A fluorosilicone-based rubber hose material and a method for producing the same

Abstract

This invention relates to the field of polymer plastic pipes, and provides a fluorosilicone elastic rubber hose material and its preparation method, aiming to solve the problems of insufficient tensile strength and chemical corrosion resistance of existing hose materials. The material is composed of a fluorosilicone rubber matrix, silica, carbon black, fluorinated graphite, nano-calcium fluoride, fluorinated plasticizer, silane coupling agent, antioxidant, and silicone flow modifier. The material ratio is reasonable, synergistically constructing a reinforced interface and dense network structure. The fluorosilicone rubber matrix is ​​polymerized by containing vinyl silsesquioxane, F-organosilicon polymer, and F-crosslinking agent under the action of a catalyst. This method, through multi-component synergistic reinforcement and optimized molding process, significantly improves the material's tensile strength, elongation at break, and resistance to chemical corrosion in media with a pH range of 1-14, making it suitable for high-performance sealing, transmission, and other fields.

Description

A rubber hose material based on fluorosilicone elasticity and its preparation method Technical Field

[0001] This invention relates to the field of polymer plastic pipes, specifically to a rubber hose material based on fluorosilicone elasticity and its preparation method. Background Technology

[0002] In high-temperature, high-pressure, and complex corrosive environments such as aerospace, rail transportation, automotive engine compartments, precision chemicals, and high-end equipment manufacturing, rubber hoses, as key flexible connections and sealing elements, are widely used in fuel, lubricating oil, coolant, and chemical media delivery systems. Their performance directly affects the operational stability and safety of the entire system. In these applications, hose materials must withstand frequent mechanical stress, dynamic bending, and vibration impacts, as well as long-term resistance to high temperatures, hot oxygen, oils, and corrosive media. Therefore, more stringent requirements are placed on the tensile strength and heat resistance of the materials. On the one hand, excellent tensile strength ensures that the hose does not break, deform, or leak under high-pressure delivery and dynamic loads, improving service life and structural reliability. On the other hand, good heat resistance is a core indicator for ensuring that the material maintains mechanical stability and sealing performance under high-temperature conditions. As equipment systems develop towards higher power, lighter weight, and greater intelligence, material performance also needs continuous iteration and breakthroughs. Therefore, developing new rubber hose materials that combine high strength and high heat resistance can not only meet the urgent needs of key fields 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 various modified rubber materials have been applied to hose manufacturing, attempting to improve their comprehensive performance through filler reinforcement, blending modification, or cross-linking structure regulation, significant shortcomings remain in meeting the dual requirements of high strength and heat resistance. For example, Chinese patent CN119775784A discloses a fluorosilicone rubber, a fluorosilicone rubber hose, its preparation method, and its application. It employs a synergistic reinforcement system of inorganic fillers and organosilicon resin to improve the mechanical properties and thermal stability of the hose. However, it suffers from limited tensile strength improvement and insufficient structural stability at high temperatures, making it difficult to meet the requirements of long-term use under harsh conditions. The root cause of these problems lies in the uneven dispersion of fillers, weak interfacial bonding, or imperfect cross-linking networks in the material system. This results in the reinforcing units being unable to efficiently bear loads and transfer stress, thus limiting the improvement of mechanical properties. Simultaneously, some reinforcing components are prone to thermal aging or structural rearrangement at high temperatures, not only reducing the material's thermal stability but also potentially causing failure behaviors such as interfacial debonding and microcrack propagation. Furthermore, existing manufacturing processes are still insufficient in terms of component synergistic design and structural compactness control, making it difficult to achieve synergistic optimization of mechanical reinforcement and thermal stability. Therefore, how to construct fluorosilicone elastic hose materials with excellent interfacial compatibility, stable three-dimensional cross-linked structure and highly thermally stable micronetwork remains an important technical problem that urgently needs to be solved in the field of materials research and development. Summary of the Invention

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

[0005] (2) Technical solution: In order to achieve the above objectives, the present invention provides the following technical solution:

[0006] A rubber hose material based on fluorosilicone elasticity comprises the following raw materials in parts by weight: 100.0 parts of fluorosilicone rubber matrix prepolymer, 15.0~45.0 parts of silica 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;

[0007] The fluorinated silicone rubber matrix prepolymer is a partially crosslinked polymer prepared by a pre-crosslinking reaction of vinyl polyhedral oligomeric silsesquioxane, F-organosilicon polymer and F-crosslinking agent under the action of a catalyst;

[0008] The vinyl polyhedral oligomeric silsesquioxane is prepared by acid-catalyzed hydrolysis-condensation reaction of vinyltrimethoxysilane and methyltrimethoxysilane followed by recrystallization purification.

[0009] The F-organosilicon polymer is a fluorinated vinyl siloxane copolymer prepared by anionic ring-opening polymerization reaction using octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane and tetramethyltetravinylcyclotetrasiloxane as the main raw materials.

[0010] The F-crosslinking agent is a fluorine-functionalized oligomeric siloxane prepared by ring-opening polymerization of octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capping with hexamethyldisiloxane.

[0011] Further, the preparation method of the F-organosilicon polymer is as follows: 240.0-260.0 parts by weight of octamethylcyclotetrasiloxane, 400.0-450.0 parts by weight of trifluoropropylmethylcyclotrisiloxane, and 12.0-15.0 parts by weight of tetramethyltetravinylcyclotetrasiloxane are reacted at a temperature of 80.0-90.0°C under an argon atmosphere for 45.0-60.0 min. Then, 2.1-2.5 parts by weight of tetramethylammonium hydroxide initiator and 1.1-1.5 parts by weight of tetramethyldivinyldisiloxane are added, and the reaction is carried out at a stirring rate of 250.0-300.0 rpm for 240.0-300.0 min. The temperature is then raised to 145.0-150.0°C and maintained under vacuum for 20.0-24.0 h. Finally, the mixture is purified 2.0-3.0 times with methanol under a vacuum of 0.1-1.0 degrees Celsius. F-organosilicon polymer was obtained by vacuum drying at kPa and a drying temperature of 60.0~80.0°C for 8.0~12.0 h.

