Rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanization alloy, preparation method thereof and tire inner liner

Abstract

The invention relates to the field of high polymer materials, and particularly discloses a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanization alloy and a preparation method and application thereof. The preparation method of the rubber and plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy comprises the following steps: mixing dispersed phase halogenated butyl rubber with gas barrier resin, a compatibilizer and a thermal antioxidant at a high temperature, cooling, mixing liquid rubber, a dynamic vulcanizing agent and stannous chloride, and dynamically vulcanizing to obtain thermoplastic vulcanized halogenated butyl rubber; and uniformly mixing with continuous-phase halogenated butyl rubber and a heat-resistant oxygen agent at a high temperature, cooling, sequentially adding zinc oxide, stearic acid, an anti-aging agent, carbon black, a lamellar inorganic filler, liquid rubber, protective wax, a vulcanizing agent and an auxiliary agent, and uniformly mixing to obtain the dynamic vulcanized alloy. The dynamically vulcanized alloy prepared by the invention has excellent gas barrier property, good ductility and adhesion property, can be applied to the existing rubber rolling equipment and process, and can be used for forming a novel DVA tire inner liner with the thickness as low as 0.3 mm.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, and more specifically, to a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanization alloy, its preparation method, and a tire airtight layer. Background Technology

[0002] With the rapid development of the automotive industry, especially new energy vehicles, higher requirements are being placed on new tire technologies such as low rolling resistance, self-healing technology, and intelligent monitoring. For every 10% reduction in tire rolling resistance, the range of electric vehicles can increase by 5%-8%. Structural optimization designs such as tire flattening and rim width can reduce rolling resistance. Improvements in tire material production processes, such as reducing molecular chain entanglement through chemical rubber refining processes and combining modified solution-polymerized styrene-butadiene rubber with silica, can also reduce tire rolling resistance.

[0003] The airtight layer of a tire is an air barrier layer located on the inner surface of the tire to maintain the internal pressure of the tire. It is usually made of rubber composition made of butyl rubber or halogenated butyl rubber, which can provide the mechanical properties required for the tire airtight layer and good gas barrier performance. However, traditional vulcanized halogenated butyl rubber technology has difficulty in further improving gas barrier performance, reducing the thickness of the airtight layer, and ensuring the tire's pressure retention performance.

[0004] ExxonMobil pioneered a new gas-tight layer material called Dynamically Vulcanized Alloy (DVA), which is prepared by dynamically vulcanizing nylon resin and butyl rubber. Halogenated butyl rubber is used as the dispersed phase and nylon as the continuous phase. It is processed into a thinner gas-tight layer using plastic extrusion, casting, or blow molding processes. At the same time, the material has high gas barrier properties, enabling the design of thinner and lighter tires. This technology was first applied by Yokohama Tire in Japan.

[0005] Ethylene-vinyl alcohol copolymer (EVOH) possesses excellent gas barrier properties. In the prior art, Chinese invention patent application CN201180068893.8 discloses a thermoplastic elastomer and vulcanized rubber based on EVOH, which is made from EVOH and butyl rubber or halogenated butyl rubber. Although both halogenated butyl rubber and EVOH copolymers are materials with excellent gas barrier properties, the thermoplastic vulcanizate prepared from them through dynamic vulcanization has even better gas barrier performance. However, halogenated butyl rubber and EVOH copolymers have poor compatibility. Therefore, improving the compatibility and reducing the hardness of the halogenated butyl rubber / EVOH copolymer system is a challenge. Typically, compatibilizers are added during the preparation of butyl rubber / EVOH TPV to improve the compatibility and obtain products with good performance. In the prior art, Chinese invention patent application number CN201210509704.2 discloses a gas-barrier and water vapor-resistant EPDM / EVOH-MAA dynamically vulcanized thermoplastic elastomer. EPDM and EVOH-MAA are dynamically vulcanized, and maleic anhydride is grafted onto EPDM rubber as a compatibilizer to improve compatibility and prepare EVOH system DVA.

[0006] The aforementioned technology describes the use of butyl rubber and barrier resin as main raw materials, through compatibilizer optimization and dynamic vulcanization technology to prepare DVA materials with barrier resin as the continuous phase and vulcanized rubber as the dispersed phase. Compared with traditional halogenated butyl rubber, it has significant advantages in gas barrier performance. Thinner film products can be produced through plastic casting or blown film molding. However, this type of dynamically vulcanized thermoplastic elastomer with a single thermoplastic resin as the continuous phase is incompatible with existing tire molding processes and equipment. According to the feeding, cutting, and bonding methods of existing tire molding machines for roll materials, under normal temperature conditions, traditional vulcanized halogenated butyl rubber gas-tight layer materials can achieve better butt joints and joint pressing adhesion due to the unvulcanized compound. Under high pressure, the rubber flows, and after high-temperature vulcanization, the joint is completely integrally formed. Dynamically vulcanized DVA airtight layer films with a single thermoplastic resin as the continuous phase cannot achieve joint bonding and adhesion at room temperature on existing tire forming machines. Although fusion bonding can be achieved by heating the material above its melting point using auxiliary equipment, or by fusion welding of the joints on the tire forming machine using laser equipment, laser welding requires the material to possess the contradictory properties of laser transmittance and absorption. The material bonding interface forms a molten bonding area under the action of laser, which is highly difficult to achieve. Moreover, because the film made of dynamically vulcanized thermoplastic elastomer material has poor extensibility and no adhesion compared to the compounded rubber materials of other tire layers, abnormal phenomena such as peeling, wrinkling, and air intake can occur after the overall shape of the tire body expands and recovers during the tire forming process. This leads to delamination, airtight layer wrinkles, and air bubbles after tire vulcanization. Unless the entire tire forming process is completely changed, industrialization is extremely difficult.

[0007] In the prior art, Chinese invention patent application number 20111019350.9 discloses a tire airtight layer composite material, which is an alternating multilayer structure composed of a barrier layer of polyvinyl alcohol (PVOH) and a base layer of rubber. This multilayer structure or laminated material composed of barrier materials improves gas barrier performance. However, the multilayer alternating coating process is complex and time-consuming, and the extrusion of wide, thin rubber films is difficult. Therefore, whether coated or laminated, the orderliness, integrity, and material performance stability of the material's microstructure are difficult to guarantee in actual production. The multilayer barrier resin limits the ductility and elastic recovery of the multilayer structure material, making it difficult to meet the requirements of tire molding processes. This necessitates a complete overhaul of the entire tire molding process.

[0008] Regarding the aforementioned technologies, the inventors believe there is an urgent need to provide a new type of DVA material that possesses excellent ductility and adhesion under traditional tire molding conditions, can be made into a thinner, gas-tight layer with strong gas barrier capabilities, and is compatible with existing tire production equipment and processes. Summary of the Invention

[0009] In order to prepare a tire airtight layer that has both ductility and adhesion under normal temperature tire molding conditions, and can achieve equivalent or better gas barrier performance with only 1 / 2 the thickness of the traditional airtight layer without changing the entire tire molding process, this application provides a rubber-plastic dual continuous heterogeneous cross-linked dynamic vulcanization alloy, its preparation method and a tire airtight layer.

