Rubber hose material based on fluorosilicone elasticity and preparation method thereof

Abstract

The invention relates to the field of polymer plastic pipes, provides a fluorosilicone elasticity-based rubber hose material and a preparation method thereof, and aims to solve the problems of insufficient tensile strength and chemical corrosion resistance of the existing rubber hose material. The material is composed of a fluorinated silicone rubber matrix, white carbon black, carbon black, graphite fluoride, nano calcium fluoride, a fluorinated plasticizer, a silane coupling agent, an antioxidant and a silicone flow modifier, the material ratio is reasonable, and a reinforced interface and a compact network structure are cooperatively constructed. The fluorinated silicone rubber matrix is formed by polymerizing vinyl-containing silsesquioxane, an F-organosilicon polymer and an F-cross-linking agent under the action of a catalyst. According to the method, the tensile strength, the elongation at break and the chemical corrosion resistance of a medium in the pH range of 1-14 of the material are remarkably improved through multi-component synergistic enhancement and an optimized forming process, and the method is suitable for the fields of high-performance sealing, transmission and the like.

Description

Technical Field

[0001] The present invention relates to the field of polymer plastic pipes, and in particular to a rubber hose material based on fluorosilicone elasticity and a preparation method thereof. Background Art

[0002] In high-temperature, high-pressure, and complex corrosive environments such as aerospace, rail transportation, automobile engine compartments, precision chemicals, and high-end equipment manufacturing, rubber hoses, as key flexible connection and sealing components, are widely used in the transportation systems of fuel, lubricants, coolants, and chemical media. Their performance directly affects the operational stability and safety of the entire system. In the above-mentioned application scenarios, the hose material must not only withstand frequent mechanical stress, dynamic bending, and vibration shock, but also must withstand long-term erosion by high temperatures, hot oxygen, oil products, and corrosive media. Therefore, more stringent requirements are placed on the tensile strength and heat resistance of the material. On the one hand, excellent tensile properties can ensure that the hose does not break, deform, or leak under high-pressure transportation and dynamic loads, thereby improving its service life and structural reliability. On the other hand, good heat resistance is the core indicator to ensure that the material maintains mechanical stability and sealing performance under high-temperature conditions. As equipment systems develop towards high power, lightweight and intelligent directions, material performance also needs continuous iteration and breakthroughs. Therefore, the development of new rubber hose materials with both high strength and high heat resistance can not only meet the urgent needs of key areas for adaptability to extreme environments, but also has important practical significance and strategic value for promoting the upgrading of high-end manufacturing technology and ensuring the safe operation of industrial systems.

[0003] Although a variety of modified rubber materials have been used in the preparation of hoses, attempts have been made to improve their comprehensive performance through filler reinforcement, blending modification or cross-linking structure regulation, but there are still significant deficiencies in meeting the dual performance requirements of high strength and heat resistance. For example, the Chinese patent with publication number CN119775784A discloses a fluorosilicone rubber, a fluorosilicone rubber hose and its preparation method and application, which uses an inorganic filler and an organic silicone resin synergistic reinforcement system to improve the mechanical properties and thermal stability of the hose. However, there are problems such as limited improvement in tensile strength and insufficient structural stability at high temperatures, making it difficult to adapt to the requirements of long-term use under harsh working conditions. The root cause of such problems is that the filler is unevenly dispersed in the material system, the interface bonding force is weak or the cross-linking network is imperfect, resulting in the inability of the reinforcement unit to efficiently bear the load and transfer stress, thereby limiting the improvement of mechanical properties; at the same time, some reinforcement components are prone to thermal aging or structural rearrangement at high temperatures, which not only reduces the thermal stability of the material, but also may cause failure behaviors such as interface debonding and microcrack propagation. In addition, the existing preparation process is still insufficient in component collaborative design and structural density control, making it difficult to achieve synergistic optimization of mechanical enhancement and thermal stability. Therefore, how to construct fluorosilicone elastic hose materials with excellent interface compatibility, stable three-dimensional cross-linked structure and high thermal stability micronetwork is still an important technical problem that needs to be solved urgently in the current field of material research and development. Summary of the Invention

[0004] (1) Technical problems to be solved: The purpose of the present invention is to provide a rubber hose material based on fluorosilicone elasticity and a preparation method thereof, so as to solve the problem that the current rubber hose material has insufficient tensile strength and heat resistance.

[0005] (2) Technical solution: In order to achieve the above-mentioned object, the present invention provides the following technical solution: A fluorosilicone elastic rubber hose material comprises the following raw materials in parts by weight: 100.0 parts of a fluorosilicone rubber matrix prepolymer, 15.0-45.0 parts of a white carbon black reinforcing agent, 2.0-8.0 parts of a silane coupling agent, 5.0-25.0 parts of a carbon black reinforcing agent, 1.0-5.0 parts of an antioxidant, 3.0-15.0 parts of a fluorinated plasticizer, 2.0-10.0 parts of fluorinated graphite, 1.0-8.0 parts of nano-calcium fluoride, and 0.5-3.0 parts of a silicone flow modifier; The fluorine-containing silicone rubber matrix prepolymer is a partially cross-linked polymer prepared by a pre-cross-linking reaction of a vinyl-containing polyhedral oligomeric silsesquioxane, an F-organic silicon polymer and an F-cross-linking agent under the action of a catalyst; The vinyl-containing polyhedral oligomeric silsesquioxane is prepared by acid-catalyzed hydrolysis and condensation of vinyltrimethoxysilane and methyltrimethoxysilane and then purified by recrystallization; The F-organic silicon polymer is a fluorine-containing vinyl siloxane copolymer prepared by anionic ring-opening polymerization using octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane and tetramethyltetravinylcyclotetrasiloxane as main raw materials; The F-crosslinking agent is a fluorine-containing functional end group oligosiloxane prepared by ring-opening polymerization of octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capping with hexamethyldisiloxane.

[0006] Further, the preparation method of the F-organic silicon polymer is as follows: in parts by weight, 240.0-260.0 parts of octamethylcyclotetrasiloxane, 400.0-450.0 parts of trifluoropropylmethylcyclotrisiloxane and 12.0-15.0 parts of tetramethyltetravinylcyclotetrasiloxane are reacted at a reaction temperature of 80.0-90.0°C under an argon atmosphere for 45.0-60.0 min, and then 2.1-2.5 parts of tetramethylammonium hydroxide initiator and 1.1-1.5 parts of tetramethyldivinyldisiloxane are added and reacted at a stirring rate of 250.0-300.0 rpm for 240.0-300.0 min, then the temperature is raised to 145.0-150.0°C and maintained under vacuum conditions for 20.0-24.0 h, and finally purified with methanol 2.0-3.0 times and heated to a vacuum degree of 0.1-1.0 kPa and a drying temperature of 60.0-80.0°C under vacuum drying for 8.0-12.0 h to obtain F-organic silicon polymer.

