A perfluoroether rubber composite and a method for producing the same

Abstract

The present application relates to the technical field of perfluoroether rubber, and particularly relates to a perfluoroether rubber composite material and a preparation method thereof.The perfluoroether rubber composite material provided by the present application comprises modified perfluoroether rubber and a matrix material, and the method for obtaining the modified perfluoroether rubber comprises sequentially performing plasma activation and surface modification treatment on the perfluoroether rubber, and the surface modification method comprises at least one of coupling agent modification and nano filler coating.The present application obtains modified perfluoroether rubber by treating the perfluoroether rubber, reduces the interfacial energy of the perfluoroether rubber, and effectively improves the compatibility of the perfluoroether rubber and the matrix material;the present application forms a uniform nanoscale rough structure and active sites on the surface of the perfluoroether rubber through plasma activation, and then performs surface modification on the activated perfluoroether rubber by using coupling agent surface modification or nano filler coating, thereby improving the processing stability and mechanical properties of the perfluoroether rubber composite material.

Description

Technical Field

[0001] This invention relates to the field of perfluoroether rubber technology, and specifically to a perfluoroether rubber composite material and its preparation method. Background Technology

[0002] Perfluoroelastomer (FFKM) is widely used in semiconductor manufacturing, aerospace, and chemical equipment due to its excellent high-temperature resistance, chemical corrosion resistance, and extremely low volatility. However, the high chemical stability of FFKM makes it difficult to uniformly compound with conventional polymer matrices, resulting in certain limitations in its processing performance, mechanical strength, and the stability of the final product.

[0003] With the rise of the semiconductor industry, perfluoroelastomer (PFE) rubber, as a key material in semiconductor equipment, has its performance directly related to the reliability, yield, and lifespan of semiconductor equipment. However, the current performance of PFE rubber cannot meet the above requirements, resulting in high processing difficulty and unstable material mechanical properties.

[0004] Furthermore, while the excellent chemical stability of perfluoroelastomers endows materials with superior properties, it also presents challenges for their recycling after disposal. Currently used methods such as solvent dissolution and high-temperature incineration suffer from low resource utilization and high energy consumption, and the actual recycling results are insufficient to meet the requirements of sustainable development. This current state of affairs not only wastes resources but also falls short of green environmental protection principles. Summary of the Invention

[0005] Therefore, in order to overcome the defect of poor compatibility between perfluoroether rubber and high-performance polymers in the prior art, the present invention provides a perfluoroether rubber composite material, its preparation method and application.

[0006] Meanwhile, in order to address the shortcomings of existing technologies that cannot fully recycle waste perfluoroether rubber, this invention provides a perfluoroether rubber composite material, its preparation method, and its application.

[0007] On one hand, the present invention provides a perfluoroether rubber composite material, comprising modified perfluoroether rubber and a matrix material. The method for obtaining the modified perfluoroether rubber includes sequentially subjecting the perfluoroether rubber to plasma activation and surface modification treatment. The surface modification method includes at least one of coupling agent modification and nanofiller coating.

[0008] In some embodiments, the content of the modified perfluoroether rubber is 5 wt% to 30 wt% based on the mass of the perfluoroether rubber composite material.

[0009] In some embodiments, the matrix material comprises a polymer. Preferably, the polymer has properties such as high mechanical strength, high temperature resistance, and chemical resistance.

[0010] In some embodiments, the matrix material includes at least one of polytetrafluoroethylene, polyetheretherketone, or polyphenylene sulfide.

[0011] In some embodiments, the plasma includes argon plasma, preferably argon plasma and oxygen plasma, wherein the argon plasma and oxygen plasma flow rate ratio is 30-100:1-5.

[0012] In some embodiments, the coupling agent includes at least one of a silane coupling agent or a titanate coupling agent.

[0013] In some embodiments, the nanofiller includes at least one of silicon dioxide or aluminum oxide, and the particle size of the nanofiller is 10 nm to 100 nm.