[0012] Further, 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. Under an argon atmosphere, the reaction temperature is raised to 80~90.0°C and maintained for 45~60 min to reach the initiation temperature. Then, 0.25~0.35 parts of tetramethylammonium hydroxide initiator are added to the reactor at a stirring speed of 250~300.0 rpm and a reaction temperature of 85~90.0°C to start the reaction. The reaction is then carried out using a dropping funnel under vigorous stirring at 0.5... Within h, 10.0~20.0 parts of tetramethylcyclotetrasiloxane were added dropwise to the reaction solution, followed by 5.0~10.0 parts of hexamethyldisiloxane end-capping agent. The reaction was continued with stirring at a temperature of 85~90.0°C for 90~120 min. After the reaction was completed, the product was heated to 145~150.0°C and maintained under vacuum for 20~24.0 h to remove unreacted reactants and initiators. Finally, the product was purified with methanol to eliminate cyclic monomer impurities and obtain F-crosslinking agent.

[0013] Further, the preparation method of the vinyl-containing polyhedral oligomeric silsesquioxane is as follows: 45.0-55.0 parts by weight of vinyltrimethoxysilane and 40.0-50.0 parts by weight of methyltrimethoxysilane are dissolved in 450.0-550.0 parts by weight of acetone solvent. The mixture is 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. Then, 50.0-80.0 parts by weight of a 0.5-2.0 mol / L hydrochloric acid solution are added dropwise over 120.0-180.0 min to carry out a hydrolysis-condensation reaction. The reaction is then continued at 35.0-45.0°C for 30.0-38.0 min. h, then filtered and separated, and washed with ethanol, deionized water and acetone 3.0 to 5.0 times each, then dried at 55.0 to 65.0°C for 12.0 to 16.0 h, then recrystallized and purified with a 1:3 dichloromethane-acetone mixed solvent and allowed to stand for 20.0 to 24.0 h, finally filtered, collected and dried to obtain vinyl polyhedral oligomeric silsesquioxane.

[0014] Further, the preparation method of the fluorinated silicone rubber matrix prepolymer is as follows: by weight, 2.5-5.0 parts of vinyl polyhedral oligomeric silsesquioxane are dissolved in 22.0-32.0 parts of tetrahydrofuran solvent, then 280.0-295.0 parts of F-organosilicon polymer and 5.0-15.0 parts of F-crosslinking agent are added sequentially and mixed evenly. Then, degassing is carried out at a vacuum degree of 0.1-1.0 kPa and a degassing temperature of 100.0°C for 90-120 min. Subsequently, 0.1-0.15 parts of caster catalyst are added and mixed evenly at a stirring rate of 250-300 rpm. Finally, the tetrahydrofuran solvent is removed under reduced pressure to obtain the fluorinated silicone rubber matrix prepolymer.

[0015] This invention employs a design combining a vinyl polyhedral oligomeric silsesquioxane-modified fluorosilicone rubber matrix prepolymer with a multi-component filler reinforcement system, primarily used to enhance the tensile strength and heat resistance of rubber hose materials. This technical solution, through a synergistic reinforcement strategy of molecular structure design and multi-scale structure regulation, aims to address the key issues of insufficient mechanical properties and limited thermal stability of traditional fluorosilicone rubber materials under extreme environments. The constructed fluorosilicone rubber matrix prepolymer is based on a rigid-flexible three-dimensional crosslinked network. The vinyl polyhedral oligomeric silsesquioxane, with its unique cage-like siloxane skeleton structure, serves as a rigid crosslinking node, forming a stable chemical connection with the flexible segments of the F-organosilicon polymer, significantly improving the material's modulus and thermal stability while maintaining excellent flexibility and processability. The trifluoropropyl side chains introduced into the F-organosilicon polymer endow the molecular chains with excellent chemical inertness and resistance to media corrosion, and their main chain structure provides sufficient reactivity for the construction of the crosslinked network, ensuring the integrity and uniformity of the network structure. The introduction of F-crosslinking agents further constructed a dense covalent bond network, enhancing the overall structural stability and mechanical strength of the matrix. Based on this, the multi-component filler reinforcement system significantly improved the comprehensive performance of the composite material through meticulous design. Silica, through the interfacial regulation effect of silane coupling agents, achieved a strong bond with the matrix, improving filler dispersion and stress transfer efficiency. Carbon black, with its unique aggregated structure, provided additional structural support and reinforcement. Fluorinated graphite, with its layered structure, constructed an effective physical barrier network within the material, significantly improving its barrier ability against corrosive media. Nano-calcium fluoride, through its surface properties, formed good interfacial compatibility with the matrix and significantly improved the structural rigidity of the material. The introduction of fluorinated plasticizers enhanced the chemical stability of the system while maintaining the material's flexibility. Silicone flow modifiers further optimized the material's processing flowability and molding performance, while antioxidants effectively delayed the thermo-oxidative aging process of the material under high-temperature environments. Ultimately, the components achieve an organic unity in terms of molecular structure design, interface regulation, and macroscopic performance synergy, enabling the composite material to achieve a significant improvement in tensile strength and heat resistance while maintaining excellent flexibility, thus meeting the increasingly stringent technical requirements of high-performance flexible sealing materials for high-end application environments.

[0016] Furthermore, the weight ratio of the silica reinforcing agent to the carbon black reinforcing agent is 2:1 to 4:1.

[0017] Furthermore, the silane coupling agent is KH-550 silane coupling agent or KH-151 silane coupling agent;

[0018] The antioxidant is 2,6-di-tert-butyl-p-cresol or N,N-diphenyl-p-phenylenediamine;

[0019] The fluorinated plasticizer is a perfluoropolyether;

[0020] The silicone flow modifier mentioned is hydroxyl silicone oil.

[0021] This 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 with a silica reinforcing agent and a silane coupling agent in a mixer at a mixing temperature of 40-60°C for 15-25 min; then sequentially adding a silica reinforcing agent, fluorinated graphite, and nano-calcium fluoride and continuing to mix for 10-20 min; next, adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing evenly; and then hot-pressing the mixture at a molding temperature of 160-180°C and a molding pressure of 8-15 MPa for 10-20 min to obtain the rubber hose material.

[0022] Furthermore, the rubber hose has a service 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.

