous solution evenly, and react at 30 - 40 °C for a period of time to obtain Component B.

[0137] It should be noted that the order of the above steps S221 - 223 and steps S224 - 225 is not specifically limited. It can be that steps S221 - 223 are carried out first, and then steps S224 - 225; or, steps S224 - 225 can be carried out first, and then steps S221 - 223; or, steps S221 - 223 and steps S224 - 225 can be carried out simultaneously.

[0138] The following provides a specific preparation process of a spoke-type non-pneumatic tire:

[0139] 1. Preparation of Component A:

[0140] (1). Heat the internal mixer to 50 - 60 °C, add olefin rubber for internal mixing, heat up to 80 - 90 °C, add antioxidant, accelerator, activator and reinforcing agent, continue internal mixing and heat up to 150 - 160 °C, and discharge the rubber to obtain the first rubber compound.

[0141] (2). After the first rubber compound is parked at 20 - 25 °C for 8 - 10 h, further mix it in an open mill.

[0142] (3). Heat the open mill to 50 - 60 °C, add the first rubber compound and the crosslinking agent, and knead. Then heat it to 90 - 100 °C, take out the rubber, and let it stand at room temperature for 8 - 10 h for standby to obtain the second rubber compound.

[0143] (4). In the reaction kettle, mix the second rubber compound with solvent A until homogeneous to obtain component A.

[0144] 2. Preparation of component B:

[0145] (1). Dehydrate the epoxy resin at 110 - 120 °C, -0.1 MPa, and a rotation speed of 80 - 100 r / min for 2 h. After cooling to 50 - 60 °C, add the fatty amine to obtain the modified epoxy resin. Then cool it to 20 - 30 °C and add solvent B for mixing to obtain a homogeneous solution.

[0146] (2). Dehydrate the polyol at 110 - 120 °C, -0.1 MPa, and a rotation speed of 80 - 100 r / min for 2 h. After cooling to 50 - 60 °C, add the isocyanate to obtain a mixture containing isocyanate groups at the end. Mix this mixture with the component in (1) and react at 30 - 40 °C for 60 min to obtain a homogeneous solution, which is component B.

[0147] 3. Mixing of component A and component B:

[0148] (1). Mix component A and component B at 50 - 70 r / min in a ratio of 100:30 - 100:80 until homogeneous to obtain the adhesive.

[0149] 4. Combination of the adhesive, the tread and the spoke:

[0150] (1). Surface cleaning: Dip a lint - free cloth in dichloromethane (CH2Cl2) and wipe the rubber surface to be bonded. After placing it for 5 min, blow the surface clean with compressed air.

[0151] (2). Coating: Use a coating device to coat the adhesive on the rubber surface. The coating times are 1 - 2 times, and the dry film thickness is 10 - 35 μm.

[0152] (3). Pretreatment: Place the coated sample at ambient temperature or in a constant - temperature device at 15 - 35 °C for more than 30 min. Wait until the surface is dry and then bond.

[0153] (4). Bonding: Fit the rubber surface coated with the adhesive to the spoke and maintain it at a pressure of 0.5 - 5 MPa and a temperature of 40 - 170 °C for 3 min - 25 min.

[0154] (5). Finished product: After placing the bonded product at 80 - 120 °C for 10 - 20 min, the finished product is obtained.

[0155] (6). Injection molding process: Inject the finished product in an injection molding machine.

[0156] It should be noted that the descriptions of olefin rubber, anti - aging agent, accelerator, cross - linker, activator, reinforcing agent, Solvent A, epoxy resin, fatty amine, polyol, isocyanate, and Solvent B in the embodiments of this application can refer to the above - mentioned embodiments and will not be elaborated here.

[0157] The following uses multiple specific examples to illustrate the adhesives / rim - type non - pneumatic tires and their preparation methods and applications of the embodiments of this application and the comparative examples.

[0158] Example 1

[0159] (1). Heat the internal mixer to 50 °C, add natural rubber for internal mixing, heat up to 80 °C, add anti - aging agent, accelerator, activator, and reinforcing agent, continue internal mixing and heat up to 155 °C, then discharge the rubber to obtain the first rubber compound.

[0160] (2). After storing the first rubber compound at 20 - 22 °C for 8 h, further mix it in an open mill.

[0161] (3). Heat the open mill to 55 °C, add the first rubber compound and cross - linker for open milling, heat up to 95 °C, discharge the rubber, and let it stand at room temperature for 8 h for standby to obtain the second rubber compound.

[0162] (4). In a reaction kettle, mix the second rubber compound with Solvent A until homogeneous to obtain Component A.

[0163] (5). Dehydrate epoxy resin at 120 °C, - 0.1 MPa, and a rotation speed of 80 r / min for 2 h. After cooling to 50 °C, add fatty amine. After obtaining the modified epoxy resin, further cool to 25 °C and add Solvent B for mixing to obtain a homogeneous solution.