[0007] Further, the preparation method of the F-crosslinking agent is as follows: in parts by weight, octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane are added to a four-necked reaction flask equipped with a mechanical stirrer and a reflux condenser in a weight ratio of 1.0:1.5~2.0, under the protection of an argon atmosphere, the reaction temperature is raised to 80~90.0 ° C and maintained for 45~60 min to reach the initiation temperature, and then 0.25~0.35 parts of tetramethylammonium hydroxide initiator are added to the reactor at a stirring rate of 250~300.0 rpm and a reaction temperature of 85~90.0 ° C to start the reaction, and then a dropping funnel is used to stir vigorously at 0.5 10.0-20.0 parts of tetramethylcyclotetrasiloxane were dropwise added to the reaction solution within 1 h, followed by the addition of 5.0-10.0 parts of hexamethyldisiloxane end-capping agent to the reactor. The reaction was continued with stirring at a reaction temperature of 85-90.0°C for 90-120 min. After completion of the reaction, the product was heated to 145-150.0°C and maintained under vacuum for 20-24.0 h to remove unreacted reactants and initiator. Finally, the product was purified with methanol to eliminate cyclic monomer impurities to obtain the F-crosslinker.

[0008] Furthermore, the preparation method of the vinyl-containing polyhedral oligomeric silsesquioxane is as follows: in parts by weight, 45.0-55.0 parts of vinyltrimethoxysilane and 40.0-50.0 parts of methyltrimethoxysilane are dissolved in 450.0-550.0 parts of acetone solvent, stirred at a stirring rate of 280.0-320.0 rpm under an argon atmosphere at a reaction temperature of 35.0-45.0°C, and then 50.0-80.0 parts of a hydrochloric acid solution with a concentration of 0.5-2.0 mol / L is added dropwise over 120.0-180.0 min to carry out a hydrolysis-condensation reaction, and then the reaction is continued at a reaction temperature of 35.0-45.0°C for 30.0-38.0 min. h, and then filtered and separated and washed with ethanol, deionized water and acetone for 3.0 to 5.0 times respectively, followed by drying at a drying temperature of 55.0 to 65.0 ° C for 12.0 to 16.0 h, and then recrystallized and purified using a dichloromethane-acetone mixed solvent with a volume ratio of 1:3 and allowed to stand for 20.0 to 24.0 h. Finally, it was collected by filtration and dried to obtain vinyl-containing polyhedral oligomeric silsesquioxane.

[0009] Furthermore, the preparation method of the fluorine-containing silicone rubber matrix prepolymer is as follows: in parts by weight, 2.5 to 5.0 parts of vinyl-containing polyhedral oligomeric silsesquioxane are dissolved in 22.0 to 32.0 parts of tetrahydrofuran solvent, and then 280.0 to 295.0 parts of F-organic silicone polymer and 5.0 to 15.0 parts of F-crosslinking agent are added in sequence and mixed evenly, followed by degassing for 90 to 120 minutes at a vacuum degree of 0.1 to 1.0 kPa and a degassing temperature of 100.0°C, followed by adding 0.1 to 0.15 parts of Custer catalyst and mixing evenly at a stirring rate of 250 to 300 rpm, and finally removing the tetrahydrofuran solvent under reduced pressure to obtain a fluorine-containing silicone rubber matrix prepolymer.

[0010] The present invention adopts the design of a fluorosilicone rubber matrix prepolymer modified with vinyl polyhedral oligomeric silsesquioxane combined with a multi-filler reinforcement system, which is mainly used to enhance the tensile strength and heat resistance of rubber hose materials. This technical solution aims to solve the key problems of insufficient mechanical properties and limited thermal stability of traditional fluorosilicone rubber materials in extreme environments through a synergistic enhancement strategy of molecular structure design and multi-scale structure regulation. The constructed fluorosilicone rubber matrix prepolymer is centered on a three-dimensional cross-linked network that is both rigid and flexible. The vinyl polyhedral oligomeric silsesquioxane, with its unique cage-like siloxane skeleton structure, acts as a rigid cross-linking node to form a stable chemical connection with the flexible chain segment of the F-silicone polymer, significantly improving the modulus and thermal stability of the material while maintaining excellent flexibility and processability. The trifluoropropyl side chain introduced into the F-silicone polymer gives the molecular chain excellent chemical inertness and resistance to medium corrosion. Its main chain structure provides sufficient reactivity for the construction of the cross-linked network, ensuring the integrity and uniformity of the network structure. The introduction of F-crosslinking agents further constructs a dense covalent bond network, enhancing the overall structural stability and mechanical strength of the matrix. On this basis, the multi-filler reinforcement system significantly improves the comprehensive performance of the composite material through fine design. White carbon black achieves a strong bond with the matrix through the interface regulation effect of the silane coupling agent, improving the filler dispersion and stress transfer efficiency, while carbon black provides additional structural support and reinforcement through its unique aggregated structure. Graphite fluoride, with its layered structure, constructs an effective physical barrier network within the material, greatly improving its barrier capacity to corrosive media. Nano-calcium fluoride forms good interfacial compatibility with the matrix through its surface properties and significantly improves the structural rigidity of the material. The introduction of fluorinated plasticizers enhances the chemical stability of the system while maintaining the flexibility of the material. Silicone flow modifiers further optimize the processing fluidity and molding properties of the material. Antioxidants effectively delay the thermal oxidative aging process of the material in high-temperature environments. Ultimately, the components form an organic unity in terms of molecular structure design, interface regulation and macroscopic performance synergy, allowing the composite material to achieve significant improvements in tensile strength and heat resistance while maintaining excellent flexibility, meeting the increasingly stringent technical requirements for high-performance flexible sealing materials in high-end application environments.

[0011] Furthermore, the weight ratio of the white carbon black reinforcing agent to the carbon black reinforcing agent is 2:1 to 4:1.

[0012] Furthermore, the silane coupling agent is KH-550 silane coupling agent or KH-151 silane coupling agent; The antioxidant is 2,6-di-tert-butyl-p-cresol or N,N-diphenyl-p-phenylenediamine; The fluorinated plasticizer is perfluoropolyether; The silicone flow modifier is hydroxy silicone oil.

[0013] The present invention also discloses a method for preparing a rubber hose material based on fluorosilicone elasticity, comprising the following steps: pre-mixing a fluorosilicone rubber matrix prepolymer, a white carbon black reinforcing agent, and a silane coupling agent in a mixer at a mixing temperature of 40-60°C for 15-25 minutes, then sequentially adding the carbon black reinforcing agent, graphite fluoride, and nano-calcium fluoride and continuing to mix for 10-20 minutes, then adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing evenly, and then hot-pressing for 10-20 minutes at a molding temperature of 160-180°C and a molding pressure of 8-15 MPa to obtain the rubber hose material.