[0023] (3) Beneficial technical effects: 1. The present invention significantly improves the tensile strength and heat resistance of hose materials by synergistically constructing a three-dimensional network structure with fluorosilicone prepolymer and multi-functional filler, and has the advantages of flexibility, processability and environmental adaptability, making it suitable for sealing applications under extreme working conditions. Attached Figure Description

[0024] Figure 1 is the infrared Fourier spectrum of the F-organosilicon polymer prepared in Example 1 of the present invention.

[0025] Figure 2 is the infrared Fourier spectrum of the F-crosslinking agent prepared in Example 1 of the present invention.

[0026] Figure 3 is the infrared Fourier spectrum of the vinyl polyhedral oligomeric silsesquioxane prepared in Example 1 of the present invention.

[0027] Figure 4 is a morphology diagram of the vinyl polyhedral oligomeric silsesquioxane prepared in Example 1 of the present invention.

[0028] Figure 5 is a physical image of the rubber pipe prepared in Example 1 of the present invention.

[0029] Figure 6 is a tensile test image of the rubber pipe specimen prepared in Example 1 of the present invention during tensile testing. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.

[0031] Example 1: A rubber hose material based on fluorosilicone elasticity, comprising the following raw materials in parts by weight: 100.0 parts of fluorosilicone rubber matrix prepolymer, 15.0 parts of silica reinforcing agent, 2.0 parts of 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 carbon black reinforcing agent, 1.0 part of 2,6-di-tert-butyl-p-cresol, 3.0 parts of perfluoropolyether, 2.0 parts of fluorinated graphite, 1.0 part of nano-calcium fluoride, and 0.5 parts of hydroxyl silicone oil;

[0032] In this embodiment, the fluorinated silicone rubber matrix prepolymer is a partially crosslinked polymer prepared by a pre-crosslinking reaction of vinyl polyhedral oligomeric silsesquioxane, F-organosilicon polymer, and F-crosslinking agent under the action of a catalyst; the vinyl polyhedral oligomeric silsesquioxane is prepared by acid-catalyzed hydrolysis and condensation reaction of vinyltrimethoxysilane and methyltrimethoxysilane and then purified by recrystallization; the F-organosilicon polymer is a fluorinated vinyl siloxane copolymer prepared by anionic ring-opening polymerization reaction of octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane, and tetramethyltetravinylcyclotetrasiloxane as the main raw materials; the F-crosslinking agent is a fluorinated functionalized oligomeric siloxane prepared by ring-opening polymerization of octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capped with hexamethyldisiloxane.

[0033] The preparation method of the F-organosilicon polymer in this embodiment is as follows: 240.0 parts by weight of octamethylcyclotetrasiloxane, 400.0 parts by weight of trifluoropropylmethylcyclotrisiloxane and 12.0 parts by weight of tetramethyltetravinylcyclotetrasiloxane were reacted at 80.0°C for 45.0 min under an argon atmosphere. Then, 2.1 parts by weight of tetramethylammonium hydroxide initiator and 1.1 parts by weight of tetramethyldivinyldisiloxane were added and reacted at a stirring rate of 250.0 rpm for 240.0 min. The temperature was then raised to 145.0°C and maintained under vacuum for 20.0 h. Finally, the polymer was purified twice with methanol 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-organosilicon polymer.

[0034] The preparation method of the F-crosslinking agent in this embodiment is as follows: Octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane were 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. Under an argon atmosphere, the reaction temperature was raised to 83.0°C and maintained for 50 minutes to reach the initiation temperature. Then, 0.28 parts of tetramethylammonium hydroxide initiator were added to the reactor at a stirring rate of 265 rpm and a reaction temperature of 87.0°C to start the reaction. Next, 13 parts of tetramethylcyclotetrasiloxane were added dropwise to the reaction solution over 0.5 hours under vigorous stirring using a dropping funnel. Subsequently, 7 parts of hexamethyldisiloxane end-capping agent were added to the reactor. The reaction was continued at 87.0°C for 99 minutes with stirring. After the reaction was completed, the product was heated to 147.0°C and maintained under vacuum for 21 minutes. h removes unreacted reactants and initiators, and finally the product is purified with methanol to eliminate cyclic monomer impurities to obtain F-crosslinking agent.

[0035] The preparation method of the vinyl polyhedral oligomeric silsesquioxane in this embodiment is as follows: 48 parts by weight of vinyltrimethoxysilane and 43 parts by weight of methyltrimethoxysilane are dissolved in 480 parts by weight of acetone solvent. The mixture is stirred at a stirring rate of 292 rpm and a reaction temperature of 38.0°C under an argon atmosphere. Then, 59 parts by weight of 1.0 mol / L hydrochloric acid solution are added dropwise over 138 min to carry out a hydrolysis-condensation reaction. The reaction is then continued at 38.0°C for 32 h. The mixture is then filtered and washed four times each with ethanol, deionized water, and acetone. The mixture is then dried at 58.0°C for 13 h. It is then purified by recrystallization using a 1:3 volume ratio dichloromethane-acetone mixed solvent and allowed to stand for 21 h. Finally, the mixture is filtered, collected, and dried to obtain the vinyl polyhedral oligomeric silsesquioxane.

[0036] The preparation method of the fluorinated silicone rubber matrix prepolymer in this embodiment is as follows: by weight, 3.3 parts of vinyl polyhedral oligomeric silsesquioxane are dissolved in 25 parts of tetrahydrofuran solvent, then 285 parts of F-organosilicon polymer and 8 parts of F-crosslinking agent are added sequentially and mixed evenly. Then, degassing is carried out for 99 min under vacuum of 0.4 kPa and degassing temperature of 100.0°C. Subsequently, 0.11 parts of caster catalyst are added and mixed evenly at a stirring rate of 265 rpm. Finally, the tetrahydrofuran solvent is removed under reduced pressure to obtain the fluorinated silicone rubber matrix prepolymer.

[0037] This embodiment describes a method for preparing a rubber hose material based on fluorosilicone elasticity, comprising the following steps: pre-mixing a fluorosilicone rubber matrix prepolymer with a silica reinforcing agent and a silane coupling agent in a mixer at a mixing temperature of 46°C for 18 min; then sequentially adding a silica reinforcing agent, fluorinated graphite, and nano-calcium fluoride and continuing mixing for 13 min; next, adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing evenly; and then hot-pressing at a molding temperature of 166°C and a molding pressure of 10 MPa for 13 min to obtain the rubber hose material.