[0010] In a first aspect, this application provides a method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanization alloy, employing the following technical solution: A method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy includes the following steps; S1. The dispersed phase halogenated butyl rubber is mixed evenly with gas barrier resin, compatibilizer and first heat-resistant antioxidant at high temperature to obtain high temperature mixed rubber. The mixing temperature is 10-20℃ higher than the melting point of gas barrier resin. S2. After the high-temperature mixed rubber obtained in S1 is cooled by open milling, it is then mixed evenly with the first liquid rubber, dynamic vulcanizing agent and stannous chloride to obtain the mixed rubber. S3. The compound obtained in S2 is subjected to dynamic vulcanization to obtain thermoplastic vulcanized halogenated butyl rubber. S4. The thermoplastic vulcanized halogenated butyl rubber obtained in S3 is directly mixed with the continuous phase halogenated butyl rubber and the second heat-resistant oxygen agent at high temperature and uniformly. The mixing temperature is 10-20℃ higher than the melting point of the gas barrier resin. S5. After cooling the high-temperature mixture obtained in S4 through open milling, zinc oxide, stearic acid, antioxidant, carbon black, lamellar inorganic filler, second liquid rubber and protective wax, vulcanizing agent and vulcanizing aid are added in stages in sequence and mixed evenly to obtain a dynamic vulcanized alloy of rubber and plastic bicontinuous heterogeneous crosslinking.

[0011] By adopting the above technical solution, the halogenated butyl rubber and the gas barrier resin are inherently poorly compatible. Using a compatibilizer can reduce the interfacial tension between the two phases, promoting the formation of uniform and fine phase domains at the microscale, creating a prerequisite for the subsequent formation of a bicontinuous phase. Therefore, under the action of the compatibilizer, the dispersed phase halogenated butyl rubber and the gas barrier resin are thoroughly mixed to form a well-compatible initial rubber-plastic mixture. This mixture is then dynamically vulcanized with the first liquid rubber, a dynamic vulcanizing agent, and the catalyst stannous chloride through a twin-screw extruder. The liquid rubber acts as a softener and processing aid, and... After a portion of the halogenated butyl rubber is mixed, the viscosity of the material system is reduced. Under the action of high temperature and high shear, the rubber phase is dispersed into micron-sized vulcanized rubber particles. The barrier resin forms a continuous phase under high temperature and shear, which encapsulates the vulcanized rubber particles. After direct high-temperature discharge, it is blended with the reintroduced continuous phase of halogenated butyl rubber, and mixed with the formed vulcanized rubber particles and the barrier resin continuous phase to form a two-phase mixture of vulcanized rubber particles and newly added unvulcanized rubber. Finally, it is mixed with zinc oxide, stearic acid, filler, and liquid rubber to form a heterogeneous structure. Therefore, the above process can obtain a dynamic vulcanization alloy with halogenated butyl rubber particles as the dispersed phase and halogenated butyl rubber and barrier resin as the bicontinuous phases. The continuous rubber phase and the dispersed phase of vulcanized halogenated butyl rubber particles form a heterogeneous phase structure. This microstructure enables the material to simultaneously possess ductility and adhesion properties as well as high barrier properties. Existing rubber calendering equipment and processes can be used to obtain DVA films with a thickness as low as 0.3 mm. These films can then be composited with a transition layer or used alone, cut to specified widths, and fed into a tire forming machine for tire vulcanization to produce a new type of DVA airtight tire. The interface between the continuous halogenated butyl rubber phase and the dispersed halogenated butyl rubber undergoes a cross-linking reaction again, further strengthening this heterogeneous cross-linking structure. Combined with the continuous barrier resin, a tire airtight layer with excellent continuous performance and good gas barrier properties is obtained. Compared with traditional pneumatic tires, the pneumatic tire prepared in this application achieves significant weight reduction, pressure retention, and rolling resistance reduction. Equipping the DVA pneumatic tire of this application can improve the fuel efficiency of fuel vehicles and enhance the energy efficiency and driving range of new energy vehicles with heavy weight and high tire pressure.

[0012] Preferably, the mixing temperature in steps S2 and S5 is below 80°C.

[0013] Preferably, in step S3, the screw speed during extrusion vulcanization is 300-500 rpm, and the temperature in each zone is ±20℃ of the melting point of the gas barrier resin.

[0014] Preferably, in the preparation of the rubber-plastic bicontinuous heterogeneous crosslinking dynamic vulcanization alloy, the raw materials are as follows by weight: The components are: 50-70 parts dispersed phase halogenated butyl rubber, 30-50 parts gas barrier resin, 2-10 parts compatibilizer, 0.4-1 part first heat antioxidant, 2-10 parts first liquid rubber, 3-8 parts dynamic vulcanizing agent, 1-4 parts stannous chloride, 80-100 parts continuous phase halogenated butyl rubber, 0.4-1 part second heat antioxidant, 2-6 parts zinc oxide, 2-4 parts stearic acid, 5-50 parts carbon black, 5-40 parts lamellar inorganic filler, 2-10 parts second liquid rubber, 1-6 parts antioxidant, 2-4 parts protective wax, 2-5 parts vulcanizing agent, and 2-5 parts vulcanizing auxiliaries.

[0015] By adopting the above technical solution, the amounts of dispersed halogenated butyl rubber and continuous halogenated butyl rubber are appropriate, while the amount of gas barrier resin is sufficient to form a continuous network, providing higher gas barrier properties, without excessive dosage leading to material stiffness and loss of elasticity. This constructs a structure with gas barrier resin as the continuous phase and uncured rubber as a bicontinuous phase, reinforced by partially vulcanized rubber particles as the dispersed phase. This structure gives the material good ductility and adhesion properties, allowing the application of existing rubber calendering equipment and processes to obtain DVA films with thicknesses as low as 0.3 mm. This better matches the stable feeding requirements of subsequent tire molding machines, and producing films with a thickness of 0.5 mm is more advantageous for existing tire production processes and equipment, far below the current industry standard of 1 mm. Applied to tire molding, the interface between the continuous halogenated butyl rubber phase and the dispersed halogenated butyl rubber undergoes a cross-linking reaction again, further strengthening this heterogeneous cross-linking structure. Combined with the continuous barrier resin, this results in a tire airtight layer with excellent continuous performance and good gas barrier properties.

[0016] Preferably, the dispersed phase halogenated butyl rubber and gas barrier resin account for 50-70 wt% and 30-50 wt% of their total content, respectively.

[0017] Preferably, the dispersed phase, halogenated butyl rubber, and gas barrier resin account for 60 wt% and 40 wt% of their total weight, respectively.

[0018] Preferably, the dispersed phase, halogenated butyl rubber, and gas barrier resin account for 65 wt% and 35 wt% of their total weight, respectively.

[0019] Preferably, the dispersed phase, halogenated butyl rubber, and gas barrier resin account for 70 wt% and 30 wt% of their total weight, respectively.

[0020] Preferably, the dispersed phase, halogenated butyl rubber, and gas barrier resin account for 50 wt% and 50 wt% of their total weight, respectively.

[0021] Preferably, the total amount of the dispersed phase halogenated butyl rubber and the gas barrier resin is in a mass ratio of 100:100 to the continuous phase halogenated butyl rubber.

[0022] Preferably, the halogen content of both the dispersed phase halogenated butyl rubber and the continuous phase halogenated butyl rubber is 0.3-1.8 wt%, and both are selected from at least one of brominated butyl rubber, chlorinated butyl rubber, and brominated polyisobutylene-p-methylstyrene rubber. The gas barrier resin is selected from at least one of PA6, PA6 / PA66 binary copolymer, and EVOH.

[0023] By adopting the above technical solutions, halogenated butyl rubber with a halogen content of 0.3-1.8wt% can ensure the activity of dynamic vulcanization reaction and avoid the risk of processing scorching or later aging caused by excessive halogen. Brominated / chlorinated butyl rubber and brominated polyisobutylene-p-methylstyrene rubber have the advantages of low gas permeability, excellent elasticity and aging resistance. PA6, PA6 / PA66 binary blends, and EVOH are all high-barrier resins that can specifically reduce the permeability of gases such as oxygen and carbon dioxide. They form a bicontinuous phase with halogenated butyl rubber through dynamic vulcanization, which can simultaneously retain the barrier properties of the resin and the strength and toughness of the rubber. Moreover, the preferred gas barrier resin with a melting point below 190°C can also reduce the halogen loss that may occur during the high-temperature mixing stage of halogenated butyl rubber.