[0014] Furthermore, the rubber hose has an operating temperature range of -50~250°C, a tensile strength of ≥15 MPa, an elongation at break of ≥200%, and can withstand corrosion from media with a pH value of 1~14.

[0015] (3) Beneficial technical effects: 1. The present invention significantly improves the tensile strength and heat resistance of the hose material by synergistically constructing a three-dimensional network structure through fluorosilicone prepolymer and multifunctional fillers, and has flexibility, processability and environmental adaptability, and is suitable for sealing applications in extreme working conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is the infrared Fourier spectrum of the F-organic silicon polymer prepared in Example 1 of the present invention.

[0017] Figure 2 This is the infrared Fourier spectrum of the F-crosslinking agent prepared in Example 1 of the present invention.

[0018] Figure 3 This is the infrared Fourier spectrum of the vinyl-containing polyhedral oligomeric silsesquioxane prepared in Example 1 of the present invention.

[0019] Figure 4 This is a morphology diagram of the vinyl-containing polyhedral oligomeric silsesquioxane prepared in Example 1 of the present invention.

[0020] Figure 5 This is a physical picture of the rubber tube prepared in Example 1 of the present invention.

[0021] Figure 6 This is a diagram showing the rubber tube tensile specimen prepared in Example 1 of the present invention during stretching. DETAILED DESCRIPTION

[0022] To make the objectives, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

[0023] Example 1: A fluorosilicone elastic rubber hose material, comprising the following raw materials in parts by weight: 100.0 parts of a fluorosilicone rubber matrix prepolymer, 15.0 parts of a white carbon black reinforcing agent, 2.0 parts of a KH-550 silane coupling agent, 0.5 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2.0 parts of triallyl isocyanurate, 5.0 parts of a carbon black reinforcing agent, 1.0 parts of 2,6-di-tert-butyl-p-cresol, 3.0 parts of a perfluoropolyether, 2.0 parts of a fluorinated graphite, 1.0 parts of a nano-calcium fluoride, and 0.5 parts of a hydroxy silicone oil; The fluorine-containing silicone rubber matrix prepolymer of this embodiment is a partially cross-linked polymer prepared by a pre-cross-linking reaction of a vinyl-containing polyhedral oligomeric silsesquioxane, an F-organic silicone polymer and an F-cross-linking agent under the action of a catalyst; the vinyl-containing polyhedral oligomeric silsesquioxane is prepared by an acid-catalyzed hydrolysis and condensation reaction of vinyltrimethoxysilane and methyltrimethoxysilane and then purified by recrystallization; the F-organic silicone polymer is a fluorine-containing vinyl siloxane copolymer prepared by anionic ring-opening polymerization with octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane and tetramethyltetravinylcyclotetrasiloxane as the main raw materials; the F-cross-linking agent is a fluorine-containing functional end group oligosiloxane prepared by ring-opening polymerization with octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as the initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capped with hexamethyldisiloxane.

[0024] The preparation method of the F-organic silicon polymer of this embodiment is as follows: in parts by weight, 240.0 parts of octamethylcyclotetrasiloxane, 400.0 parts of trifluoropropylmethylcyclotrisiloxane, and 12.0 parts of tetramethyltetravinylcyclotetrasiloxane are reacted at a reaction temperature of 80.0° C. for 45.0 min under an argon atmosphere, then 2.1 parts of tetramethylammonium hydroxide initiator and 1.1 parts of tetramethyldivinyldisiloxane are added, and the reaction is carried out at a stirring rate of 250.0 rpm for 240.0 min. The temperature is then raised to 145.0° C. and maintained under vacuum for 20.0 h. Finally, the polymer is purified with methanol 2.0 times and vacuum dried at a vacuum degree of 0.1 kPa and a drying temperature of 60.0° C. for 8.0 h to obtain the F-organic silicon polymer.

[0025] The preparation method of the F-crosslinking agent of this embodiment is as follows: in parts by weight, octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane are added to a four-necked reaction flask equipped with a mechanical stirrer and a reflux condenser in a weight ratio of 1.0:1.7, and the reaction temperature is raised to 83.0°C under argon atmosphere and maintained for 50 minutes to reach the initiation temperature. Then, 0.28 parts of tetramethylammonium hydroxide initiator are added to the reactor at a stirring rate of 265 rpm and a reaction temperature of 87.0°C to start the reaction. Then, 13 parts of tetramethylcyclotetrasiloxane are added dropwise to the reaction solution under vigorous stirring over 0.5 hours using a dropping funnel. Subsequently, 7 parts of hexamethyldisiloxane end-capping agent are added to the reactor. After the reaction temperature is 87.0°C, stirring is continued for 99 minutes. After the reaction is completed, the product is heated to 147.0°C and maintained under vacuum for 21 minutes. h to remove unreacted reactants and initiators, and finally the product is purified using methanol to eliminate cyclic monomer impurities to obtain F-crosslinker.

[0026] The preparation method of the vinyl-containing polyhedral oligomeric silsesquioxane of this embodiment is as follows: in parts by weight, 48 parts of vinyltrimethoxysilane and 43 parts of methyltrimethoxysilane are dissolved in 480 parts of an acetone solvent, and the mixture is stirred at a stirring rate of 292 rpm at a reaction temperature of 38.0 ° C. under an argon atmosphere, and then 59 parts of a 1.0 mol / L hydrochloric acid solution are added dropwise over 138 minutes to carry out a hydrolysis condensation reaction, followed by continuing the reaction at a reaction temperature of 38.0 ° C. for 32 hours, followed by filtration and separation, and washing with ethanol, deionized water and acetone four times each, followed by drying at a drying temperature of 58.0 ° C. for 13 hours, and then recrystallization and purification using a dichloromethane-acetone mixed solvent with a volume ratio of 1:3 and standing for 21 hours. Finally, filtration, collection and drying are performed to obtain the vinyl-containing polyhedral oligomeric silsesquioxane.

[0027] The preparation method of the fluorinated silicone rubber matrix prepolymer of this embodiment is as follows: 3.3 parts of vinyl-containing polyhedral oligomeric silsesquioxane are dissolved in 25 parts of tetrahydrofuran solvent, and then 285 parts of F-organic silicone polymer and 8 parts of F-crosslinker are added in sequence and mixed evenly. Then, the mixture is degassed at a vacuum degree of 0.4 kPa and a degassing temperature of 100.0°C for 99 min, and then 0.11 parts of Custer catalyst are added and mixed evenly at a stirring rate of 265 rpm. Finally, the tetrahydrofuran solvent is removed under reduced pressure to obtain a fluorinated silicone rubber matrix prepolymer.