[0038] As can be seen from the infrared Fourier spectrum of the F-organosilicon polymer in Figure 1, a strong absorption peak belonging to the asymmetric stretching vibration of the siloxane backbone (-Si--O--Si--) appears in the range of 1130-1000 cm⁻¹. At the same time, the 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-organosilicon polymer has successfully introduced trifluoropropyl side chains and methyl groups. The infrared Fourier spectrum of the F-crosslinker in Figure 2 also shows the strong absorption band of the asymmetric stretching vibration of --Si--O--Si-- 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--. Particularly important is the observation of the characteristic absorption peak of the Si--H bond at 2245 cm⁻¹, confirming the successful preparation of a short-chain siloxane crosslinker containing methyl, trifluoropropyl and hydrogen groups. Figure 3 shows the infrared Fourier transform spectrum of the vinyl-containing polyhedral oligomeric silsesquioxane. A single strong absorption peak at 1110 cm⁻¹, attributed to the --Si--O--Si-- group in the cage-like structure, absorption peaks of the --C=C-- group appear at 1000 and 1616 cm⁻¹, and a Si--CH₃ peak is observed at 824 cm⁻¹, confirming the successful synthesis of polyhedral oligomeric silsesquioxanes with a defined vinyl ratio. Figure 4 shows the morphology of the vinyl-containing polyhedral oligomeric silsesquioxanes, indicating that all POSS samples have a cubic structure, consistent with the structural characteristics reported in the literature, further confirming the successful preparation and structural integrity of the POSS. Figure 5 shows the actual rubber pipe prepared in Example 1 of this invention. The material surface is smooth and uniform, with consistent color and no obvious defects, exhibiting good molding quality and appearance characteristics. Figure 6 shows a tensile diagram of the rubber pipe tensile specimen. As can be seen from the figure, the specimen maintains good deformation uniformity during the tensile process, and there is no obvious stress concentration or local failure phenomenon. This indicates that the material has excellent mechanical properties and toughness, which verifies the effectiveness of the technical solution of the present invention and the excellent comprehensive performance of the material.

[0039] Example 2: A rubber hose material based on fluorosilicone elasticity, comprising the following raw materials in parts by weight: 100.0 parts of fluorosilicone rubber matrix prepolymer, 24 parts of silica reinforcing agent, 4 parts of KH-151 silane coupling agent, 11 parts of carbon black reinforcing agent, 2.2 parts of N,N-diphenyl-p-phenylenediamine, 7 parts of perfluoropolyether, 4 parts of fluorinated graphite, 3.1 parts of nano-calcium fluoride, and 1.3 parts of hydroxyl silicone oil;

[0040] In this embodiment, the fluorinated silicone rubber matrix prepolymer is a partially crosslinked polymer prepared by a pre-crosslinking reaction of vinyl polyhedral oligomeric silsesquioxane, F-organosilicon polymer, and F-crosslinking agent under the action of a catalyst; the vinyl polyhedral oligomeric silsesquioxane is prepared by acid-catalyzed hydrolysis and condensation reaction of vinyltrimethoxysilane and methyltrimethoxysilane and then purified by recrystallization; the F-organosilicon polymer is a fluorinated vinyl siloxane copolymer prepared by anionic ring-opening polymerization reaction of octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane, and tetramethyltetravinylcyclotetrasiloxane as the main raw materials; the F-crosslinking agent is a fluorinated functionalized oligomeric siloxane prepared by ring-opening polymerization of octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capped with hexamethyldisiloxane.

[0041] The preparation method of the F-organosilicon polymer in this embodiment is as follows: 246 parts by weight of octamethylcyclotetrasiloxane, 415 parts by weight of trifluoropropylmethylcyclotrisiloxane and 13 parts by weight of tetramethyltetravinylcyclotetrasiloxane were reacted at 83.0°C for 50 min under an argon atmosphere. Then, 2.2 parts by weight of tetramethylammonium hydroxide initiator and 1.2 parts by weight of tetramethyldivinyldisiloxane were added and reacted at a stirring rate of 265 rpm for 258 min. The temperature was then raised to 147.0°C and maintained under vacuum for 21 h. Finally, the polymer was 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 h to obtain the F-organosilicon polymer. The preparation method of the F-crosslinking agent in this embodiment is as follows: Octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane were 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. Under an argon atmosphere, the reaction temperature was raised to 80°C and maintained for 45 minutes to reach the initiation temperature. Then, 0.25 parts of tetramethylammonium hydroxide initiator were added to the reactor at a stirring speed of 250 rpm and a reaction temperature of 85°C to start the reaction. Next, 10.0 parts of tetramethylcyclotetrasiloxane were added dropwise to the reaction solution over 0.5 hours under vigorous stirring using a dropping funnel. Subsequently, 5.0 parts of hexamethyldisiloxane end-capping agent were added to the reactor. The reaction was continued at 85°C for 90 minutes with stirring. After the reaction was completed, the product was heated to 145°C and maintained under vacuum for 20 minutes. h removes unreacted reactants and initiators, and finally the product is purified with methanol to eliminate cyclic monomer impurities to obtain F-crosslinking agent.

[0042] The preparation method of the vinyl polyhedral oligomeric silsesquioxane in this embodiment is as follows: 45.0 parts by weight of vinyltrimethoxysilane and 40.0 parts by weight of methyltrimethoxysilane are dissolved in 450.0 parts by weight of acetone solvent. The mixture is stirred at a stirring rate of 280.0 rpm and a reaction temperature of 35.0°C under an argon atmosphere. Then, 50.0 parts by weight of 0.5 mol / L hydrochloric acid solution are added dropwise over 120.0 min to carry out a hydrolysis-condensation reaction. The reaction is then continued at 35.0°C for 30.0 h. The mixture is then filtered and washed 3.0 times each with ethanol, deionized water, and acetone. The mixture is then dried at 55.0°C for 12.0 h. Finally, it is purified by recrystallization using a 1:3 volume ratio dichloromethane-acetone mixed solvent and allowed to stand for 20.0 h. The mixture is then filtered, collected, and dried to obtain the vinyl polyhedral oligomeric silsesquioxane.