[0024] Preferably, the compatibilizer is selected from at least one of ethylene-methyl acrylate copolymer grafted glycidyl acrylate, polypropylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and maleic anhydride grafted polyolefin elastomer.

[0025] By adopting the above technical solutions, the glycidyl acrylate grafted onto the ethylene-methyl acrylate copolymer contains highly reactive epoxy groups, which readily undergo ring-opening reactions with the amino or carboxyl groups at the ends of barrier resins such as EVOH and nylon, forming strong covalent bonds. This improves the compatibility between the barrier resin and halogenated butyl rubber, and reduces the interfacial tension between the two phases. Meanwhile, the polypropylene-maleic anhydride copolymer and maleic anhydride-grafted polyolefin elastomer exhibit excellent compatibility with the barrier resin, strong interfacial anchoring effect, and can effectively promote the dispersion of the rubber phase in the plastic phase, stabilize the phase morphology, and prevent phase aggregation. The styrene-maleic anhydride copolymer is highly polar and has excellent compatibility with the barrier resin, being partially miscible. During compatibilization, it can strongly embed itself into the barrier resin and react with the resin through the anhydride groups. The styrene segments on the other side interact with the rubber phase, thereby strengthening the interfacial layer, improving the tensile strength, tear strength, and impact toughness of the alloy, blocking the channels for gas permeation between the phase interfaces, and ensuring airtightness.

[0026] Preferably, both the first liquid rubber and the second liquid rubber are selected from at least one of liquid polyisobutylene rubber and liquid butyl rubber with a viscosity-average molecular weight of 10,000-100,000.

[0027] By adopting the above technical solutions, liquid rubber with a viscosity-average molecular weight of 10,000-100,000 can remain in a liquid state to ensure fluidity, while having sufficiently long molecular chains to provide good cohesion and elasticity. The first liquid rubber can adjust the viscosity of the initial blend, making high-intensity mechanical shearing and dynamic vulcanization reactions easier to carry out, which helps to form a uniform and fine vulcanized rubber dispersion phase. The second liquid rubber can effectively improve the processing fluidity and adhesion of the material and reduce hardness, ensuring the smooth progress of subsequent calendering, molding and other processes. Compared with small molecule oil-based processing aids, it provides the above-mentioned improvements in processing performance while also ensuring that the final vulcanized product has better mechanical properties, elasticity and gas barrier properties.

[0028] Preferably, both the first and second anti-oxidant agents comprise a primary antioxidant or a primary antioxidant and a secondary antioxidant in any proportion. The primary antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-thionylethylene glycol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 1,3,5-tris(4-tert-butyl-3-hydroxyphenyl)propionate. At least one of (-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,2H,5H)-trione; the co-antioxidant is selected from at least one of tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, dioctadecyl thiodipropionate, dioctadecyl thiodipropionate and pentaerythritol tetra(3-lauryl thiopropionate); The antioxidant is selected from at least one of N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester, 2,2,4-trimethyl-1,2-dihydroquinoline polymer and 2-mercaptobenzimidazole; The lamellar inorganic filler is selected from at least one of diisopropyl oxide lamellar carbon, talc, modified aluminum magnesium hydrotalcite, modified clay, and modified montmorillonite. The protective wax is selected from at least one of paraffin wax and microcrystalline wax.

[0029] By adopting the above technical solution, aluminum-magnesium hydrotalcite belongs to layered bimetallic hydroxides. It has a unique layered structure and excellent gas barrier ability, but its surface polarity is high and it is prone to agglomeration, resulting in poor compatibility with the rubber matrix. Therefore, it needs to be modified to enhance compatibility and improve air tightness.

[0030] Preferably, the modified aluminum-magnesium hydrotalcite is prepared by the following method: Aluminum magnesium hydrotalcite and nitrogen-containing heterocyclic compounds were added to N,N-dimethylformamide, stirred evenly, centrifuged, washed, and dried to obtain an intermediate. The intermediate was dispersed in water at 60-70℃, and polyhexane glycol (PEG4000) was added. The mixture was stirred at 60-70℃ for 4-8 hours, centrifuged, dried, and ground to obtain modified aluminum-magnesium hydrotalcite.

[0031] By adopting the above technical solution, the nitrogen-containing groups in the nitrogen-containing heterocyclic compound molecules form a strong bond with the hydroxyl groups on the surface of aluminum-magnesium hydrotalcite through selective hydrogen bonding. Moreover, the nitrogen-containing heterocyclic compound can introduce functional groups that can react with rubber on the surface of hydrotalcite. PEG4000 is adsorbed onto the remaining surface sites through hydrogen bonding, and its long-chain polyether segments further enhance steric hindrance. At the same time, the long-chain molecules of PEG interact with the anchored nitrogen-containing heterocycles through hydrogen bonding to form a softer coating layer. Its -CH2-CH2-O- segments have little polarity difference with rubber, and as an interfacial transition layer, it reduces the interfacial tension with rubber. Furthermore, the long molecular chains of PEG4000 extend in the rubber matrix, forming a repulsion region around the aluminum-magnesium hydrotalcite, preventing the contact and aggregation of aluminum-magnesium hydrotalcite. It also physically entangles and interacts with the rubber molecular chains through van der Waals forces, improving interfacial bonding and stress transmission, enhancing mechanical strength, extending the gas diffusion path, reducing gas permeability, and improving thermal stability.

[0032] The mass ratio of the aluminum-magnesium hydrotalcite, nitrogen-containing heterocyclic compound, and PEG40000 is 1:0.2-0.3:0.05-0.2.

[0033] By adopting the above technical solution, the three substances in the above ratio can ensure that the nitrogen-containing heterocyclic compound can be fully anchored on the aluminum-magnesium hydrotalcite, and that PEG4000 can form an effective coating layer.

[0034] Preferably, the first and second anti-oxidant are both antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0035] Preferably, the sheet-like inorganic filler comprises talc powder and diisopropyl oxide sheet carbon in a mass ratio of 1.5:1.

[0036] By adopting the above technical solution, talc powder and diisopropyl oxide layered carbon are used in combination. Talc powder acts as a processing modifier and reinforcing agent to help improve air tightness, while diisopropyl oxide layered carbon enhances air tightness, reduces gas permeation, and improves heat resistance and durability. When used together, the micron-sized talc sheets and nano-sized layered carbon sheets can form a double tortuous path in the vulcanized alloy, increasing the gas permeation path and improving the gas barrier effect.

[0037] Secondly, this application provides a rubber-plastic bicontinuous heterogeneous crosslinking dynamic vulcanization alloy, which adopts the following technical solution: A rubber-plastic bicontinuous heterogeneous crosslinking dynamic vulcanizing alloy is prepared using the aforementioned preparation method.

[0038] By adopting the above technical solution, the above preparation method can obtain a dynamic vulcanization alloy in which some of the dynamically vulcanized cross-linked halogenated butyl rubber particles are dispersed phases, and the other part of the halogenated butyl rubber and barrier resin are bicontinuous phases. The continuous rubber phase and the dispersed phase of the vulcanized halogenated butyl rubber particles form a heterogeneous phase structure, which can obtain better ductility and adhesion properties. It is suitable for existing tire production and can be made into thinner DVA films for airtight layers, which can reduce tire weight, reduce rolling resistance and achieve better pressure retention effect.