[0028] The present embodiment provides a method for preparing a fluorosilicone elastic rubber hose material, comprising the following steps: premixing a fluorosilicone rubber matrix prepolymer with a white carbon black reinforcing agent and a silane coupling agent in a mixer at a mixing temperature of 46° C. for 18 minutes, then sequentially adding the carbon black reinforcing agent, graphite fluoride, and nano-calcium fluoride and continuing to mix for 13 minutes, then adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing uniformly, and then hot pressing the mixture at a molding temperature of 166° C. and a molding pressure of 10 MPa for 13 minutes to obtain the rubber hose material.

[0029] from Figure 1 From the infrared Fourier spectrum of the F-organic silicon polymer, it can be seen that a strong absorption peak attributable to the asymmetric stretching vibration of the siloxane main chain --Si--O--Si-- appears in the range of 1130-1000 cm⁻¹. At the same time, a characteristic absorption peak of the --CF3 group is observed at 1210 cm⁻¹, the absorption peak of Si--CH3 is at 1226 cm⁻¹, the absorption peak of the --CH bond in --CH3 is at 2960 cm⁻¹, the absorption peak of the --CH2--CH2-- bond is at 1315 cm⁻¹, and the absorption peak of the C--H bond in --CH2-- is at 1128 cm⁻¹. The presence of these characteristic peaks confirms that the F-organic silicon polymer has successfully introduced trifluoropropyl side chains and methyl groups. Figure 2 The infrared Fourier spectrum of the F-crosslinker also shows a strong absorption band of --Si--O--Si-- asymmetric stretching vibration in the range of 1130-1000 cm⁻¹, as well as the corresponding absorption peaks of C--H bonds in --CF3, Si--CH3, --CH2--CH2-- and --CH2--. Of particular importance is the characteristic absorption peak of the Si--H bond observed at 2245 cm⁻¹, confirming the successful preparation of a short-chain siloxane crosslinker containing methyl, trifluoropropyl and hydrogen groups. Figure 3 The infrared Fourier spectrum of the vinyl-containing polyhedral oligomeric silsesquioxane showed a single strong absorption peak at 1110 cm⁻¹ attributed to --Si--O--Si-- in the cage structure, absorption peaks of the --C=C-- group appeared at 1000 and 1616 cm⁻¹, and a Si--CH3 peak was observed at 824 cm⁻¹, confirming the successful synthesis of polyhedral oligomeric silsesquioxane with a certain vinyl ratio. Figure 4 The morphology of vinyl-containing polyhedral oligomeric silsesquioxanes shows that all POSS samples have a cubic structure, which is consistent with the structural characteristics reported in the literature, further confirming the successful preparation and structural integrity of POSS. Figure 5 The actual rubber tube prepared in Example 1 of the present invention is displayed. It can be observed that the surface of the material is smooth and uniform, the color is consistent, and there are no obvious defects, showing good molding quality and appearance characteristics. Figure 6This is a tensile display diagram of a rubber tube tensile specimen. From the figure, it can be seen that the specimen maintains good deformation uniformity during the stretching process, and no obvious stress concentration or local damage occurs, indicating that the material has excellent mechanical properties and toughness, verifying the effectiveness of the technical solution of the present invention and the excellent comprehensive performance of the material.

[0030] Example 2: A fluorosilicone elastic rubber hose material, comprising the following raw materials in parts by weight: 100.0 parts of a fluorosilicone rubber matrix prepolymer, 24 parts of a white carbon black reinforcing agent, 4 parts of a KH-151 silane coupling agent, 11 parts of a carbon black reinforcing agent, 2.2 parts of N,N-diphenyl-p-phenylenediamine, 7 parts of a perfluoropolyether, 4 parts of a fluorinated graphite, 3.1 parts of nano-calcium fluoride, and 1.3 parts of a hydroxy silicone oil; The fluorine-containing silicone rubber matrix prepolymer of this embodiment is a partially cross-linked polymer prepared by a pre-cross-linking reaction of a vinyl-containing polyhedral oligomeric silsesquioxane, an F-organic silicone polymer and an F-cross-linking agent under the action of a catalyst; the vinyl-containing polyhedral oligomeric silsesquioxane is prepared by an acid-catalyzed hydrolysis and condensation reaction of vinyltrimethoxysilane and methyltrimethoxysilane and then purified by recrystallization; the F-organic silicone polymer is a fluorine-containing vinyl siloxane copolymer prepared by anionic ring-opening polymerization with octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane and tetramethyltetravinylcyclotetrasiloxane as the main raw materials; the F-cross-linking agent is a fluorine-containing functional end group oligosiloxane prepared by ring-opening polymerization with octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as the initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capped with hexamethyldisiloxane.

[0031] The preparation method of the F-organic silicon polymer of this embodiment is as follows: 246 parts by weight of octamethylcyclotetrasiloxane, 415 parts of trifluoropropylmethylcyclotrisiloxane, and 13 parts of tetramethyltetravinylcyclotetrasiloxane are reacted at a reaction temperature of 83.0°C under an argon atmosphere for 50 minutes, and then 2.2 parts of tetramethylammonium hydroxide initiator and 1.2 parts of tetramethyldivinyldisiloxane are added, and the reaction is carried out at a stirring rate of 265 rpm for 258 minutes. The temperature is then raised to 147.0°C and maintained under vacuum for 21 hours. Finally, the polymer is purified with methanol 2.3 times and vacuum dried at a vacuum degree of 0.4 kPa and a drying temperature of 66.0°C for 9 hours to obtain the F-organic silicon polymer. The preparation method of the F-crosslinking agent of this embodiment is as follows: in parts by weight, octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane are added to a four-necked reaction flask equipped with a mechanical stirrer and a reflux condenser in a weight ratio of 1.0:1.5, and the reaction temperature is raised to 80°C under argon atmosphere and maintained for 45 minutes to reach the initiation temperature. Then, 0.25 parts of tetramethylammonium hydroxide initiator are added to the reactor at a stirring rate of 250 rpm and a reaction temperature of 85°C to start the reaction. Then, 10.0 parts of tetramethylcyclotetrasiloxane are dropwise added to the reaction solution under vigorous stirring over 0.5 hours using a dropping funnel. Subsequently, 5.0 parts of hexamethyldisiloxane end-capping agent are added to the reactor. After the reaction temperature is 85°C, the stirring reaction time is continued for 90 minutes. After the reaction is completed, the product is heated to 145°C and maintained under vacuum for 20 minutes. h to remove unreacted reactants and initiators, and finally the product is purified using methanol to eliminate cyclic monomer impurities to obtain F-crosslinker.