[0014] In some embodiments, the coupling agent content is 3wt%-8wt% based on the mass of the modified perfluoroether rubber.

[0015] In some embodiments, the coating amount of the nanofiller is 1wt%-5wt% based on the mass of the modified perfluoroether rubber.

[0016] In some embodiments, the silane coupling agent includes at least one of a fluorinated silane coupling agent and an aminosilane coupling agent. Preferably, the coupling agent and the matrix material are configured as follows: when the matrix material is polytetrafluoroethylene, the coupling agent is a fluorinated silane coupling agent; when the matrix material is polyetheretherketone, the coupling agent is an aminosilane coupling agent; when the matrix material is polyphenylene sulfide, the coupling agent is a titanate coupling agent.

[0017] In some embodiments, the fluorinated silane coupling agent includes at least one of perfluoroalkyltrimethoxysilane, perfluoroalkylethoxysilane, fluorinated aromatic silane, and partially fluorinated alkylsilane; more preferably, the aminosilane coupling agent includes at least one of γ-aminopropyltriethoxysilane, diaminosilane, phenylaminosilane, and long-chain alkylaminosilane.

[0018] On the other hand, the present invention provides a method for preparing a perfluoroether rubber composite material, comprising the following steps: mixing modified perfluoroether rubber and matrix material to carry out a densification reaction; obtaining the perfluoroether rubber composite material through a molding process; wherein the densification reaction includes at least one of melting or sintering.

[0019] In some embodiments, the preparation method of the perfluoroether rubber composite material further includes a post-treatment step, which includes annealing and heat treatment. The annealing temperature is 250℃-280℃ for 2-4 hours, and the heat treatment temperature is 290℃-310℃ for 8-12 hours. This invention controls the annealing temperature at 250-280℃ and sets the annealing time to 2-4 hours to release internal stress and improve dimensional stability. Simultaneously, a secondary heat treatment step is included, with the secondary heat treatment temperature controlled at 290-310℃ and the heat treatment time at 8-12 hours to improve chemical corrosion resistance and thermal stability.

[0020] In some embodiments, when the densification reaction is a melting process, the melting temperature is 320°C-380°C and the melting time is 0.1-1h.

[0021] In some embodiments, when the densification reaction is sintering, the sintering temperature is 360°C-400°C and the sintering time is 2h-5h.

[0022] In some embodiments, the preparation method of the modified perfluoroether rubber includes the following steps: S1, the perfluoroether rubber is subjected to plasma activation treatment to obtain an intermediate; S2, the intermediate obtained in step S1 and the coupling agent are subjected to heat treatment to obtain the modified perfluoroether rubber; or, the intermediate obtained in step S1 is coated with nanofiller by sol-gel method or ultrasonic dispersion method.

[0023] In some embodiments, the preparation method of the modified perfluoroether rubber includes the following steps: S1, the perfluoroether rubber is subjected to plasma treatment to obtain an intermediate; S2, the intermediate and coupling agent are subjected to heat treatment to obtain the modified perfluoroether rubber; S3, the modified perfluoroether rubber obtained in step S2 is coated with nanofillers using sol-gel method or ultrasonic dispersion method.

[0024] In some embodiments, the step of obtaining an intermediate by plasma treatment of perfluoroether rubber includes: the plasma modification power is 100W-300W, the modification treatment time is 1min-10min, the internal pressure of the plasma modification treatment is 5Pa-50Pa, and the plasma flow rate is 30sccm-110sccm.

[0025] In some embodiments, the specific steps of heat-treating the intermediate and coupling agent include: under stirring, the heat treatment temperature is 60°C-80°C, the stirring speed is 200rpm-400rpm, and the treatment time is 2h-4h.