[0164] (6). Dehydrate polyol at 120 °C, - 0.1 MPa, and a rotation speed of 80 r / min for 2 h. After cooling to 50 °C, add isocyanate to obtain a mixture with terminal isocyanate groups and containing isocyanate. Mix this mixture with the components in (1) and react at 30 °C for 60 min to obtain a homogeneous solution, which is Component B.

[0165] (7). Mix Component A and Component B at 70 r / min in a ratio of 100:30 until homogeneous to obtain the adhesive.

[0166] (8) Injection molding process: The rubber surface coated with the adhesive is bonded to the spoke to obtain the finished product, and the finished product is maintained in an injection molding machine at 70 °C and 4 MPa for 15 min.

[0167] Example 2

[0168] (1). Heat the internal mixer to 55 °C, add natural rubber for internal mixing, heat up to 90 °C, add antioxidant, accelerator, activator and reinforcing agent, continue internal mixing and heat up to 155 °C, discharge the rubber to obtain the first rubber compound.

[0169] (2). After the first rubber compound is parked at 22 °C for 8 h, it is further mixed in an open mill.

[0170] (3). Heat the open mill to 60 °C, add the first rubber compound and crosslinking agent for open milling, heat up to 95 °C, discharge the rubber, place it at room temperature for 10 h for standby to obtain the second rubber compound.

[0171] (4). In the reaction kettle, mix the second rubber compound with solvent A until uniform to obtain component A.

[0172] (5). Dehydrate the epoxy resin at 110 °C, -0.1 MPa and a rotation speed of 80 r / min for 2 h. After cooling to 55 °C, add fatty amine. After obtaining the modified epoxy resin, then cool to 25 °C and add solvent B for mixing to obtain a uniform solution.

[0173] (6). Dehydrate the polyol at 110 °C, -0.1 MPa and a rotation speed of 80 r / min for 2 h. After cooling to 55 °C, add isocyanate to obtain a mixture containing terminal isocyanate groups and isocyanate. Mix this mixture with the components in (1) and react at 33 °C for 60 min to obtain a uniform solution, namely component B.

[0174] (7). Mix component A and component B at 70 r / min in a ratio of 100:30 until uniform to obtain the adhesive.

[0175] (8) Injection molding process: The rubber surface coated with the adhesive is bonded to the spoke to obtain the finished product, and the finished product is maintained in an injection molding machine at 40 °C and 5 MPa for 25 min.

[0176] Example 3

[0177] (1). Heat the internal mixer to 60 °C, add natural rubber for internal mixing, heat up to 90 °C, add antioxidant, accelerator, activator and reinforcing agent, continue internal mixing and heat up to 155 °C, discharge the rubber to obtain the first rubber compound.

[0178] (2). After the first rubber compound is parked at 25 °C for 10 h, it is further mixed in an open mill.

[0179] (3) Heat the mixing mill to 60°C, add the first rubber compound and the cross-linking agent for mixing, heat to 100°C, discharge the rubber, and place it at room temperature for 10 hours to obtain the second rubber compound.

[0180] (4) In a reaction kettle, mix the second rubber material and solvent A until they are uniform to obtain component A.

[0181] (5) The epoxy resin was dehydrated at 100°C, -0.1MPa, and a rotation speed of 100r / min for 2h. After cooling to 60°C, a fatty amine was added to obtain a modified epoxy resin. The epoxy resin was then cooled to 30°C and solvent B was added and mixed to obtain a uniform solution.

[0182] (6) The polyol is dehydrated at 100°C, -0.1MPa, and a rotation speed of 100r / min for 2h. After cooling to 60°C, isocyanate is added to obtain a mixture containing terminal isocyanate groups and isocyanate. The mixture is mixed with the components in (1) and reacted at 35°C for 60min to obtain a uniform solution, i.e., component B.

[0183] (7) Mix component A and component B at 50 r / min until they are uniform to obtain an adhesive.

[0184] (8) Injection molding process: The rubber surface coated with the adhesive is bonded to the wheel spoke to obtain a finished product, and the finished product is maintained at 170°C and 2 MPa for 3 minutes in an injection molding machine.

[0185] Comparative Example 1

[0186] Commercially available polyurethane was used as the adhesive.

[0187] The spoke-type non-pneumatic tires obtained in Examples 1-3 and Comparative Example 1 were tested for peel strength, and the results are shown in Table 1 below.

[0188] Among other things, the peel strength test was performed according to standard ISO 814:2007.

[0189] Table 1

[0190]

[0191] It can be seen from Table 1 that, compared with Comparative Example 1, the peel strengths of Examples 1-3 under different injection molding conditions are greater, and the bonding strength of the adhesive in the spoke-type non-pneumatic tires prepared in Examples 1-3 is very good.

[0192] This application only introduces the contents related to the invention. The remaining structures can be obtained by referring to the relevant technologies and will not be described in detail here.

[0193] As used herein, "embodiment" means that the specific features, structures or characteristics described in connection with the embodiments are included in at least one embodiment of the present application.

[0194] In the specification provided herein, a large number of specific details are set forth. However, it will be understood that embodiments of the present application may be practiced without these specific details. In some instances, well-known methods, structures and techniques have not been shown in detail so as not to obscure the understanding of this specification.