[0032] The preparation method of the vinyl-containing polyhedral oligomeric silsesquioxane of this embodiment is as follows: in parts by weight, 45.0 parts of vinyltrimethoxysilane and 40.0 parts of methyltrimethoxysilane are dissolved in 450.0 parts of acetone solvent, and stirred at a reaction temperature of 35.0 ° C. at a stirring rate of 280.0 rpm under an argon atmosphere, and then 50.0 parts of a 0.5 mol / L hydrochloric acid solution are added dropwise over 120.0 min to carry out a hydrolysis condensation reaction, followed by continuing the reaction at a reaction temperature of 35.0 ° C. for 30.0 h, followed by filtration and separation, and washing with ethanol, deionized water and acetone 3.0 times each, followed by drying at a drying temperature of 55.0 ° C. for 12.0 h, and then recrystallization and purification using a dichloromethane-acetone mixed solvent with a volume ratio of 1:3 and standing for 20.0 h. Finally, filtration, collection and drying are performed to obtain the vinyl-containing polyhedral oligomeric silsesquioxane.

[0033] The preparation method of the fluorinated silicone rubber matrix prepolymer of this embodiment is as follows: in parts by weight, 2.5 parts of vinyl-containing polyhedral oligomeric silsesquioxane are dissolved in 22.0 parts of tetrahydrofuran solvent, and then 280.0 parts of F-organic silicone polymer and 5.0 parts of F-crosslinker are added in sequence and mixed uniformly, followed by degassing at a vacuum degree of 0.1 kPa and a degassing temperature of 100.0°C for 90 min, followed by adding 0.1 parts of Custer catalyst and mixing uniformly at a stirring rate of 250 rpm, and finally removing the tetrahydrofuran solvent under reduced pressure to obtain a fluorinated silicone rubber matrix prepolymer.

[0034] The present embodiment provides a method for preparing a fluorosilicone elastic rubber hose material, comprising the following steps: pre-mixing a fluorosilicone rubber matrix prepolymer, a white carbon black reinforcing agent, and a silane coupling agent in a mixer at a mixing temperature of 40° C. for 15 minutes, then sequentially adding the carbon black reinforcing agent, graphite fluoride, and nano-calcium fluoride and continuing to mix for 10 minutes, then adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing uniformly, and then hot pressing the mixture at a molding temperature of 160° C. and a molding pressure of 8 MPa for 10 minutes to obtain the rubber hose material.

[0035] Example 3: A fluorosilicone elastic rubber hose material, comprising the following raw materials in parts by weight: 100.0 parts of a fluorosilicone rubber matrix prepolymer, 33 parts of a white carbon black reinforcing agent, 6 parts of a KH-550 silane coupling agent, 17 parts of a carbon black reinforcing agent, 3.4 parts of 2,6-di-tert-butyl-p-cresol, 10 parts of a perfluoropolyether, 7 parts of fluorinated graphite, 5.2 parts of nano-calcium fluoride, and 2.0 parts of a hydroxy silicone oil; The fluorine-containing silicone rubber matrix prepolymer of this embodiment is a partially cross-linked polymer prepared by a pre-cross-linking reaction of a vinyl-containing polyhedral oligomeric silsesquioxane, an F-organic silicone polymer and an F-cross-linking agent under the action of a catalyst; the vinyl-containing polyhedral oligomeric silsesquioxane is prepared by an acid-catalyzed hydrolysis and condensation reaction of vinyltrimethoxysilane and methyltrimethoxysilane and then purified by recrystallization; the F-organic silicone polymer is a fluorine-containing vinyl siloxane copolymer prepared by anionic ring-opening polymerization with octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane and tetramethyltetravinylcyclotetrasiloxane as the main raw materials; the F-cross-linking agent is a fluorine-containing functional end group oligosiloxane prepared by ring-opening polymerization with octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as the initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capped with hexamethyldisiloxane.

[0036] The preparation method of the F-organic silicon polymer of this embodiment is as follows: 252 parts by weight of octamethylcyclotetrasiloxane, 430 parts of trifluoropropylmethylcyclotrisiloxane, and 14 parts of tetramethyltetravinylcyclotetrasiloxane are reacted at a reaction temperature of 86.0°C for 54 minutes under an argon atmosphere, and then 2.3 parts of tetramethylammonium hydroxide initiator and 1.3 parts of tetramethyldivinyldisiloxane are added, and the reaction is carried out at a stirring rate of 280 rpm for 276 minutes. The temperature is then raised to 148.0°C and maintained under vacuum for 22 hours. Finally, the polymer is purified with methanol 2.6 times and vacuum dried at a vacuum degree of 0.6 kPa and a drying temperature of 72.0°C for 10 hours to obtain the F-organic silicon polymer.

[0037] The preparation method of the F-crosslinking agent of this embodiment is as follows: in parts by weight, octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane are added in a weight ratio of 1.0:2.0 to a four-necked reaction flask equipped with a mechanical stirrer and a reflux condenser, the reaction temperature is raised to 90.0°C under argon atmosphere and maintained for 60 min to reach the initiation temperature, then 0.35 parts of tetramethylammonium hydroxide initiator are added to the reactor at a stirring rate of 300.0 rpm and a reaction temperature of 90.0°C to start the reaction, then 20.0 parts of tetramethylcyclotetrasiloxane are added dropwise to the reaction solution under vigorous stirring over 0.5 h using a dropping funnel, then 10.0 parts of hexamethyldisiloxane end-capping agent are added to the reactor, and the reaction temperature is continued to stir at 90.0°C for 120 min. After the reaction is completed, the product is heated to 150.0°C and maintained at 24.0°C under vacuum. h to remove unreacted reactants and initiators, and finally the product is purified using methanol to eliminate cyclic monomer impurities to obtain F-crosslinker.

[0038] The preparation method of the vinyl-containing polyhedral oligomeric silsesquioxane of the present embodiment is as follows: in parts by weight, 55.0 parts of vinyltrimethoxysilane and 50.0 parts of methyltrimethoxysilane are dissolved in 550.0 parts of an acetone solvent, and the mixture is stirred at a stirring rate of 320.0 rpm at a reaction temperature of 45.0°C under an argon atmosphere, and then 80.0 parts of a 2.0 mol / L hydrochloric acid solution is added dropwise over 180.0 min to carry out a hydrolysis condensation reaction, followed by continuing the reaction at a reaction temperature of 45.0°C for 38.0 h, followed by filtration and separation, and washing with ethanol, deionized water, and acetone 5 times each, followed by drying at a drying temperature of 65.0°C for 16.0 h, and then recrystallization and purification using a dichloromethane-acetone mixed solvent with a volume ratio of 1:3 and standing for 24.0 h. Finally, filtration, collection, and drying are performed to obtain the vinyl-containing polyhedral oligomeric silsesquioxane.

[0039] The preparation method of the fluorinated silicone rubber matrix prepolymer of this embodiment is as follows: 5.0 parts of vinyl-containing polyhedral oligomeric silsesquioxane are dissolved in 32.0 parts of tetrahydrofuran solvent, and then 295.0 parts of F-organic silicone polymer and 15.0 parts of F-crosslinker are added in sequence and mixed uniformly. Then, degassing is carried out at a vacuum degree of 1.0 kPa and a degassing temperature of 100.0°C for 120 min, followed by adding 0.15 parts of Custer catalyst and mixing uniformly at a stirring rate of 300 rpm. Finally, the tetrahydrofuran solvent is removed under reduced pressure to obtain a fluorinated silicone rubber matrix prepolymer.