[0026] In some embodiments, the sol-gel method is used to coat intermediates or modified perfluoroether rubber with nanofillers. Specifically, this includes the following steps: immersing the intermediate or modified perfluoroether rubber in a sol for 2-6 hours under stirring at a speed of 200-400 rpm and a temperature of 30-50°C. After immersion, the mixture is aged, dried, and then heat-treated in an inert atmosphere for 2-3 hours at a temperature of 250-300°C. Preferably, the sol preparation method includes stirring the materials at 40-60°C and 400-600 rpm for 2-4 hours in a molar ratio of tetraethyl orthosilicate, anhydrous ethanol, deionized water, and hydrochloric acid of 1:4-6:1.5-2.5:0.05-0.2. More preferably, the specific steps of the sol-gel method include: (1) ultrasonically cleaning the perfluoroether rubber particles in anhydrous ethanol for 30-60 minutes to remove surface contaminants; (2) preparing a nanofiller precursor sol: mixing tetraethyl orthosilicate, anhydrous ethanol, deionized water and hydrochloric acid in a molar ratio of 1:4-6:1.5-2.5:0.05-0.2, and stirring at 400rpm-600rpm for 2-4 hours at 40℃-60℃ to form a uniform and transparent sol. (3) Immerse the cleaned perfluoroether rubber particles in the sol and soak them for 2-6 hours at 30℃-50℃ and 200rpm-400rpm stirring conditions; (4) Take out the soaked particles, let them stand at room temperature for 24-48 hours, and then dry them by gradient temperature increase: dry at 60℃ for 1 hour and at 120℃ for 1 hour; (5) Finally, heat-treat them at 250℃-300℃ for 2-3 hours under nitrogen protection to form a dense nanofiller coating layer.

[0027] In some embodiments, the mass ratio of the intermediate or modified perfluoroether rubber to tetraethyl orthosilicate is 100:5-15.

[0028] In some embodiments, ultrasonic dispersion is used to coat intermediates or modified perfluoroether rubber with nanofillers. Specifically, this involves the following steps: ultrasonically treating the intermediates or modified perfluoroether rubber in a sol at 300W-600W power for 30-60 minutes, with the temperature controlled between 30℃ and 50℃. This invention optimizes the dispersion and loading effect of nano-silica through ultrasonic treatment. High-frequency oscillation effectively breaks down the agglomerates of the nano-silica precursor, achieving monodispersity in the sol. The microjets generated by ultrasound enhance the penetration of the silica sol into the micropores and etched structures of the FFKM surface, improving the bonding strength of the coating layer.

[0029] In some embodiments, the perfluoroether rubber is obtained by low-temperature treatment and pulverization of perfluoroether rubber. The low-temperature treatment temperature is -196℃ to -50℃, the treatment time is 30min to 60min, and the particle size of the pulverized perfluoroether rubber is 5μm to 50μm. The perfluoroether rubber is waste perfluoroether rubber. Perfluoroelastomer (PFE) rubber exhibits high elasticity at room temperature but requires significant energy to pulverize. High-speed shearing generates heat that can lead to localized incorporation and the formation of irregular particles. This invention utilizes low-temperature pulverization technology, cooling PFE rubber to below its glass transition temperature (Tg≈-10℃) to transform the material from a highly elastic state to a brittle state. At this point, the molecular chain mobility decreases, making it more easily broken under external force, thus obtaining microparticles with uniform particle size (5μm-50μm). This improves the uniformity of subsequent mixing with the matrix (e.g., PTFE / PEEK). Particles larger than 50μm can cause interfacial stress concentration, reducing the mechanical properties of the composite material (e.g., tensile strength, elongation at break) and making it prone to sedimentation and uneven dispersion during processing. Particles smaller than 5μm have increased specific surface area, leading to enhanced van der Waals forces and a tendency to agglomerate, resulting in decreased processing fluidity, difficulty in melt blending, and ultimately, defects in the final product.