[0039] Thirdly, this application provides a tire airtight layer, which adopts the following technical solution: A tire airtight layer is made from the aforementioned rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy as raw material, through extrusion sheeting and calendering.

[0040] Preferably, the tire airtight layer is combined with the transition layer or used alone as an inner liner, and is vulcanized with the belt layer, cord layer, bead, sidewall rubber, tread rubber and intertread rubber after tire molding to obtain the tire.

[0041] By adopting the above technical solution, compared with traditional airtight tires, the tire airtight layer made of the rubber-plastic dual continuous heterogeneous cross-linked dynamic vulcanization alloy of this application, due to its unique microstructure, requires only half the thickness of a traditional airtight layer to achieve equivalent or better gas barrier performance. This results in a reduction in overall tire weight, thereby reducing rolling resistance and energy loss. For gasoline vehicles, the reduction in rolling resistance and vehicle weight reduces the amount of fuel consumed by the engine when driving the vehicle, thus improving fuel efficiency. For new energy vehicles with higher weight and tire pressure, the pressure-holding performance of the tire airtight layer ensures that the tire maintains stable pressure under high pressure, reducing energy loss caused by pressure fluctuations. Simultaneously, it achieves weight reduction and rolling resistance reduction, enabling new energy vehicles to utilize electrical energy more effectively, improving energy efficiency, extending vehicle range, and increasing vehicle driving efficiency.

[0042] In summary, this application has the following beneficial effects: 1. Because this application uses a method of first dynamically vulcanizing the dispersed phase halogenated butyl rubber and the gas barrier resin, and then mixing them with the continuous phase halogenated butyl rubber, the dispersed phase halogenated butyl rubber forms tiny, dispersed crosslinked particles. These particles act as reinforcing points, providing strength, thermal stability, and creep resistance, while the continuous phase halogenated butyl rubber is slightly vulcanized to form a soft, continuous rubber network, responsible for providing ductility and adhesion properties. Existing rubber calendering equipment and processes can be used to obtain DVA films with lower thicknesses, which can be used as airtight layers in tire molding. The interface between the continuous halogenated butyl rubber phase and the dispersed halogenated butyl rubber undergoes another crosslinking reaction, further strengthening this heterogeneous crosslinked structure. Combined with the continuous barrier resin, a tire airtight layer with excellent continuous performance and good gas barrier properties is obtained.

[0043] 2. In this application, talc powder and diisopropyl oxide layered carbon are preferably used in a specific ratio as layered inorganic fillers. Talc powder can improve processability, rigidity and air tightness, while layered carbon can enhance melt strength and rigidity. The combination of the two can increase the gas permeation path and improve the gas barrier effect.

[0044] 3. In this application, nitrogen-containing heterocyclic compounds and PEG4000 are preferably used to modify aluminum-magnesium hydrotalcite. The nitrogen-containing heterocyclic compounds form hydrogen bonds or coordination bonds with aluminum-magnesium hydrotalcite, while PEG4000 is adsorbed on the remaining surface sites through hydrogen bonds, further enhancing steric hindrance, thereby improving the dispersibility of aluminum-magnesium hydrotalcite in the alloy material, and thus improving the mechanical strength and gas barrier ability of the alloy material. Attached Figure Description

[0045] Figure 1 A schematic diagram of the microstructure of a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy. Figure 1 The blue area represents the rubber phase.

[0046] Figure 2 The adhesion of the tire airtight layer joint made of the rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanization alloy prepared in Example 5.

[0047] Figure 3 The image shows the joint condition after vulcanization molding of the tire airtight layer made from the rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanization alloy prepared in Example 5.

[0048] Figure 4 Two-dimensional imager imaging of the cross-section of a novel DVA tire containing an airtight layer made of a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy as described in Example 5.

[0049] Figure 5 This is a peel strength test diagram. Detailed Implementation

[0050] The present application will be further described in detail below with reference to the embodiments.

[0051] Preparation Examples of Modified Aluminum Magnesium Hydrotalcite 1-4 In the following preparation examples, the aluminum-magnesium hydrotalcite was selected from Hubei Langbowan Biotechnology, model LBW-3453, and PEG000 was selected from Nanjing Yingguan New Materials, model PEG4000.

[0052] Preparation Example 1: (1) 4g of aluminum magnesium hydrotalcite and 1g of nitrogen-containing heterocyclic compound 1,2,4-triazole were added to 30mL of DMF, stirred for 6h, centrifuged, washed 5 times with distilled water, and dried at 60℃ for 24h to obtain the intermediate; (2) Disperse the intermediate in 50 mL of water at 70 °C, add 0.6 g PEG4000, stir at 70 °C for 6 h, centrifuge, vacuum dry at 60 °C for 24 h, pulverize, grind, and pass through a 200 mesh sieve to obtain modified aluminum magnesium hydrotalcite.

[0053] Preparation Example 2: (1) 4g of aluminum magnesium hydrotalcite and 0.6g of PEG4000 were added to 50mL of water at 70℃, stirred at 70℃ for 6h, centrifuged, and vacuum dried at 60℃ to obtain the intermediate; (2) The intermediate and 1g of nitrogen-containing heterocyclic compound 1,2,4-triazole were added to 30mL of LDMF, stirred for 6h, washed 5 times with distilled water, centrifuged, dried at 60℃ for 24h, pulverized, ground and passed through a 200-mesh sieve to obtain modified aluminum magnesium hydrotalcite.

[0054] Preparation Example 3: 4g of aluminum-magnesium hydrotalcite and 1g of nitrogen-containing heterocyclic compound 1,2,4-triazole were added to 30mL of DMF, stirred for 6h, centrifuged, washed 5 times with distilled water, dried at 60℃ for 24h, pulverized, ground, and passed through a 200-mesh sieve to obtain modified aluminum-magnesium hydrotalcite.

[0055] Preparation Example 4: 4g of aluminum-magnesium hydrotalcite and 0.6g of PEG4000 were added to 50mL of water at 70℃, stirred at 70℃ for 6h, centrifuged, vacuum dried at 60℃, pulverized, ground, and passed through a 200-mesh sieve to obtain modified aluminum-magnesium hydrotalcite. Example

[0056] In the following examples and comparative examples, unless otherwise specified, all raw materials used were commercially available products: brominated butyl rubber (BIIR), selected from Lanxess / Allantech, grade 2030; The ethylene-vinyl alcohol copolymer (EVOH) was selected from Changchun Chemical Company, with the grade EV3815F; The PA6 / PA66 binary copolymer was selected from Ube Industries, Ltd. of Japan, with the grade name PA5033B. The phenolic resin was selected from Liben Company, with the brand name SP-1045; The ethylene-methyl acrylate copolymer grafted with glycidyl acrylate (EMA-g-GMA) was selected from Hangzhou Haiyi Polymer Materials, with the grade name H810. The polypropylene-maleic anhydride copolymer (PP-g-MAH) was selected from DuPont, with the grade 353D. The styrene elastomer-maleic anhydride copolymer (SEBS-g-MAH) was selected from Kraton, brand name 1901; Maleic anhydride-grafted polyolefin elastomer (POE-g-MAH) is selected from Coais Chemical, brand name W1A; The carbon black was selected from Corbett Company, grade N660; The diisopropyl oxide sheet carbon was selected from Shandong Dike Chemical Technology Co., Ltd., with the grade SD1517. The talc powder was selected from Jiangmen Jicai Chemical Co., Ltd., and its grade was 815LD. The liquid polyisobutylene rubber was selected from Anhui Shunhang New Materials, with the grade SDG-8450.