[0043] The preparation method of the fluorinated silicone rubber matrix prepolymer in this embodiment is as follows: 2.5 parts by weight of vinyl polyhedral oligomeric silsesquioxane are dissolved in 22.0 parts of tetrahydrofuran solvent. Then, 280.0 parts of F-organosilicon polymer and 5.0 parts of F-crosslinking agent are added sequentially and mixed evenly. Next, degassing is carried out for 90 min under a vacuum of 0.1 kPa and a degassing temperature of 100.0°C. Subsequently, 0.1 parts of caster catalyst are added and mixed evenly with a stirring rate of 250 rpm. Finally, the tetrahydrofuran solvent is removed under reduced pressure to obtain the fluorinated silicone rubber matrix prepolymer.

[0044] This embodiment describes a method for preparing a rubber hose material based on fluorosilicone elasticity, comprising the following steps: pre-mixing a fluorosilicone rubber matrix prepolymer with a silica reinforcing agent and a silane coupling agent in a mixer at a mixing temperature of 40°C for 15 min; then sequentially adding a silica reinforcing agent, fluorinated graphite, and nano-calcium fluoride and continuing mixing for 10 min; next, adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing evenly; and then hot-pressing at a molding temperature of 160°C and a molding pressure of 8 MPa for 10 min to obtain the rubber hose material.

[0045] Example 3: A rubber hose material based on fluorosilicone elasticity, comprising the following raw materials in parts by weight: 100.0 parts of fluorosilicone rubber matrix prepolymer, 33 parts of silica reinforcing agent, 6 parts of KH-550 silane coupling agent, 17 parts of carbon black reinforcing agent, 3.4 parts of 2,6-di-tert-butyl-p-cresol, 10 parts of perfluoropolyether, 7 parts of fluorinated graphite, 5.2 parts of nano-calcium fluoride, and 2.0 parts of hydroxyl silicone oil;

[0046] In this embodiment, the fluorinated silicone rubber matrix prepolymer is a partially crosslinked polymer prepared by a pre-crosslinking reaction of vinyl polyhedral oligomeric silsesquioxane, F-organosilicon polymer, and F-crosslinking agent under the action of a catalyst; the vinyl polyhedral oligomeric silsesquioxane is prepared by acid-catalyzed hydrolysis and condensation reaction of vinyltrimethoxysilane and methyltrimethoxysilane and then purified by recrystallization; the F-organosilicon polymer is a fluorinated vinyl siloxane copolymer prepared by anionic ring-opening polymerization reaction of octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane, and tetramethyltetravinylcyclotetrasiloxane as the main raw materials; the F-crosslinking agent is a fluorinated functionalized oligomeric siloxane prepared by ring-opening polymerization of octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capped with hexamethyldisiloxane.

[0047] The preparation method of the F-organosilicon polymer in this embodiment is as follows: 252 parts by weight of octamethylcyclotetrasiloxane, 430 parts by weight of trifluoropropylmethylcyclotrisiloxane and 14 parts by weight of tetramethyltetravinylcyclotetrasiloxane were reacted at 86.0°C for 54 min under an argon atmosphere. Then, 2.3 parts by weight of tetramethylammonium hydroxide initiator and 1.3 parts by weight of tetramethyldivinyldisiloxane were added and reacted at a stirring rate of 280 rpm for 276 min. The temperature was then raised to 148.0°C and maintained under vacuum for 22 h. Finally, the polymer was purified 2.6 times with methanol and vacuum dried at a vacuum degree of 0.6 kPa and a drying temperature of 72.0°C for 10 h to obtain the F-organosilicon polymer.

[0048] The preparation method of the F-crosslinking agent in this embodiment is as follows: Octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane were added to a four-necked reaction flask equipped with a mechanical stirrer and a reflux condenser in a weight ratio of 1.0:2.0. Under an argon atmosphere, the reaction temperature was raised to 90.0°C and maintained for 60 min to reach the initiation temperature. Then, 0.35 parts of tetramethylammonium hydroxide initiator were added to the reactor at a stirring rate of 300.0 rpm and a reaction temperature of 90.0°C to start the reaction. Next, 20.0 parts of tetramethylcyclotetrasiloxane were added dropwise to the reaction solution over 0.5 h using a dropping funnel under vigorous stirring. Subsequently, 10.0 parts of hexamethyldisiloxane end-capping agent were added to the reactor. The reaction was continued at a reaction temperature of 90.0°C for 120 min. After the reaction was completed, the product was heated to 150.0°C and maintained under vacuum for 24.0°C. h removes unreacted reactants and initiators, and finally the product is purified with methanol to eliminate cyclic monomer impurities to obtain F-crosslinking agent.

[0049] The preparation method of the vinyl polyhedral oligomeric silsesquioxane in this embodiment is as follows: 55.0 parts by weight of vinyltrimethoxysilane and 50.0 parts by weight of methyltrimethoxysilane are dissolved in 550.0 parts by weight of acetone solvent. The mixture is stirred at a stirring rate of 320.0 rpm and a reaction temperature of 45.0°C under an argon atmosphere. Then, 80.0 parts by weight of 2.0 mol / L hydrochloric acid solution are added dropwise over 180.0 min to carry out a hydrolysis-condensation reaction. The reaction is then continued at 45.0°C for 38.0 h. The mixture is then filtered and washed 5.0 times each with ethanol, deionized water, and acetone. The mixture is then dried at 65.0°C for 16.0 h. It is then purified by recrystallization using a 1:3 volume ratio dichloromethane-acetone mixed solvent and allowed to stand for 24.0 h. Finally, the mixture is filtered, collected, and dried to obtain the vinyl polyhedral oligomeric silsesquioxane.

[0050] The preparation method of the fluorinated silicone rubber matrix prepolymer in this embodiment is as follows: by weight, 5.0 parts of vinyl polyhedral oligomeric silsesquioxane are dissolved in 32.0 parts of tetrahydrofuran solvent, then 295.0 parts of F-organosilicon polymer and 15.0 parts of F-crosslinking agent are added sequentially and mixed evenly. Then, degassing is carried out for 120 min under a vacuum of 1.0 kPa and a degassing temperature of 100.0°C. Subsequently, 0.15 parts of caster catalyst are added and mixed evenly at a stirring rate of 300 rpm. Finally, the tetrahydrofuran solvent is removed under reduced pressure to obtain the fluorinated silicone rubber matrix prepolymer.