[0030] The technical solution of this invention has the following advantages:

[0031] 1. This invention provides a perfluoroether rubber composite material, comprising modified perfluoroether rubber and a matrix material. The method for obtaining the modified perfluoroether rubber includes sequentially subjecting the perfluoroether rubber to plasma activation and surface modification treatments. The surface modification method includes at least one of coupling agent modification and nanofiller coating. This invention obtains modified perfluoroether rubber by plasma activation and surface modification treatment, reducing the interfacial energy of the perfluoroether rubber and effectively improving the compatibility between the perfluoroether rubber and the matrix material. Specifically, this invention forms a uniform nanoscale rough structure and active sites on the surface of the perfluoroether rubber through plasma activation, and then performs surface modification of the activated perfluoroether rubber using coupling agent surface modification or nanofiller coating. This improves the dispersibility of the perfluoroether rubber in the matrix material and enhances the processing stability and mechanical properties of the perfluoroether rubber material.

[0032] 2. This invention provides a perfluoroether rubber composite material, wherein the matrix material is polytetrafluoroethylene (PTFE), and the coupling agent is a fluorinated silane coupling agent; the matrix material is polyetheretherketone (PEEK), and the coupling agent is an aminosilane coupling agent; the matrix material is polyphenylene sulfide (PPS), and the coupling agent is a titanate coupling agent. When the matrix material is PTFE, using a fluorinated silane coupling agent allows the fluorine segments of the coupling agent to have a similar chemical structure to PTFE, which can more effectively reduce interfacial energy differences and improve dispersibility. When the matrix material is PPEK, using an aminosilane coupling agent allows the amino (-NH) groups in the coupling agent to form hydrogen bonds with the ketone groups of PPEK, which can enhance interfacial bonding and effectively reduce interfacial energy. When the matrix material is PPEK, using a titanate coupling agent allows the chelating effect of the coupling agent to bond with the sulfide groups of PPEK, reducing interfacial defects and effectively reducing interfacial energy.

[0033] 3. This invention provides a method for preparing a perfluoroether rubber composite material, which involves mixing modified perfluoroether rubber and a matrix material, and then carrying out a densification reaction to obtain the perfluoroether rubber composite material. This invention combines modified perfluoroether rubber and a matrix material to form a perfluoroether rubber composite material; the steps are simple and the processing performance is stable.

[0034] 4. This invention provides a method for preparing a perfluoroether rubber composite material, wherein the method for preparing the modified perfluoroether rubber includes the following steps: S1, the perfluoroether rubber is subjected to plasma treatment to obtain an intermediate; S2, the intermediate and a coupling agent are subjected to heat treatment to obtain a modified perfluoroether rubber; S3, the modified perfluoroether rubber obtained in step S2 is coated with nanofillers using a sol-gel method or an ultrasonic dispersion method. This invention employs a series of steps: plasma treatment, coupling agent modification, and nanofiller coating, to obtain modified perfluoroether rubber. First, plasma treatment introduces free radical active sites and polar groups onto the surface of the perfluoroether rubber, enhancing its surface energy and interfacial reactivity. Subsequently, coupling agent modification utilizes the active groups in the coupling agent molecules to form chemical bonds with the plasma-treated rubber surface, while the other end of the coupling agent is compatible with the matrix material, thereby reducing the interfacial energy difference and achieving a uniform interfacial transition through chemical bond bridging. Finally, nanofiller coating constructs a uniform nano-reinforcing layer on the rubber surface, improving not only interfacial compatibility but also enhancing the mechanical properties of the composite material through the rigidity enhancement and stress dispersion effects of nanoparticles. This organic combination of processes synergistically improves interfacial compatibility from three dimensions: physical morphology, chemical bonding, and nano-reinforcement, enabling the modified perfluoroether rubber to be uniformly dispersed in the matrix material, thus significantly improving the processing stability and mechanical properties of the composite material. This multi-stage modification process achieves efficient composite and performance enhancement of perfluoroether rubber and matrix materials through a synergistic mechanism of "surface activation-interface optimization-nano-reinforcement."