[0057] Example 1: A method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, comprising the following steps: S1. The dispersed phase halogenated butyl rubber, gas barrier resin, compatibilizer and first heat-resistant antioxidant are mixed evenly in an internal mixer at 190°C according to the amounts in Table 1 to obtain a high-temperature mixed rubber. The dispersed phase halogenated butyl rubber is brominated butyl rubber with a bromine content of 1.8%, the gas barrier resin is EVOH with a melting point of 173°C, the heat-resistant antioxidant is antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, and the compatibilizer is polypropylene-maleic anhydride graft copolymer. S2. The high-temperature mixed rubber obtained in S1 is cooled by an open mill, and the first liquid rubber, dynamic vulcanizing agent and stannous chloride are added. The material temperature is kept below 80°C during mixing, and the mixture is mixed evenly to obtain a compound. The first liquid rubber is liquid polyisobutylene rubber. S3. The compound obtained in S2 is fed into a twin-screw extruder through a conical twin-screw forced feeding device. The extrusion temperature is: Zone 1 160°C, Zone 2 165°C, Zone 3 170°C, Zone 4 175°C, Zone 5 180°C, Zone 7 185°C, Zone 8 190°C, Zone 9 190°C, Zone 10 190°C, Zone 11 190°C, Zone 12 190°C, and the die head 190°C. The screw speed is 400 rpm. Dynamic vulcanization is carried out. The die head of the twin-screw extruder is not equipped with an extrusion nozzle and the material is discharged directly to obtain thermoplastic vulcanized halogenated butyl rubber. S4. The thermoplastic vulcanized halogenated butyl rubber obtained in S3 is mixed with the continuous phase halogenated butyl rubber and the second heat-resistant antioxidant, and then mixed evenly at 190°C to obtain a high-temperature mixture. The continuous phase halogenated butyl rubber is brominated butyl rubber, and the second heat-resistant antioxidant includes antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1. S5. After cooling the high-temperature mixture obtained in S4 through a two-roll mill, zinc oxide, stearic acid, antioxidant, carbon black, lamellar inorganic filler, second liquid rubber and protective wax, vulcanizing agent and vulcanization accelerator are added in stages. The mixture is then mixed evenly below 80°C to obtain a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy. The antioxidant is antioxidant 4010, the second liquid rubber is liquid polyisobutylene rubber, the vulcanizing agent is sulfur, the vulcanization accelerator is DM, and the lamellar inorganic filler is talc.

[0058] Table 1 Example 2: A method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, comprising the following steps: S1. The dispersed phase halogenated butyl rubber, gas barrier resin, compatibilizer and first heat-resistant antioxidant are mixed uniformly in an internal mixer at 200°C according to the amounts in Table 2 to obtain a high-temperature mixed rubber. The dispersed phase halogenated butyl rubber is brominated butyl rubber with a bromine content of 1.8%. The gas barrier resin is a PA6 / PA66 binary copolymer with a melting point of 196°C. The heat-resistant antioxidant is antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1. The compatibilizer is ethylene-methyl acrylate copolymer grafted with glycidyl acrylate. S2. The high-temperature mixed rubber obtained in S1 is cooled by an open mill, and the first liquid rubber, dynamic vulcanizing agent and stannous chloride are added. The material temperature is kept below 80°C during mixing, and the mixture is mixed evenly to obtain a compound. The first liquid rubber is liquid polyisobutylene rubber. S3. The compound obtained in S2 is fed into a twin-screw extruder through a conical twin-screw forced feeding device. The extrusion temperature is: Zone 1 180°C, Zone 2 185°C, Zone 3 190°C, Zone 4 195°C, Zone 5 195°C, Zone 7 190°C, Zone 9 200°C, Zone 10 200°C, Zone 11 200°C, Zone 12 200°C, and the die head 195°C. The screw speed is 400 rpm. Dynamic vulcanization is carried out. The die head of the twin-screw extruder is not equipped with an extrusion nozzle and the material is discharged directly to obtain thermoplastic vulcanized halogenated butyl rubber. S4. The thermoplastic vulcanized halogenated butyl rubber obtained in S3 is mixed with the continuous phase halogenated butyl rubber and the second heat-resistant antioxidant, and then mixed evenly at 200°C to obtain a high-temperature mixture. The continuous phase halogenated butyl rubber is brominated butyl rubber, and the second heat-resistant antioxidant includes antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1. S5. After cooling the high-temperature mixture obtained in S4 through a two-roll mill, zinc oxide, stearic acid, antioxidant, carbon black, lamellar inorganic filler, second liquid rubber and protective wax, vulcanizing agent and vulcanization accelerator are added in stages. The mixture is then mixed evenly below 80°C to obtain a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy. The antioxidant is antioxidant 4010, the second liquid rubber is liquid polyisobutylene rubber, the vulcanizing agent is sulfur, the vulcanization accelerator is DM, and the lamellar inorganic filler is talc.

[0059] Table 2 Example 3: A method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, comprising the following steps: S1. The dispersed phase halogenated butyl rubber, gas barrier resin, compatibilizer and first heat-resistant antioxidant are mixed uniformly in an internal mixer at 190°C according to the amounts in Table 3 to obtain a high-temperature mixed rubber. The dispersed phase halogenated butyl rubber is brominated butyl rubber with a bromine content of 1.8%, the gas barrier resin is EVOH with a melting point of 173°C, the heat-resistant antioxidant is antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, and the compatibilizer is polypropylene-maleic anhydride graft copolymer. S2. The high-temperature mixed rubber obtained in S1 is cooled by an open mill, and the first liquid rubber, dynamic vulcanizing agent and stannous chloride are added. The material temperature is kept below 80°C during mixing, and the mixture is mixed evenly to obtain a compound. The first liquid rubber is liquid polyisobutylene rubber. S3. The compound obtained in S2 is fed into a twin-screw extruder through a conical twin-screw forced feeding device. The extrusion temperature is: Zone 1 160°C, Zone 2 165°C, Zone 3 170°C, Zone 4 175°C, Zone 5 180°C, Zone 7 185°C, Zone 9 190°C, Zone 10 190°C, Zone 11 190°C, Zone 12 190°C, and the die head 190°C. The screw speed is 400 rpm. Dynamic vulcanization is carried out. The die head of the twin-screw extruder is not equipped with an extrusion nozzle and the material is discharged directly to obtain thermoplastic vulcanized halogenated butyl rubber. S4. The thermoplastic vulcanized halogenated butyl rubber obtained in S3 is mixed with the continuous phase halogenated butyl rubber and the second heat-resistant antioxidant, and then mixed evenly at 190°C to obtain a high-temperature mixture. The continuous phase halogenated butyl rubber is brominated butyl rubber, and the second heat-resistant antioxidant includes antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1. S5. After cooling the high-temperature mixture obtained in S4 through a two-roll mill, zinc oxide, stearic acid, antioxidant, carbon black, lamellar inorganic filler, second liquid rubber and protective wax, vulcanizing agent and vulcanization accelerator are added in stages. The mixture is then mixed evenly below 80°C to obtain a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy. The antioxidant is antioxidant 4010, the second liquid rubber is liquid polyisobutylene rubber, the vulcanizing agent is sulfur, the vulcanization accelerator is DM, and the lamellar inorganic filler is talc.