[0051] This embodiment describes a method for preparing a rubber hose material based on fluorosilicone elasticity, comprising the following steps: pre-mixing a fluorosilicone rubber matrix prepolymer with a silica reinforcing agent and a silane coupling agent in a mixer at a mixing temperature of 60°C for 25 min; then sequentially adding a silica reinforcing agent, fluorinated graphite, and nano-calcium fluoride and continuing mixing for 20 min; next, adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing evenly; and finally hot-pressing at a molding temperature of 180°C and a molding pressure of 15 MPa for 20 min to obtain the rubber hose material.

[0052] Example 4: A rubber hose material based on fluorosilicone elasticity, comprising the following raw materials in parts by weight: 100.0 parts of fluorosilicone rubber matrix prepolymer, 45.0 parts of silica reinforcing agent, 8.0 parts of KH-550 silane coupling agent, 25.0 parts of carbon black reinforcing agent, 5.0 parts of N,N-diphenyl-p-phenylenediamine, 15.0 parts of perfluoropolyether, 10.0 parts of fluorinated graphite, 8.0 parts of nano-calcium fluoride, and 3.0 parts of hydroxyl silicone oil;

[0053] In this embodiment, the fluorinated silicone rubber matrix prepolymer is a partially crosslinked polymer prepared by a pre-crosslinking reaction of vinyl polyhedral oligomeric silsesquioxane, F-organosilicon polymer, and F-crosslinking agent under the action of a catalyst; the vinyl polyhedral oligomeric silsesquioxane is prepared by acid-catalyzed hydrolysis and condensation reaction of vinyltrimethoxysilane and methyltrimethoxysilane and then purified by recrystallization; the F-organosilicon polymer is a fluorinated vinyl siloxane copolymer prepared by anionic ring-opening polymerization reaction of octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane, and tetramethyltetravinylcyclotetrasiloxane as the main raw materials; the F-crosslinking agent is a fluorinated functionalized oligomeric siloxane prepared by ring-opening polymerization of octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as initial raw materials under the catalysis of tetramethylammonium hydroxide and end-capped with hexamethyldisiloxane.

[0054] The preparation method of the F-organosilicon polymer in this embodiment is as follows: 260.0 parts by weight of octamethylcyclotetrasiloxane, 450.0 parts by weight of trifluoropropylmethylcyclotrisiloxane and 15.0 parts by weight of tetramethyltetravinylcyclotetrasiloxane were reacted at 90.0°C for 60.0 min under an argon atmosphere. Then, 2.5 parts by weight of tetramethylammonium hydroxide initiator and 1.5 parts by weight of tetramethyldivinyldisiloxane were added and reacted at a stirring rate of 300.0 rpm for 300.0 min. The temperature was then raised to 150.0°C and maintained under vacuum for 24.0 h. Finally, the polymer was purified 3.0 times with methanol 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-organosilicon polymer.

[0055] The preparation method of the F-crosslinking agent in this embodiment is as follows: Octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane were added to a four-necked reaction flask equipped with a mechanical stirrer and a reflux condenser in a weight ratio of 1.0:1.8. Under an argon atmosphere, the reaction temperature was raised to 86.0°C and maintained for 54 minutes to reach the initiation temperature. Then, 0.31 parts of tetramethylammonium hydroxide initiator were added to the reactor at a stirring speed of 280 rpm and a reaction temperature of 88.0°C to start the reaction. The reaction was then carried out using a dropping funnel under vigorous stirring at 0.5... Within h, 16 parts of tetramethylcyclotetrasiloxane were added dropwise to the reaction solution, followed by 8 parts of hexamethyldisiloxane end-capping agent. The reaction was continued at 88.0°C for 108 min with stirring. 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 initiators. Finally, the product was purified with methanol to remove cyclic monomer impurities and obtain F-crosslinking agent.

[0056] The preparation method of the vinyl polyhedral oligomeric silsesquioxane in this embodiment is as follows: 51 parts by weight of vinyltrimethoxysilane and 46 parts by weight of methyltrimethoxysilane are dissolved in 510 parts by weight of acetone solvent. The mixture is stirred at a stirring rate of 304 rpm and a reaction temperature of 41.0°C under an argon atmosphere. Then, 68 parts by weight of 1.4 mol / L hydrochloric acid solution are added dropwise over 156 min to carry out a hydrolysis-condensation reaction. The reaction is then continued at 41.0°C for 35 h. The mixture is then filtered and washed four times each with ethanol, deionized water, and acetone. The mixture is then dried at 61.0°C for 14 h. It is then recrystallized and purified using a 1:3 volume ratio dichloromethane-acetone mixed solvent and allowed to stand for 22 h. Finally, the mixture is filtered, collected, and dried to obtain the vinyl polyhedral oligomeric silsesquioxane.

[0057] The preparation method of the fluorinated silicone rubber matrix prepolymer in this embodiment is as follows: by weight, 4.0 parts of vinyl polyhedral oligomeric silsesquioxane are dissolved in 28 parts of tetrahydrofuran solvent, then 289 parts of F-organosilicon polymer and 11 parts of F-crosslinking agent are added sequentially and mixed evenly. Then, degassing is carried out for 108 min under a vacuum of 0.6 kPa and a degassing temperature of 100.0°C. Subsequently, 0.12 parts of caster catalyst are added and mixed evenly at a stirring rate of 280 rpm. Finally, the tetrahydrofuran solvent is removed under reduced pressure to obtain the fluorinated silicone rubber matrix prepolymer.

[0058] This embodiment describes a method for preparing a rubber hose material based on fluorosilicone elasticity, comprising the following steps: pre-mixing a fluorosilicone rubber matrix prepolymer with a silica reinforcing agent and a silane coupling agent in a mixer at a mixing temperature of 52°C for 21 min; then sequentially adding a silica reinforcing agent, fluorinated graphite, and nano-calcium fluoride and continuing mixing for 16 min; next, adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing evenly; and then hot-pressing at a molding temperature of 172°C and a molding pressure of 12 MPa for 16 min to obtain the rubber hose material.