[0035] 5. This invention provides a method for preparing a perfluoroether rubber composite material, which employs plasma modification of the perfluoroether rubber. The plasma includes at least one of argon, oxygen, and ammonia. The plasma modification power is 100W-250W, the modification time is 5min-15min, and the plasma flow rate is 30sccm-60sccm. Adjusting the plasma parameters significantly affects the modification effect of the perfluoroether rubber. The researchers of this invention have found that appropriately increasing the power (e.g., 200W) and extending the treatment time (10 minutes) may enhance surface etching and the introduction of chemical groups, increasing the bonding strength between the material and the matrix by more than 50%. However, if the power is too high (>250W) or the time is too long (>15 minutes), it may damage the rubber's structure, leading to a 30% decrease in chemical resistance. The choice of gas type is particularly crucial: mixing oxygen and ammonia may unexpectedly generate nitrogen-oxygen complex groups, significantly enhancing interfacial reactivity, but may also accelerate the material's damp-heat aging due to byproducts. Furthermore, excessively low gas flow rates (<30 sccm) may result in "patchy" defects due to uneven plasma distribution, while turbulence effects at specific flow rates (e.g., 40 sccm) may impart superhydrophobic properties (contact angle >150°). Therefore, after treatment with plasma containing at least one of argon, oxygen, and ammonia, at a power of 100W-250W, a treatment time of 5-15 minutes, and a plasma flow rate of 30-60 sccm, the surface of perfluoroether rubber can be effectively modified, and its chemical properties can be enhanced. Detailed Implementation

[0036] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0037] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0038] The perfluoroether rubber products used in the embodiments and comparative examples of this invention mainly come from: retired sealing rings from high-cleanliness environments such as semiconductor production lines, such as O-rings and valve seals; and unqualified products produced by manufacturers of perfluoroether rubber products, mainly rubber rings with only appearance problems such as defects or wire diameter not meeting requirements as determined during final inspection.

[0039] Example 1

[0040] This embodiment provides a method for preparing a perfluoroether rubber composite material, the specific steps and parameters of which are as follows:

[0041] (1) The perfluoroether rubber was treated in a liquid nitrogen environment at -196℃ for 45 minutes and then pulverized by a high-speed ball mill until the particle size of the perfluoroether rubber was 20μm-50μm. In this embodiment, the perfluoroether rubber was a waste perfluoroether rubber product.

[0042] (2) The pulverized perfluoroether rubber was activated by plasma under the conditions of argon plasma flow rate of 50 sccm, chamber pressure of 30 Pa, and power of 180 W for 10 min.

[0043] (3) The activated perfluoroether rubber and γ-aminopropyltriethoxysilane (APTES) coupling agent were stirred at 350 rpm for 4 h at 70 °C to obtain modified perfluoroether rubber. The amount of coupling agent was 3 wt% of the mass of the activated perfluoroether rubber.

[0044] (4) According to the mass ratio of the matrix material and the modified perfluoroether rubber being 85:15, the matrix material polyetheretherketone (brand: 450G) and the mixture are mixed in a twin-screw extruder and extruded through the twin-screw extruder. The twin-screw extruder has a screw length-to-diameter ratio of 40, and the extrusion temperature is set to 350℃ (feed) → 365℃ (middle section) → 380℃ (end), the screw speed is 120 rpm, and the mixing time is 8 min to obtain the extrudate.

[0045] The extrudate was cooled with water and then pelletized to obtain 2mm composite particles;

[0046] The composite particles were injection molded at 300℃, with the mold temperature at 160℃, the pressure at 10MPa, and the holding time at 5min.

[0047] The molded composite material was subjected to annealing, cooling, and heat treatment sequentially to obtain a perfluoroether rubber composite material. The annealing temperature was 280℃ and the annealing time was 2h. After annealing, the temperature was cooled to 180℃ at a rate not exceeding 5℃ / min and held for 0.5h. Subsequently, heat treatment was performed at a temperature of 300℃ for 10h.

[0048] Example 2

[0049] This embodiment provides a method for preparing a perfluoroether rubber composite material, the specific steps and parameters of which are as follows:

[0050] (1) The perfluoroether rubber was treated in a liquid nitrogen environment at -196℃ for 45 minutes and then pulverized by a high-speed ball mill until the particle size of the perfluoroether rubber was 20μm-50μm.