[0040] The present embodiment provides a method for preparing a fluorosilicone elastic rubber hose material, comprising the following steps: premixing a fluorosilicone rubber matrix prepolymer with a white carbon black reinforcing agent and a silane coupling agent in a mixer at a mixing temperature of 60° C. for 25 minutes, then sequentially adding the carbon black reinforcing agent, graphite fluoride, and nano-calcium fluoride and continuing to mix for 20 minutes, then adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing uniformly, and then hot pressing the mixture at a molding temperature of 180° C. and a molding pressure of 15 MPa for 20 minutes to obtain the rubber hose material.

[0041] Example 4: A fluorosilicone elastic rubber hose material, comprising the following raw materials in parts by weight: 100.0 parts of a fluorosilicone rubber matrix prepolymer, 45.0 parts of a white carbon black reinforcing agent, 8.0 parts of a KH-550 silane coupling agent, 25.0 parts of a carbon black reinforcing agent, 5.0 parts of N,N-diphenyl-p-phenylenediamine, 15.0 parts of a perfluoropolyether, 10.0 parts of a fluorinated graphite, 8.0 parts of nano-calcium fluoride, and 3.0 parts of a hydroxy silicone oil; The fluorine-containing silicone rubber matrix prepolymer of this embodiment is a partially cross-linked polymer prepared by a pre-cross-linking reaction of a vinyl-containing polyhedral oligomeric silsesquioxane, an F-organic silicone polymer and an F-cross-linking agent under the action of a catalyst; the vinyl-containing polyhedral oligomeric silsesquioxane is prepared by an acid-catalyzed hydrolysis and condensation reaction of vinyltrimethoxysilane and methyltrimethoxysilane and then purified by recrystallization; the F-organic silicone polymer is a fluorine-containing vinyl siloxane copolymer prepared by anionic ring-opening polymerization with octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane and tetramethyltetravinylcyclotetrasiloxane as the main raw materials; the F-cross-linking agent is a fluorine-containing functional end group oligosiloxane prepared by ring-opening polymerization with octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as the initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capped with hexamethyldisiloxane.

[0042] The preparation method of the F-organic silicon polymer of this embodiment is as follows: in parts by weight, 260.0 parts of octamethylcyclotetrasiloxane, 450.0 parts of trifluoropropylmethylcyclotrisiloxane, and 15.0 parts of tetramethyltetravinylcyclotetrasiloxane are reacted at a reaction temperature of 90.0° C. for 60.0 min under an argon atmosphere, then 2.5 parts of tetramethylammonium hydroxide initiator and 1.5 parts of tetramethyldivinyldisiloxane are added, and the reaction is carried out at a stirring rate of 300.0 rpm for 300.0 min. The temperature is then raised to 150.0° C. and maintained under vacuum for 24.0 h. Finally, the mixture is purified with methanol 3.0 times and vacuum dried at a vacuum degree of 1.0 kPa and a drying temperature of 80.0° C. for 12.0 h to obtain the F-organic silicon polymer.

[0043] The preparation method of the F-crosslinking agent of this embodiment is as follows: octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane are added in a weight ratio of 1.0:1.8 in a four-necked reaction flask equipped with a mechanical stirrer and a reflux condenser, and the reaction temperature is raised to 86.0°C under argon atmosphere and maintained for 54 minutes to reach the initiation temperature. Then, 0.31 parts of tetramethylammonium hydroxide initiator are added to the reactor at a stirring rate of 280 rpm and a reaction temperature of 88.0°C to start the reaction. Then, a dropping funnel is used to stir vigorously at 0.5 16 parts of tetramethylcyclotetrasiloxane were added dropwise to the reaction solution within 1 h, and then 8 parts of hexamethyldisiloxane end-capping agent were added to the reactor. The reaction temperature was continued to stir at 88.0°C for 108 min. After the reaction was completed, the product was heated to 148.0°C and maintained under vacuum for 22 h to remove unreacted reactants and initiator. Finally, the product was purified with methanol to eliminate cyclic monomer impurities to obtain F-crosslinker.

[0044] The preparation method of the vinyl-containing polyhedral oligomeric silsesquioxane of this embodiment is as follows: in parts by weight, 51 parts of vinyltrimethoxysilane and 46 parts of methyltrimethoxysilane are dissolved in 510 parts of an acetone solvent, and the mixture is stirred at a stirring rate of 304 rpm at a reaction temperature of 41.0 ° C. under an argon atmosphere, and then 68 parts of a 1.4 mol / L hydrochloric acid solution are added dropwise over 156 minutes to carry out a hydrolysis condensation reaction, followed by continuing the reaction at a reaction temperature of 41.0 ° C. for 35 hours, followed by filtration and separation, and washing with ethanol, deionized water and acetone four times each, followed by drying at a drying temperature of 61.0 ° C. for 14 hours, and then recrystallization and purification using a dichloromethane-acetone mixed solvent with a volume ratio of 1:3 and standing for 22 hours. Finally, filtration, collection and drying are performed to obtain the vinyl-containing polyhedral oligomeric silsesquioxane.

[0045] The preparation method of the fluorinated silicone rubber matrix prepolymer of this embodiment is as follows: 4.0 parts of vinyl-containing polyhedral oligomeric silsesquioxane are dissolved in 28 parts of tetrahydrofuran solvent, and then 289 parts of F-organic silicone polymer and 11 parts of F-crosslinker are added in sequence and mixed evenly. Then, the mixture is degassed at a vacuum degree of 0.6 kPa and a degassing temperature of 100.0°C for 108 minutes, and then 0.12 parts of Custer catalyst are added and mixed evenly at a stirring rate of 280 rpm. Finally, the tetrahydrofuran solvent is removed under reduced pressure to obtain a fluorinated silicone rubber matrix prepolymer.

[0046] The present embodiment provides a method for preparing a fluorosilicone elastic rubber hose material, comprising the following steps: premixing a fluorosilicone rubber matrix prepolymer with a white carbon black reinforcing agent and a silane coupling agent in a mixer at a mixing temperature of 52° C. for 21 minutes, then sequentially adding the carbon black reinforcing agent, graphite fluoride, and nano-calcium fluoride and continuing to mix for 16 minutes, then adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing uniformly, and then hot pressing the mixture at a molding temperature of 172° C. and a molding pressure of 12 MPa for 16 minutes to obtain the rubber hose material.

[0047] Comparative Example 1: Basically the same as Example 1, except that the fluorine-containing silicone rubber matrix prepolymer is replaced by an ordinary methyl silicone rubber matrix prepolymer, and the ordinary methyl silicone rubber matrix prepolymer is prepared by octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane and a hydrogen-containing silicone oil crosslinker under the action of a platinum catalyst, and does not contain a trifluoropropyl structure.