[0059] Comparative Example 1: Basically the same as Example 1, except that the fluorinated silicone rubber matrix prepolymer is replaced by a common methyl silicone rubber matrix prepolymer, which is prepared by octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane and hydrogen-containing silicone oil crosslinking agent under the action of a platinum catalyst, and does not contain a trifluoropropyl structure.

[0060] Comparative Example 2: It is basically the same as Example 1, except that no vinyl polyhedral oligomeric silsesquioxane is added during the preparation of the fluorinated silicone rubber matrix prepolymer. It is prepared by pre-crosslinking reaction of F-organosilicon polymer and F-crosslinking agent under the action of caster catalyst.

[0061] Comparative Example 3: It is basically the same as Example 1, except that trifluoropropylmethylcyclotrisiloxane is not added in the preparation of F-organosilicon polymer. Instead, 400.0 parts of octamethylcyclotetrasiloxane and 12.0 parts of tetramethyltetravinylcyclotetrasiloxane are used as raw materials for anionic ring-opening polymerization.

[0062] Comparative Example 4: Basically the same as Example 1, except that the reaction temperature during the preparation of the F-organosilicon polymer was 120.0°C.

[0063] Comparative Example 5: Basically the same as Example 1, except that the initial reaction time in the preparation of F-organosilicon polymer was 120.0 min.

[0064] Comparative Example 6: It is basically the same as Example 1, except that the weight ratio of octamethylcyclotetrasiloxane to trifluoropropylmethylcyclotrisiloxane is 1.0:0.8 in the preparation of F-crosslinking agent.

[0065] Comparative Example 7: Basically the same as Example 1, except that hexamethyldisiloxane is not used as the end-capping agent in the preparation of F-crosslinking agent, but octamethylcyclotetrasiloxane is used for end-capping treatment.

[0066] Comparative Example 8: It is basically the same as Example 1, except that the amount of vinyl polyhedral oligomeric silsesquioxane used in the preparation of the fluorinated silicone rubber matrix prepolymer is 8.0 parts.

[0067] Comparative Example 9: It is basically the same as Example 1, except that the degassing temperature during the preparation of the fluorinated silicone rubber matrix prepolymer is 130.0°C, which exceeds the specified temperature of 100.0°C.

[0068] Comparative Example 10: Basically the same as Example 1, except that the weight ratio of silica reinforcing agent to carbon black reinforcing agent is 1:1.

[0069] Comparative Example 11: Basically the same as Example 1, except that fluorinated graphite was not added, and the amounts of other components remained unchanged.

[0070] Comparative Example 12: Basically the same as Example 1, except that the premixing temperature in the preparation method is 80.0°C.

[0071] Performance Testing: Tensile Strength and Elongation at Break Testing: A universal testing machine was used to test the tensile properties of the rubber hose material. The test specimens were dumbbell-shaped and prepared according to standards. The test was conducted in accordance with GB / T 528-2009 standard. The specimen thickness was 2±0.2 mm, the gauge length was 25 mm, the tensile speed was set to 500 mm / min, and the test was conducted at room temperature (23±2°C). The maximum stress value at fracture was recorded as the tensile strength, and the elongation at fracture was also measured. At least five specimens were tested in each group, and the average value was taken.

[0072] Heat resistance aging test: Rubber hose material samples were placed in a high-temperature aging chamber for heat aging tests. The test objects were square samples with dimensions of 15mm × 15mm × 2mm. The test was conducted according to GB / T 3512-2014 standard, with the aging temperature set at 200°C and the aging times set at 168h, 336h, and 504h. The tensile strength and elongation at break of the samples were measured before and after aging, and the performance retention rate was calculated to evaluate the stability and service life of the material under high-temperature conditions.

[0073] Chemical corrosion resistance test: Rubber hose materials were immersed in chemical media with different pH values ​​for corrosion testing. The test specimens were circular, 29 mm in diameter and 2 mm thick. The test followed 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 corrosive media. After immersion at 23±2°C for 168 hours, the specimens were removed, and the rate of change in mass, volume, and mechanical properties were measured to evaluate the material's corrosion resistance.

[0074] Hardness Testing: The hardness of the rubber hose material was measured using a Shore hardness tester. The test object was a flat sample surface with a thickness of not less than 6 mm. The test was conducted according to GB / T 531.1-2008 standard, using a Shore A hardness tester, at room temperature. Five hardness values ​​were measured at different locations on each sample, with a spacing of not less than 6 mm between the test points. The average value was taken as the final result to evaluate the balance between the material's rigidity and flexibility.

[0075] The properties of the rubber hoses in Examples 1-4 and Comparative Examples 1-12 are summarized in Table 1. Replacing the fluorosilicone rubber matrix prepolymer with a common methyl silicone rubber matrix prepolymer results in the material losing the protective effect of the trifluoropropyl structure, significantly reducing its chemical corrosion resistance and heat aging resistance, especially its stability in acidic and alkaline media and organic solvents. Simultaneously, the retention rate of mechanical properties at high temperatures is also significantly weakened. The absence of vinyl-containing polyhedral oligomeric silsesquioxanes causes the material to lose the reinforcing effect of rigid crosslinking nodes, leading to a significant decrease in tensile strength, insufficient overall rigidity, and a decrease in hardness, but with relatively minor effects on heat resistance and corrosion resistance. The absence of trifluoropropylmethylcyclotrisiloxanes during the preparation of F-organosilicon polymers causes the material to lose the protective effect of the fluorinated side chains, significantly reducing its resistance to chemical corrosion and adversely affecting its heat aging resistance, but with relatively limited impact on basic mechanical properties. Excessively high reaction temperatures during the preparation of F-organosilicon polymers can lead to molecular chain degradation or uneven crosslinking, affecting the final material's mechanical and processing properties, but with minimal impact on corrosion resistance. Excessive initial reaction time may lead to increased side reactions or a wider molecular weight distribution, resulting in a slight adverse effect on material properties, but the overall impact is limited. Improper raw material ratios during F-crosslinking agent preparation can affect the molecular structure and reactivity of the crosslinking agent, leading to an unsatisfactory degree of prepolymer crosslinking and ultimately affecting the mechanical properties and network structure stability of the material. Using octamethylcyclotetrasiloxane instead of hexamethyldisiloxane for end-capping can affect the end-group structure and reaction characteristics of the crosslinking agent, resulting in a certain degree of adverse effect on material properties. Excessive use of vinyl-containing polyhedral oligomeric silsesquioxanes can cause excessive rigidity in the material; although hardness and modulus increase, elongation at break decreases significantly, the material becomes brittle, and processing performance is also affected. Excessively high degassing temperatures during prepolymer preparation may cause some components to volatilize or degrade, affecting the performance stability and uniformity of the final material. An improper ratio of silica to carbon black reinforcing agent can affect the synergistic reinforcing effect of the filler, leading to a decrease in tensile strength and potentially affecting filler dispersibility. Without fluorinated graphite, the material loses the physical barrier effect of its layered structure, resulting in decreased resistance to chemical corrosion, particularly a significant reduction in its barrier properties against organic solvents. Excessively high premixing temperatures can affect the material's processing properties and component dispersion uniformity, potentially leading to performance degradation due to localized overheating, but have a relatively small impact on the fundamental properties of the final material.