[0051] (2) The pulverized perfluoroether rubber was activated by plasma under the conditions of argon plasma flow rate of 50 sccm, chamber pressure of 30 Pa, and power of 180 W for 10 min.

[0052] (3) The plasma-modified perfluoroether rubber is processed by the sol-gel method to obtain modified perfluoroether rubber, specifically including the following steps:

[0053] 3.1 The plasma-modified perfluoroether rubber was immersed in anhydrous ethanol and ultrasonically cleaned for 40 minutes at 300W power.

[0054] 3.2 Preparation of nano silica precursor sol: Tetraethyl orthosilicate, anhydrous ethanol, deionized water and hydrochloric acid were mixed in a molar ratio of 1:5:2:0.1 and stirred at 500 rpm for 3 hours at 50°C to form a uniform and transparent sol.

[0055] 3.3 The cleaned perfluoroether rubber was immersed in the sol and impregnated for 4 hours at 40°C and 300 rpm with stirring. The mass ratio of perfluoroether rubber to tetraethyl orthosilicate was 100:10.

[0056] 3.4 Remove the impregnated granules, let them stand at room temperature for 36 hours, and then dry them using a gradient temperature increase: dry at 60℃ for 1 hour and at 120℃ for 1 hour.

[0057] 3.5 Finally, under nitrogen protection, the mixture is heat-treated at 280℃ for 2.5 hours to form a dense silica coating layer with a thickness of 150-250nm, thus obtaining the modified perfluoroether rubber.

[0058] The mass fraction of nano-sized silica is 3.0 wt% based on the total amount of modified perfluoroether rubber.

[0059] (4) According to the mass ratio of matrix material to mixture of 85:15, the matrix material is polyetheretherketone (brand name: 450G) and modified perfluoroether rubber were mixed in a twin-screw extruder and extruded through the twin-screw extruder. The twin-screw extruder had a screw length-to-diameter ratio of 40, and the extrusion temperature was set to 350℃ (feed) → 365℃ (middle section) → 380℃ (end), the screw speed was 120 rpm, and the mixing time was 8 min to obtain the extrudate.

[0060] The extrudate was cooled with water and then pelletized to obtain 2mm composite particles;

[0061] The composite particles were injection molded at 300℃, with the mold temperature at 160℃, the pressure at 10MPa, and the holding time at 5min.

[0062] The molded composite material was subjected to annealing, cooling, and heat treatment sequentially to obtain a perfluoroether rubber composite material. The annealing temperature was 280℃ and the annealing time was 2h. After annealing, the temperature was cooled to 180℃ at a rate not exceeding 5℃ / min and held for 0.5h. Subsequently, heat treatment was performed at a temperature of 300℃ for 10h.

[0063] Example 3

[0064] This embodiment provides a method for preparing a perfluoroether rubber composite material, the specific steps and parameters of which are as follows:

[0065] (1) The perfluoroether rubber was treated in a liquid nitrogen environment at -196℃ for 45 minutes and then pulverized by a high-speed ball mill until the particle size of the perfluoroether rubber was 20μm-50μm. In this embodiment, the perfluoroether rubber was a waste perfluoroether rubber product.

[0066] (2) The pulverized perfluoroether rubber was activated by plasma under the conditions of argon plasma flow rate of 50 sccm, chamber pressure of 30 Pa, and power of 180 W for 10 min.

[0067] (3) The activated perfluoroether rubber and γ-aminopropyltriethoxysilane (APTES) coupling agent were stirred at 350 rpm for 4 h at 70 °C to obtain a mixture, wherein the amount of coupling agent was 3 wt% of the mass of the activated perfluoroether rubber.

[0068] (4) The surface-modified perfluoroether rubber after coupling agent surface treatment is processed by sol-gel method to obtain modified perfluoroether rubber, specifically including the following steps:

[0069] 4.1 The perfluoroether rubber after surface modification with coupling agent was immersed in anhydrous ethanol and ultrasonically cleaned for 40 minutes at 300W power.