[0060] Table 3 Example 4: A method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, comprising the following steps: S1. The dispersed phase halogenated butyl rubber, gas barrier resin, compatibilizer and first heat-resistant antioxidant are mixed uniformly in an internal mixer at 190°C according to the amounts in Table 4 to obtain a high-temperature mixed rubber. The dispersed phase halogenated butyl rubber is brominated butyl rubber with a bromine content of 1.8%, the gas barrier resin is EVOH with a melting point of 173°C, the heat-resistant antioxidant is antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, and the compatibilizer is ethylene-methyl acrylate copolymer grafted with glycidyl acrylate. S2. The high-temperature mixed rubber obtained in S1 is cooled by an open mill, and the first liquid rubber, dynamic vulcanizing agent and stannous chloride are added. The material temperature is kept below 80°C during mixing, and the mixture is mixed evenly to obtain a compound. The first liquid rubber is liquid polyisobutylene rubber. S3. The compound obtained in S2 is fed into a twin-screw extruder through a conical twin-screw forced feeding device. The extrusion temperature is: Zone 1 160°C, Zone 2 165°C, Zone 3 170°C, Zone 4 175°C, Zone 5 180°C, Zone 7 185°C, Zone 9 190°C, Zone 10 190°C, Zone 11 190°C, Zone 12 190°C, and the die head 190°C. The screw speed is 400 rpm. Dynamic vulcanization is carried out. The die head of the twin-screw extruder is not equipped with an extrusion nozzle and the material is discharged directly to obtain thermoplastic vulcanized halogenated butyl rubber. S4. The thermoplastic vulcanized halogenated butyl rubber obtained in S3 is mixed with the continuous phase halogenated butyl rubber and the second heat-resistant antioxidant, and then mixed evenly at 190°C to obtain a high-temperature mixture. The continuous phase halogenated butyl rubber is brominated butyl rubber, and the second heat-resistant antioxidant includes antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1. S5. After cooling the high-temperature mixture obtained in S4 through a two-roll mill, zinc oxide, stearic acid, antioxidant, carbon black, lamellar inorganic filler, second liquid rubber and protective wax, vulcanizing agent and vulcanization accelerator are added in stages in sequence. The mixture is then mixed evenly below 80°C to obtain a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy. The antioxidant includes antioxidant 4010 and antioxidant MB in a mass ratio of 2:1. The second liquid rubber is liquid polyisobutylene rubber. The vulcanizing agent is sulfur. The vulcanization accelerator is DM. The lamellar inorganic filler is talc.

[0061] Table 4 Example 5: A method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, comprising the following steps: S1. The dispersed phase halogenated butyl rubber, gas barrier resin, compatibilizer and first heat-resistant antioxidant are mixed uniformly in an internal mixer at 190°C according to the amounts in Table 5 to obtain a high-temperature mixed rubber. The dispersed phase halogenated butyl rubber is brominated butyl rubber with a bromine content of 1.8%, the gas barrier resin is EVOH with a melting point of 173°C, the heat-resistant antioxidant is antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, and the compatibilizer is ethylene-methyl acrylate copolymer grafted with glycidyl acrylate. S2. The high-temperature mixed rubber obtained in S1 is cooled by an open mill, and the first liquid rubber, dynamic vulcanizing agent and stannous chloride are added. The material temperature is kept below 80°C during mixing, and the mixture is mixed evenly to obtain a compound. The first liquid rubber is liquid polyisobutylene rubber. S3. The compound obtained in S2 is fed into a twin-screw extruder through a conical twin-screw forced feeding device. The extrusion temperature is: Zone 1 160°C, Zone 2 165°C, Zone 3 170°C, Zone 4 175°C, Zone 5 180°C, Zone 7 185°C, Zone 9 190°C, Zone 10 190°C, Zone 11 190°C, Zone 12 190°C, and the die head 190°C. The screw speed is 400 rpm. Dynamic vulcanization is carried out. The die head of the twin-screw extruder is not equipped with an extrusion nozzle and the material is discharged directly to obtain thermoplastic vulcanized halogenated butyl rubber. S4. The thermoplastic vulcanized halogenated butyl rubber obtained in S3 is mixed with the continuous phase halogenated butyl rubber and the second heat-resistant antioxidant, and then mixed evenly at 190°C to obtain a high-temperature mixture. The continuous phase halogenated butyl rubber is brominated butyl rubber, and the second heat-resistant antioxidant includes antioxidant 168 and antioxidant 1010 in a mass ratio of 1:1. S5. After cooling the high-temperature mixture obtained in S4 through a two-roll mill, zinc oxide, stearic acid, antioxidant, carbon black, lamellar inorganic filler, second liquid rubber and protective wax, vulcanizing agent and vulcanization accelerator are added in stages in sequence. The mixture is then mixed evenly below 80°C to obtain a rubber-plastic bicontinuous heterogeneous crosslinking dynamic vulcanized alloy. The antioxidant includes antioxidant 4010 and antioxidant RD in a mass ratio of 2:2. The second liquid rubber is liquid polyisobutylene rubber. The vulcanizing agent is sulfur. The vulcanization accelerator is DM. The lamellar inorganic filler includes talc 815LD and diisopropyl oxide lamellar carbon SD1517 in a mass ratio of 1.5:1.

[0062] Table 5 Example 6: A rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanization alloy, which differs from Example 5 in that the lamellar inorganic filler is aluminum-magnesium hydrotalcite.

[0063] Example 7: A rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, which differs from Example 5 in that the lamellar inorganic filler is a modified aluminum-magnesium hydrotalcite prepared in Preparation Example 1.

[0064] Example 8: A rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, which differs from Example 7 in that the lamellar inorganic filler is a modified aluminum-magnesium hydrotalcite prepared in Preparation Example 2.

[0065] Example 9: A rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, which differs from Example 7 in that the lamellar inorganic filler is a modified aluminum-magnesium hydrotalcite prepared in Preparation Example 3.

[0066] Example 10: A rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, which differs from Example 7 in that the lamellar inorganic filler is a modified aluminum-magnesium hydrotalcite prepared in Preparation Example 4.

[0067] Comparative Example Comparative Example 1: A method for preparing a dynamically vulcanized alloy, comprising the following steps: S1. The dispersed phase halogenated butyl rubber, gas barrier resin, compatibilizer and heat-resistant antioxidant are mixed uniformly in an internal mixer at 190°C according to the amounts in Table 6 to obtain a high-temperature mixed rubber. The dispersed phase halogenated butyl rubber is brominated butyl rubber with a bromine content of 1.8%. The gas barrier resin is EVOH with a melting point of 173°C. The heat-resistant antioxidant is antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1. The compatibilizer is ethylene-methyl acrylate copolymer grafted with glycidyl acrylate. S2. The high-temperature mixed rubber obtained in S1 is cooled by a two-milling machine, and liquid rubber, dynamic vulcanizing agent and stannous chloride are added. The material temperature is kept below 80°C during mixing and the mixture is uniformly mixed to obtain a mixed rubber. The liquid rubber is liquid polyisobutylene rubber. S3. The compound obtained in S2 is fed into a twin-screw extruder via a conical twin-screw forced feeding device. The extrusion temperatures are: Zone 1 160℃, Zone 2 165℃, Zone 3 170℃, Zone 4 175℃, Zone 5 180℃, Zone 7 185℃, Zone 9 190℃, Zone 10 190℃, Zone 11 190℃, Zone 12 190℃, and Die Head 190℃. The screw speed is 400 rpm. Dynamic vulcanization is carried out. The compound is extruded into strips through a round orifice, cooled with water, granulated, and dried to obtain thermoplastic vulcanized halogenated butyl rubber. S4. The thermoplastic vulcanized halogenated butyl rubber obtained in S3 is mixed with carbon black, lamellar inorganic filler, antioxidant, and protective wax, and granulated by a twin-screw extruder to obtain a fully vulcanized dynamic vulcanized alloy material. It cannot be formed into a film by calendering and can only be formed by plastic processing methods such as molding, extrusion, and injection molding.