[0048] Comparative Example 2: is basically the same as Example 1, except that no vinyl-containing polyhedral oligomeric silsesquioxane is added during the preparation of the fluorosilicone rubber matrix prepolymer, and it is prepared only by pre-crosslinking reaction of F-organic silicone polymer and F-crosslinker under the action of Custer catalyst.

[0049] Comparative Example 3: is basically the same as Example 1, except that trifluoropropylmethylcyclotrisiloxane is not added during the preparation of the F-organic silicone polymer, and only 400.0 parts of octamethylcyclotetrasiloxane and 12.0 parts of tetramethyltetravinylcyclotetrasiloxane are used as raw materials for anionic ring-opening polymerization.

[0050] Comparative Example 4: basically the same as Example 1, except that the reaction temperature during the preparation of the F-organic silicon polymer is 120.0°C.

[0051] Comparative Example 5: basically the same as Example 1, except that the initial reaction time during the preparation of the F-organic silicon polymer is 120.0 min.

[0052] Comparative Example 6: basically the same as Example 1, except that the weight ratio of octamethylcyclotetrasiloxane to trifluoropropylmethylcyclotrisiloxane in the preparation of the F-crosslinker is 1.0:0.8.

[0053] Comparative Example 7: Basically the same as Example 1, except that hexamethyldisiloxane is not used as a capping agent during the preparation of the F-crosslinker, but octamethylcyclotetrasiloxane is used for capping.

[0054] Comparative Example 8: Basically the same as Example 1, except that the amount of vinyl-containing polyhedral oligomeric silsesquioxane used in the preparation of the fluorine-containing silicone rubber matrix prepolymer is 8.0 parts.

[0055] Comparative Example 9: is basically the same as Example 1, except that the degassing temperature during the preparation of the fluorine-containing silicone rubber matrix prepolymer is 130.0°C, which exceeds the specified temperature of 100.0°C.

[0056] Comparative Example 10: basically the same as Example 1, except that the weight ratio of the white carbon black reinforcing agent to the carbon black reinforcing agent is 1:1.

[0057] Comparative Example 11 is basically the same as Example 1, except that no graphite fluoride is added and the amounts of other components remain unchanged.

[0058] Comparative Example 12: basically the same as Example 1, except that the pre-mixing temperature in the preparation method is 80.0°C.

[0059] Performance Testing: Tensile Strength and Elongation at Break: Tensile testing of rubber hose materials was conducted using a universal materials testing machine, using dumbbell-shaped specimens prepared according to standards. The tests were conducted in accordance with GB / T 528-2009. The specimen thickness was 2 ± 0.2 mm, the gauge length was 25 mm, and the tensile speed was set at 500 mm / min. Testing was conducted at room temperature (23 ± 2°C). The maximum stress at break was recorded as the tensile strength, and the elongation at break was also measured. At least five specimens were tested per group, and the average value was calculated.

[0060] Heat Aging Resistance Test: Rubber hose material specimens, measuring 15 mm x 15 mm x 2 mm, were subjected to heat aging tests in a high-temperature aging chamber. The test subjects were square specimens. The tests were conducted in accordance with GB / T 3512-2014, with an aging temperature of 200°C and aging times of 168, 336, and 504 hours, respectively. The tensile strength and elongation at break were measured before and after aging, and the performance retention was calculated to evaluate the material's stability and service life in high-temperature environments.

[0061] Chemical Corrosion Resistance Testing: Rubber hose materials were subjected to immersion corrosion tests using chemical media of varying pH values. Circular specimens with a diameter of 29 mm and a thickness of 2 mm were tested. The test followed the GB / T 1690-2010 standard, using hydrochloric acid solution (pH 1), sodium hydroxide solution (pH 14), and organic solvents such as toluene and acetone as the corrosive media. After immersion for 168 hours at 23±2°C, the specimens were removed and their mass and volume changes, as well as changes in mechanical properties, were measured to evaluate the corrosion resistance of the material.

[0062] Hardness Test: Rubber hose material hardness is measured using a Shore A durometer on a flat surface with a minimum thickness of 6mm. Testing is conducted at room temperature using a Shore A durometer in accordance with GB / T 531.1-2008. Hardness values are measured at five different locations on each specimen, with test points spaced at least 6mm apart. The average result is used to evaluate the material's balance between rigidity and flexibility.

[0063] The properties of the rubber hoses from Examples 1-4 and Comparative Examples 1-12 are summarized in Table 1. Using ordinary methyl silicone rubber matrix prepolymers in place of fluorosilicone rubber matrix prepolymers results in the material losing the protective effect of the trifluoropropyl structure, significantly reducing chemical corrosion resistance and heat aging resistance. In particular, stability in acidic and alkaline media and organic solvents is significantly reduced, while the mechanical property retention rate in high-temperature environments is also significantly weakened. Omitting the addition of vinyl-containing polyhedral oligomeric silsesquioxanes results in the material losing the reinforcing effect of the rigid crosslinking nodes, resulting in a significant decrease in tensile strength, insufficient overall rigidity, and a decrease in hardness, but with relatively little effect on heat resistance and corrosion resistance. Omitting trifluoropropylmethylcyclotrisiloxane during the preparation of the F-organic silicone polymers results in the material losing the protective effect of the fluorinated side chains, significantly reducing chemical corrosion resistance and adversely affecting heat aging resistance, but with a relatively limited impact on basic mechanical properties. Excessively high reaction temperatures during the preparation of the F-organic silicone polymers can lead to molecular chain degradation or uneven crosslinking, affecting the mechanical properties and processing properties of the final material, but with minimal effect on corrosion resistance. Excessively long initial reaction times may lead to increased side reactions or a broadening of the molecular weight distribution, resulting in a slight but limited negative impact on material properties. Improper raw material ratios during the preparation of F-crosslinkers can affect the crosslinker's molecular structure and reactivity, leading to suboptimal crosslinking in the prepolymer, ultimately impacting the material's mechanical properties and network stability. Using octamethylcyclotetrasiloxane instead of hexamethyldisiloxane for end-capping can affect the crosslinker's end group structure and reactivity, negatively impacting material properties to a certain extent. Excessive amounts of vinyl-containing polyhedral oligomeric silsesquioxanes can overly rigidify the material. While increasing hardness and modulus, elongation at break decreases significantly, making the material brittle and impairing processing properties. Excessively high degassing temperatures during prepolymer preparation can cause volatilization or degradation of some components, impacting the final material's performance stability and uniformity. An inappropriate ratio of silica to carbon black reinforcing agent can compromise the synergistic reinforcing effect of the filler, resulting in a decrease in tensile strength and potentially affecting filler dispersion. Without the addition of graphite fluoride, the material loses its lamellar structure's physical barrier effect, reducing its resistance to chemical media corrosion, especially its barrier properties to organic solvents. Excessively high premixing temperatures can affect the material's processing properties and component dispersion uniformity, potentially leading to performance degradation caused by localized overheating, but have relatively little impact on the final material's basic properties.