[0076] Table 1 summarizes the performance of the rubber hoses in Examples 1-4 and Comparative Examples 1-12:

[0077]

[0078]

[0079]

[0080] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that any equivalent structural transformations made under the concept of the present invention and using the contents of the specification and drawings of the present invention should be covered 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 raw materials include the following parts by weight: 100.0 parts of fluorinated silicone rubber matrix prepolymer, 15.0~45.0 parts of silica 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 fluorinated silicone rubber matrix prepolymer is a partially crosslinked polymer prepared by a pre-crosslinking reaction of vinyl polyhedral oligomeric silsesquioxane, F-organosilicon polymer, and F-crosslinking agent under the action of a catalyst; the vinyl polyhedral oligomeric silsesquioxane is prepared by acid-catalyzed hydrolysis condensation reaction of vinyltrimethoxysilane and methyltrimethoxysilane followed by recrystallization purification; the F-organosilicon... The silicone polymer is a fluorinated vinyl siloxane copolymer prepared by anionic ring-opening polymerization of octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane, and tetramethyltetravinylcyclotetrasiloxane as main raw materials. The F-crosslinking agent is a fluorinated oligomeric siloxane with fluorinated functional end groups, prepared by ring-opening polymerization of octamethylcyclotetrasiloxane and trifluoropropylmethylcyclotrisiloxane as initial raw materials under the catalysis of tetramethylammonium hydroxide, and end-capped with hexamethyldisiloxane. The preparation method of the F-organosilicon polymer is as follows: 240.0~260.0 parts by weight of octamethylcyclotetrasiloxane, 400.0~450.0 parts by weight of trifluoropropylmethylcyclotrisiloxane, and 12.0~15.0 parts by weight of tetramethyltetravinylcyclotetrasiloxane are reacted under an argon atmosphere at a reaction temperature of 80.0~90.0°C, maintained at 45.0~60.0°C. Then, 2.1–2.5 parts of tetramethylammonium hydroxide initiator and 1.1–1.5 parts of tetramethyldivinyldisiloxane were added, and the mixture was reacted at a stirring rate of 250.0–300.0 rpm for 240.0–300.0 min. The temperature was then raised to 145.0–150.0°C and maintained under vacuum for 20.0–24.0 h. Finally, the mixture was purified with methanol 2.0–3.0 times and vacuum dried at a vacuum degree of 0.1–1.0 kPa and a drying temperature of 60.0–80.0°C for 8.0–12.0 h. h yields F-organosilicon polymer; 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. Under argon atmosphere protection, the reaction temperature is raised to 80~90.0°C and maintained for 45~60 min to reach the initiation temperature. Then, under stirring speed of 250~300.0 rpm and reaction temperature of 85~90.0°C, 0.25~0.35 parts of tetramethylammonium hydroxide initiator are added to the reactor to start the reaction. Then, using a dropping funnel under vigorous stirring, 10.0~20 parts of the initiator are added over 0.5 h.0 parts of tetramethylcyclotetrasiloxane were added dropwise to the reaction solution, followed by 5.0-10.0 parts of hexamethyldisiloxane end-capping agent. The reaction was continued with stirring at 85-90.0°C for 90-120 min. After the reaction was completed, the product was heated to 145-150.0°C and maintained under vacuum for 20-24.0 h to remove unreacted reactants and initiators. Finally, the product was purified with methanol to eliminate cyclic monomer impurities to obtain F-crosslinking agent. The preparation method of the fluorinated silicone rubber matrix prepolymer is as follows: 2.5-5.0 parts of vinyl polyhedral oligomeric silsesquioxane were dissolved in 22.0-32.0 parts of tetrahydrofuran solvent, and then 280.0-295.0 parts of F-organosilicon polymer and 5.0-15.0 parts of F-crosslinking agent were added sequentially and mixed evenly. Then, the mixture was stirred under vacuum of 0.1-1.0 degrees. Degassing is performed at kPa and a degassing temperature of 100.0°C for 90-120 min. Then, 0.1-0.15 parts of a caster catalyst are added and mixed uniformly at a stirring rate of 250-300 rpm. Finally, the tetrahydrofuran solvent is removed under reduced pressure to obtain a fluorinated silicone rubber matrix prepolymer. The weight ratio of the silica reinforcing agent to the carbon black reinforcing agent is 2:1-4:

1. The preparation method of the fluorinated silicone elastic rubber hose material includes the following steps: pre-mixing the fluorinated silicone rubber matrix prepolymer with silica reinforcing agent and silane coupling agent in a mixer at a mixing temperature of 40-60°C for 15-25 min; then, sequentially adding carbon black reinforcing agent, fluorinated graphite, and nano-calcium fluoride and continuing mixing for 10-20 min; next, adding a fluorinated plasticizer, a silicone flow modifier, and an antioxidant and mixing uniformly; then, molding at a molding temperature of 160-180°C and a molding pressure of 8-15 kPa. Rubber hose material is obtained by hot pressing at MPa for 10-20 minutes.

2. The rubber hose material based on fluorosilicone elasticity as described in 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; and the silicone flow modifier is hydroxyl silicone oil.

3. The fluorosilicone elastic rubber hose material as described in claim 1, wherein the rubber hose has a service temperature range of -50~250°C, a tensile strength ≥15 MPa, an elongation at break ≥200%, and can withstand corrosion from media with a pH value of 1~14.

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