[0068] Table 6 Comparative Example 2: A method for preparing a compounded rubber composition, comprising the following steps: S1. Dispersed phase halogenated butyl rubber, gas barrier resin, compatibilizer, and first heat-oxidizing agent are mixed uniformly in an internal mixer at 190°C according to the amounts in Table 7 to obtain a high-temperature mixed rubber. The dispersed phase halogenated butyl rubber is brominated butyl rubber with a bromine content of 1.8%. The gas barrier resin is EVOH with a melting point of 173°C. The heat-oxidizing agent is antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1. The compatibilizer is ethylene-methyl acrylate copolymer grafted with glycidyl acrylate. S2. The high-temperature mixed rubber obtained in S1 is cooled by an open mill. Zinc oxide, stearic acid, carbon black, lamellar inorganic filler, liquid rubber, antioxidant, protective wax, vulcanizing agent, and vulcanizing aid are added and mixed. The material temperature is kept below 80°C during mixing and the mixture is mixed uniformly to obtain a mixed rubber composition.

[0069] Table 7 Comparative Example 3: A method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, which differs from Example 5 in that the first liquid rubber is not added in step S2 and the second liquid rubber is not added in step S5.

[0070] Comparative Example 4: A method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, which differs from Example 5 in that talc powder and diisopropyl oxide sheet carbon were not added in step S5.

[0071] Comparative Example 5: A method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy, which differs from Example 5 in that carbon black N660 is not added in step S5.

[0072] Performance testing I. Performance Testing of Rubber-Plastic Bicontinuous Heterogeneous Crosslinking Dynamic Vulcanization Alloy Dynamic vulcanized alloys were prepared according to the methods in the examples and comparative examples, and samples with thicknesses of 2 mm and 1 mm were made respectively. After being left to stand at room temperature for 24 hours, the two thicknesses of the samples obtained in Comparative Example 1 were molded using a flat vulcanizing agent under the following conditions: temperature 180°C, preheating for 10 min, pressure 15 MPa, holding pressure for 3 min, followed by cold pressing at 15 MPa for 3 min in a flat vulcanizing machine at room temperature. The samples prepared in the other examples and comparative examples were molded using a flat vulcanizing agent at a molding temperature of 180°C and a pressure of 15 MPa. The vulcanization time for the 2 mm thick sample was 5 min, and the vulcanization time for the 1 mm thick sample was 4 min. Thus, samples of different thicknesses were made. The samples made from the 2 mm thick sample were cut into dumbbell shapes and tested for Shore A hardness, tensile strength, and elongation at break. The samples made from the 1 mm thick sample were tested for gas permeability. Three parallel samples were tested for each sample, and the average value of the test results was taken. The results are recorded in Table 8. The specific test standards are as follows: 1. Shore A hardness: Tested according to GB / T531.1-2008 "Test method for indentation hardness of vulcanized rubber or thermoplastic rubber - Shore hardness tester method".

[0073] 2. Tensile strength: Tested in accordance with GB / T528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber".

[0074] 3. Elongation at break: Tested in accordance with GB / T528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber".

[0075] 4. Gas permeability coefficient: The test was conducted using a VAC-V2 gas permeability tester, referring to GB / T1038-2000 "Gas permeability test method for plastic films and sheets - differential pressure method". The test atmosphere was nitrogen, and the test environment was a constant temperature environment of 23±0.5℃.

[0076] 5. Surface Adhesion: The surface adhesion of the alloy materials is tested and graded as follows: ① No Adhesion: No adhesion is felt when the finger touches the material, and it does not stick at all even when bonded, showing no signs of adhesion; ② Weak Adhesion: The material feels slightly sticky when the finger touches it, and it is unstable after bonding and easily falls off; ③ Medium Adhesion: The material feels moderately sticky when the finger touches it, and it can wrap around the rollers normally when passing through the open mill without adhesion. It can maintain a stable adhesion state after the film is bonded; ④ Strong Adhesion: The material feels noticeably sticky when the finger touches it, and it will slightly adhere to the rollers when passing through the open mill. It is stable after bonding and requires a slight force to pull it apart; ⑤ Very Strong Adhesion: The material has a strong adhesion when the finger touches it, and it will significantly adhere to the rollers when passing through the open mill. It requires a moderate force to pull it apart after bonding.

[0077] 6. Interfacial Adhesion Peel-Off Test After Hot Pressing: After uniform refining on a two-roll mill, a sheet of approximately 1.5 mm thickness is produced. This sheet is then cut to the appropriate size and placed in a 1 mm thick flat vulcanizing mold. It is then shaped for 2 minutes at 15 MPa using a 50°C flat vulcanizing machine. Comparative Example 1 requires 190°C melt hot pressing followed by cold pressing for shaping. Two 1 mm thick samples are then overlapped, and a PTFE film less than 0.05 mm thick is sandwiched between one side to isolate the two layers. The isolation width is approximately 50 mm. The sample with one side isolated is then placed in a 2 mm thick flat vulcanizing mold and hot-pressed at 10 MPa using a 170°C flat vulcanizing machine for 5 minutes. The PTFE film is then removed from the sample, and it is cut into 25 mm wide strips to obtain peel-off test specimens with one end split in the middle (test method as follows). Figure 5 The peel strength was tested according to the method in GB / T 15254-2014 "180° Peel Test for Adhesion between Vulcanized Rubber and Metal".

[0078] Table 8 As can be seen from the data in Table 8, the alloy materials prepared using the preparation method described in this application in Examples 1-5 exhibit excellent tensile strength and elongation at break, low hardness, and significant airtightness. This demonstrates that the preparation method of this application can redesign the structure of the alloy material into a dynamic vulcanized alloy with a partially dynamically vulcanized cross-linked structure of halobutyl rubber microparticles as the dispersed phase and another part of halobutyl rubber and barrier resin as a dual continuous phase. The continuous rubber phase and the dispersed phase of vulcanized halobutyl rubber microparticles form a heterogeneous phase structure, possessing both good ductility and adhesion properties. It can be used in existing rubber calendering equipment and processes, enabling the preparation of thinner film products. After hot pressing and vulcanization, the adhered material achieves good interfacial co-vulcanization adhesion and high peel strength. During the preparation of the airtight layer, the interface between the continuous rubber phase and the dispersed rubber phase undergoes another vulcanization reaction, further strengthening this heterogeneous cross-linked structure, resulting in excellent physical and mechanical properties and gas barrier properties.

[0079] Compared with Example 5, Example 6 uses aluminum-magnesium hydrotalcite as a layered inorganic filler, which has similar hardness and mechanical strength to Example 5, and the gas permeability is not much different from that of Example 5.

[0080] Example 7 uses the modified aluminum-magnesium hydrotalcite prepared in Preparation Example 1. The aluminum-magnesium hydrotalcite is modified sequentially with nitrogen-containing heterocyclic compounds and PEG4000. It can be seen that, compared with Example 5, the alloy material prepared in Example 7 has increased tensile strength and decreased gas permeability, and the barrier performance is further improved.

[0081] In Example 8, the modified aluminum-magnesium hydrotalcite prepared in Preparation Example 2 was used. Compared with Example 7, the aluminum-magnesium hydrotalcite was first modified with PEG4000 and then with a nitrogen-containing heterocyclic compound. The tensile strength of the alloy material prepared in Example 8 decreased and the gas permeability increased. This indicates that the sequential modification of aluminum-magnesium hydrotalcite with nitrogen-containing heterocyclic compound and PEG4000 can improve its dispersibility and compatibility in rubber materials and enhance its barrier properties and mechanical strength.