[0064] Table 1 Performance summary of rubber hoses of Examples 1 to 4 and Comparative Examples 1 to 12:

[0065]

[0066]

[0067] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that any equivalent structural transformations made within the scope of the present invention using the contents of the present invention's description and drawings should be included within the scope of protection of the claims of the present invention.

Claims

1. A rubber hose material based on fluorosilicone elasticity, characterized in that: The invention comprises the following raw materials in parts by weight: 100.0 parts of fluorinated silicone rubber matrix prepolymer, 15.0-45.0 parts of white carbon black reinforcing agent, 2.0-8.0 parts of silane coupling agent, 5.0-25.0 parts of carbon black reinforcing agent, 1.0-5.0 parts of antioxidant, 3.0-15.0 parts of fluorinated plasticizer, 2.0-10.0 parts of fluorinated graphite, 1.0-8.0 parts of nano calcium fluoride, and 0.5-3.0 parts of silicone flow modifier; The fluorine-containing silicone rubber matrix prepolymer is a partially cross-linked polymer prepared by a pre-cross-linking reaction of a vinyl-containing polyhedral oligomeric silsesquioxane, an F-organic silicon polymer and an F-cross-linking agent under the action of a catalyst; The vinyl-containing polyhedral oligomeric silsesquioxane is prepared by acid-catalyzed hydrolysis and condensation of vinyltrimethoxysilane and methyltrimethoxysilane and then purified by recrystallization; The F-organic silicon polymer is a fluorine-containing vinyl siloxane copolymer prepared by anionic ring-opening polymerization using octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane and tetramethyltetravinylcyclotetrasiloxane as main raw materials; The F-crosslinking agent is a fluorine-containing functional end group oligosiloxane prepared by ring-opening polymerization of octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capping with hexamethyldisiloxane.

2. A fluorosilicone elastic rubber hose material according to claim 1, characterized in that: The preparation method of the F-organic silicon polymer is as follows: in parts by weight, 240.0-260.0 parts of octamethylcyclotetrasiloxane, 400.0-450.0 parts of trifluoropropylmethylcyclotrisiloxane and 12.0-15.0 parts of tetramethyltetravinylcyclotetrasiloxane are reacted at a reaction temperature of 80.0-90.0°C under an argon atmosphere for 45.0-60.0 min, and then 2.1-2.5 parts of tetramethylammonium hydroxide initiator and 1.1-1.5 parts of tetramethyldivinyldisiloxane are added and reacted at a stirring rate of 250.0-300.0 rpm for 240.0-300.0 min, then the temperature is raised to 145.0-150.0°C and maintained under vacuum conditions for 20.0-24.0 h, and finally purified with methanol 2.0-3.0 times and the vacuum degree is 0.1-1.0 kPa and a drying temperature of 60.0-80.0°C under vacuum drying for 8.0-12.0 h to obtain F-organic silicon polymer.

3. The fluorosilicone elastic rubber hose material according to claim 1, characterized in that: The preparation method of the F-crosslinking agent is as follows: octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane are added to a four-necked reaction flask equipped with a mechanical stirrer and a reflux condenser in a weight ratio of 1.0:1.5~2.0 in parts by weight, and the reaction temperature is raised to 80~90.0 ° C and maintained for 45~60 min under argon atmosphere to reach the initiation temperature, and then 0.25~0.35 parts of tetramethylammonium hydroxide initiator are added to the reactor at a stirring rate of 250~300.0 rpm and a reaction temperature of 85~90.0 ° C to start the reaction, and then a dropping funnel is used to stir vigorously at 0.5 10.0-20.0 parts of tetramethylcyclotetrasiloxane were dropwise added to the reaction solution within 1 h, followed by the addition of 5.0-10.0 parts of hexamethyldisiloxane end-capping agent to the reactor. The reaction was continued with stirring at a reaction temperature of 85-90.0°C for 90-120 min. After completion of the reaction, the product was heated to 145-150.0°C and maintained under vacuum for 20-24.0 h to remove unreacted reactants and initiator. Finally, the product was purified with methanol to eliminate cyclic monomer impurities to obtain the F-crosslinker.

4. The fluorosilicone elastic rubber hose material according to claim 1, characterized in that: The preparation method of the fluorine-containing silicone rubber matrix prepolymer comprises the following steps: dissolving 2.5 to 5.0 parts of a vinyl-containing polyhedral oligomeric silsesquioxane in 22.0 to 32.0 parts of a tetrahydrofuran solvent, sequentially adding 280.0 to 295.0 parts of an F-organic silicone polymer and 5.0 to 15.0 parts of an F-crosslinking agent, and mixing them uniformly; then degassing the mixture at a vacuum degree of 0.1 to 1.0 kPa and a degassing temperature of 100.0°C for 90 to 120 minutes; then adding 0.1 to 0.15 parts of a Custer catalyst, and mixing them uniformly at a stirring rate of 250 to 300 rpm; and finally removing the tetrahydrofuran solvent under reduced pressure to obtain the fluorine-containing silicone rubber matrix prepolymer.

5. The fluorosilicone elastic rubber hose material according to claim 1, characterized in that: The weight ratio of the white carbon black reinforcing agent to the carbon black reinforcing agent is 2:1 to 4:

1.

6. The fluorosilicone elastic rubber hose material according to claim 1, characterized in that: The silane coupling agent is KH-550 silane coupling agent or KH-151 silane coupling agent; The antioxidant is 2,6-di-tert-butyl-p-cresol or N,N-diphenyl-p-phenylenediamine; The fluorinated plasticizer is perfluoropolyether; The silicone flow modifier is hydroxy silicone oil.

7. The method for preparing a fluorosilicone elastic rubber hose material according to claims 1 to 6, characterized in that: The following steps are involved: The fluorinated silicone rubber matrix prepolymer, white carbon black reinforcement, and silane coupling agent were pre-mixed in a mixer at a mixing temperature of 40-60°C for 15-25 min. Then, the carbon black reinforcement, graphite fluoride, and nano-calcium fluoride were added in sequence and mixed for 10-20 min. Subsequently, the fluorinated plasticizer, silicone flow modifier, and antioxidant were added and mixed evenly. Subsequently, the rubber hose material was hot-pressed at a molding temperature of 160-180°C and a molding pressure of 8-15 MPa for 10-20 min.

8. A fluorosilicone elastic rubber hose material according to claim 1, wherein the rubber hose has an operating temperature range of -50 to 250°C, a tensile strength of ≥15 MPa, an elongation at break of ≥200%, and can withstand corrosion from media with a pH value of 1 to 14.

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