[0195] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and are not intended to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A spoke-type non-pneumatic tire, characterized in that: The spoke-type non-pneumatic tire at least comprises a wheel surface and an adhesive layer, wherein the adhesive layer is located on one side of the wheel surface and is used to be bonded to the wheel surface, the adhesive layer comprises an adhesive, the wheel surface comprises a base rubber, and the adhesive is used to be cross-linked with the base rubber; The adhesive comprises component A and component B, and the ratio of component A to component B is in the range of 100:30-100:80; The A component comprises by weight: Olefin rubber, 80-100 parts; Anti-aging agent, 3-6 parts; Accelerator, 1-3 parts; Cross-linking agent, 1-3 parts; Activator, 3-10 parts; Reinforcing agent, 40-60 parts; A solvent, 60-200 parts; The B component comprises by weight: Epoxy resin, 30-60 parts; Isocyanate, 5-30 parts; Fatty amine, 1-3 parts; the fatty amine is a fatty amine having a double active group; Polyol, 60-100 parts; the polyol is a molecule containing both olefin bonds and hydroxyl groups, and the number of hydroxyl groups is greater than or equal to 2; B solvent, 60-100 parts.

2. The spoke-type non-pneumatic tire according to claim 1, characterized in that: The peel strength of the adhesive layer is in the range of 23-33 KN / m.

3. The spoke-type non-pneumatic tire according to claim 1 or 2, characterized in that: The antioxidant includes a secondary amine antioxidant; The accelerator includes a sulfenamide accelerator; The cross-linking agent includes sulfur; The activator includes a metal inorganic activator; The reinforcing agent includes carbon black; The A solvent includes at least one of ketones and aromatic hydrocarbons.

4. The spoke-type non-pneumatic tire according to claim 1 or 2, characterized in that: The epoxy resin includes bisphenol A type epoxy resin; The isocyanate includes diisocyanate; The fatty amine includes a fatty amine having a double active group; The polyols include polyols containing both olefin bonds and multiple hydroxyl groups; The B solvent includes at least one of ketones and aromatic hydrocarbons.

5. The spoke-type non-pneumatic tire according to claim 1 or 2, characterized in that: The base rubber of the wheel tread includes natural rubber.

6. The spoke-type non-pneumatic tire according to claim 1 or 2, characterized in that: The spoke-type non-pneumatic tire further comprises a spoke, wherein the spoke is located on a side of the adhesive layer away from the wheel surface, and the adhesive layer is also used to bond with the spoke; The material of the spokes includes any one of polyurethane and modified polyurethane.

7. A method for preparing a spoke-type non-pneumatic tire according to any one of claims 1 to 6, characterized in that: The steps include: Cleaning the wheel surface of the spoke-type non-pneumatic tire; preparing the adhesive; Applying the adhesive to one side surface of the wheel surface; Laminating the wheel surface coated with the adhesive to the wheel spokes to form the spoke-type non-pneumatic tire preparation; The spoke-type non-pneumatic tire preform is injection molded to obtain the spoke-type non-pneumatic tire; wherein the injection molding temperature ranges from 130 to 260° C., the insulation time ranges from 1 to 30 minutes after injection molding, the injection molding pressure ranges from 40 to 80 MPa, and the injection mold temperature ranges from 30 to 130° C.

8. The method for preparing a spoke-type non-pneumatic tire according to claim 7, characterized in that: The preparation of the adhesive comprises: Producing the A component; Producing the B component; The component A and the component B are uniformly mixed in a ratio of 100:30-100:80 to obtain the adhesive.

9. The method for preparing a spoke-type non-pneumatic tire according to claim 8, characterized in that: The preparation of the A component comprises: The olefin rubber is kneaded at 50-60° C. for a period of time, then heated to 80-90° C., the antioxidant, the accelerator, the activator and the reinforcing agent are added, and the kneading is continued and the temperature is raised to 150-160° C., and the rubber is discharged to obtain a first rubber compound; The first rubber material is placed at 20-25° C. for a period of time, then heated to 50-60° C., the cross-linking agent is added and the mixture is mixed for a period of time, and then heated to 90-100° C. to produce the rubber material, thereby obtaining the second rubber material; The second rubber material and the A solvent are uniformly mixed to obtain the A component.

10. The method for preparing a spoke-type non-pneumatic tire according to claim 8, characterized in that: The preparation of the B component comprises: Dehydrating the epoxy resin at 110-120° C. to obtain a dehydrated epoxy resin; After cooling the dehydrated epoxy resin to 50-60° C., adding the fatty amine to obtain a modified epoxy resin; After cooling the modified epoxy resin to 20-30° C., adding the solvent B and mixing evenly to obtain a uniform solution; Dehydrating the polyol at 110-120° C. to obtain a dehydrated polyol; After cooling the dehydrated polyol to 50-60° C., adding the isocyanate to obtain a mixture containing an isocyanate group at the end and an isocyanate; The mixture containing isocyanate groups at the ends and isocyanate is mixed evenly with the uniform solution, and reacted at 30-40° C. for a period of time to obtain the B component.

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