[0082] Examples 9 and 10 used modified aluminum-magnesium hydrotalcite prepared in Examples 3 and 4, respectively. In Example 3, only nitrogen-containing heterocyclic compounds were used, and in Example 4, only PEG4000 was used. Compared with Example 7, the mechanical strength of the alloy materials prepared in Examples 9 and 10 decreased and the barrier effect was weakened.

[0083] Comparative Example 1 uses a general dynamic vulcanization process to prepare a dynamically vulcanized alloy material. Although it has good mechanical strength and gas barrier properties, it can only be processed and molded using plastics. Its ductility is insufficient, and it cannot be prepared into a film using existing rubber calendering processes and equipment. Although the liquid rubber in Comparative Example 1 is basically equivalent to Example 5, after dynamic vulcanization, the resin phase becomes a continuous phase, and the material has no adhesive properties. After film formation, it cannot be overlapped on a tire forming machine, and it also fails to achieve melt bonding after hot pressing at 170°C. Comparative Example 2 is a rubber-plastic composite material prepared by a simple rubber-plastic blending process. Its strength and barrier properties are both poor. Comparative Examples 3-5 respectively illustrate that liquid rubber materials have a relatively critical influence on gas barrier properties, processing properties, adhesion properties, and interfacial bonding strength after adhesion. The combined effect of carbon black and lamellar inorganic fillers can effectively endow the material with excellent mechanical properties and gas barrier properties.

[0084] II. Performance Testing of Airtight Tires The rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanization alloys prepared in Examples 5 and 7 were extruded into sheets and calendered to obtain the tire airtight layer. This layer was then fed into a tire forming machine and molded with other tire materials. Figure 2 As shown, after vulcanization, as Figure 3 As shown, the tire's airtight layer adheres well to the joint on the tire forming machine. After vulcanization, it is made into a tire. The tire's cross-section is as shown. Figure 4 As shown in Table 9, the performance of tires with different specifications of airtight layer was compared with that of existing tires.

[0085] Table 9 As can be seen from the data comparison in Table 9, compared with the traditional 1mm thick airtight layer, the thinner airtight layer prepared in this application has a better pressure-holding effect.

[0086] like Figure 2 As shown, the airtight layer joint is flat and intact, resulting in a tire with better friction reduction. Figure 4 As shown, thinner tires can achieve better weight reduction, thereby improving the fuel efficiency of gasoline vehicles and the energy efficiency and driving range of new energy vehicles with heavy weight and high tire pressure.

[0087] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A rubber-plastic bicontinuous heterogeneous crosslinking dynamic vulcanization alloy, characterized in that, Includes the following steps; S1. The dispersed phase halogenated butyl rubber is mixed evenly with gas barrier resin, compatibilizer and first heat-resistant antioxidant to obtain high-temperature mixed rubber. The mixing temperature is 10-20℃ higher than the melting point of gas barrier resin. S2. After the high-temperature mixed rubber obtained in S1 is cooled by open milling, it is then mixed evenly with the first liquid rubber, dynamic vulcanizing agent and stannous chloride to obtain the mixed rubber. S3. The compound obtained in S2 is subjected to dynamic vulcanization to obtain thermoplastic vulcanized halogenated butyl rubber. S4. The thermoplastic vulcanized halogenated butyl rubber obtained in S3 is directly mixed with the continuous phase halogenated butyl rubber and the second heat-resistant oxygen agent at high temperature and uniformly. The mixing temperature is 10-20℃ higher than the melting point of the gas barrier resin. S5. After cooling the high-temperature mixture obtained in S4 through open milling, zinc oxide, stearic acid, antioxidant, carbon black, lamellar inorganic filler, second liquid rubber and protective wax, vulcanizing agent and vulcanizing aid are added in stages in sequence and mixed evenly to obtain a dynamic vulcanized alloy of rubber and plastic bicontinuous heterogeneous crosslinking.

2. The method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanization alloy according to claim 1, characterized in that, The raw materials are in the following weight proportions: The components are: 50-70 parts dispersed phase halogenated butyl rubber, 30-50 parts gas barrier resin, 2-10 parts compatibilizer, 0.4-1 part first heat antioxidant, 2-10 parts first liquid rubber, 3-8 parts dynamic vulcanizing agent, 1-4 parts stannous chloride, 80-100 parts continuous phase halogenated butyl rubber, 0.4-1 part second heat antioxidant, 2-6 parts zinc oxide, 2-4 parts stearic acid, 5-50 parts carbon black, 5-40 parts lamellar inorganic filler, 2-10 parts second liquid rubber, 1-6 parts antioxidant, 2-4 parts protective wax, 2-5 parts vulcanizing agent, and 2-5 parts vulcanizing auxiliaries.

3. The method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanizing alloy according to claim 1, characterized in that: The halogen content of both the dispersed phase halogenated butyl rubber and the continuous phase halogenated butyl rubber is 0.3-1.8 wt%, and both are selected from at least one of brominated butyl rubber, chlorinated butyl rubber and brominated polyisobutylene-p-methylstyrene rubber. The gas barrier resin is selected from at least one of PA6, PA6 / PA66 binary copolymer, and EVOH.

4. The method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanizing alloy according to claim 1, characterized in that: The compatibilizer is selected from at least one of ethylene-methyl acrylate copolymer grafted glycidyl acrylate, polypropylene-maleic anhydride copolymer, styrene elastomer-maleic anhydride copolymer, and maleic anhydride grafted polyolefin elastomer.

5. The method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanizing alloy according to claim 1, characterized in that: The first liquid rubber and the second liquid rubber are both selected from at least one of liquid polyisobutylene rubber and liquid butyl rubber with a viscosity-average molecular weight of 10,000-100,000.

6. The method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanizing alloy according to claim 1, characterized in that: The dynamic vulcanizing agent is selected from at least one of thermally reactive phenolic resin and brominated phenolic resin.

7. The method for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanizing alloy according to claim 1, characterized in that: Both the first and second anti-oxidant agents comprise a primary antioxidant or a primary antioxidant and a secondary antioxidant in any proportion. The primary antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-thionyl glycol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 1,3,5-tris(4-tert-butyl-3-hydroxy-2-... At least one of (6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,2H,5H)-trione; the co-antioxidant is selected from at least one of tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol-diphosphite, dioctadecyl thiodipropionate, dioctadecyl thiodipropionate and pentaerythritol tetra(3-lauryl thiopropionate); The antioxidant is selected from at least one of N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester, 2,2,4-trimethyl-1,2-dihydroquinoline polymer and 2-mercaptobenzimidazole; The lamellar inorganic filler is selected from at least one of diisopropyl oxide lamellar carbon, talc, modified aluminum magnesium hydrotalcite, modified clay, and modified montmorillonite. The protective wax is selected from at least one of paraffin wax and microcrystalline wax.

8. A rubber-plastic bicontinuous heterogeneous crosslinking dynamic vulcanization alloy, characterized in that, It is prepared by the method described in any one of claims 1-7 for preparing a rubber-plastic bicontinuous heterogeneous crosslinked dynamic vulcanized alloy.

9. A tire airtight layer, characterized in that, The rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy prepared by any one of claims 1-7 is used as raw material and is obtained by extrusion into sheets and calendering.

10. The tire airtight layer according to claim 9, characterized in that, The tire airtight layer is combined with the transition layer or used alone as an inner liner, and is vulcanized with the belt layer, cord layer, bead, sidewall rubber, tread rubber and intertread rubber after tire molding to obtain the tire.

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