[0070] 4.2 Preparation of nano silica precursor sol: Tetraethyl orthosilicate, anhydrous ethanol, deionized water and hydrochloric acid were mixed in a molar ratio of 1:5:2:0.1 and stirred at 500 rpm for 3 hours at 50°C to form a uniform and transparent sol.

[0071] 4.3 The perfluoroether rubber after surface modification with coupling agent was immersed in sol and impregnated for 4 hours at 40°C and 300 rpm with stirring. The mass ratio of the perfluoroether rubber after surface modification with coupling agent to tetraethyl orthosilicate was 100:10.

[0072] 4.4 Remove the impregnated granules, let them stand at room temperature for 36 hours, and then dry them using a gradient temperature increase: dry at 60℃ for 1 hour and at 120℃ for 1 hour.

[0073] 4.5 Finally, under nitrogen protection, the mixture is heat-treated at 280℃ for 2.5 hours to form a dense silica coating layer with a thickness of 150-250nm;

[0074] The mass fraction of nano-sized silica is 3.0 wt% based on the total amount of modified perfluoroether rubber.

[0075] (5) According to the mass ratio of the matrix material and the modified perfluoroether rubber being 85:15, the matrix material polyetheretherketone (brand name: 450G) and the mixture are mixed in a twin-screw extruder and extruded through the twin-screw extruder. The twin-screw extruder has a screw length-to-diameter ratio of 40, and the extrusion temperature is set to 350℃ (feed) → 365℃ (middle section) → 380℃ (end), the screw speed is 120 rpm, and the mixing time is 8 min to obtain the extrudate.

[0076] The extrudate was cooled with water and then pelletized to obtain 2mm composite particles;

[0077] The composite particles were injection molded at 300℃, with the mold temperature at 160℃, the pressure at 10MPa, and the holding time at 5min.

[0078] The molded composite material was subjected to annealing, cooling, and heat treatment sequentially to obtain a perfluoroether rubber composite material. The annealing temperature was 280℃ and the annealing time was 2h. After annealing, the temperature was cooled to 180℃ at a rate not exceeding 5℃ / min and held for 0.5h. Subsequently, heat treatment was performed at a temperature of 300℃ for 10h.

[0079] Example 4

[0080] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3. The difference is that an equal mass of polyphenylene sulfide (brand name: DIC Corporation FZ-210) is used to replace the polyether ether ketone in step (5).

[0081] Example 5

[0082] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3, except that an equal mass of polytetrafluoroethylene (brand name: DuPont) is used. PTFE 7A can replace the polyetheretherketone in step (5). The specific steps are as follows:

[0083] (5) According to the mass ratio of the matrix material and the modified perfluoroether rubber of 85:15, the matrix material polytetrafluoroethylene (brand name: DuPont) is added. PTFE 7A and modified perfluoroether rubber were mixed in a high-energy mixer at 600 rpm for 30 minutes to obtain a mixture.

[0084] Subsequently, the mixture was molded at a molding temperature of 350℃, a pressure of 15MPa, and a holding time of 10min.

[0085] The shaped mixture was sintered at 390℃ for 6 hours, then cooled to 280℃ at a rate of 3℃ / min and annealed for 2 hours. It was then slowly cooled to 180℃ and held for 0.5 hours, and finally heat-treated at 300℃ for 10 hours under nitrogen protection throughout. This process resulted in a SiO2-PEEK interfacial shear strength of 35 MPa and an increase in heat distortion temperature of 8℃, yielding a perfluoroether rubber composite material.

[0086] Example 6

[0087] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 4, except that an equal mass of titanate coupling agent (model: KR-TTS (manufacturer: Kenrich Petrochemicals) replaces γ-aminopropyltriethoxysilane in step (3).

[0088] Example 7

[0089] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 5, except that an equal mass of perfluoroalkyltrimethoxysilane is used to replace γ-aminopropyltriethoxysilane in step (3).

[0090] Example 8

[0091] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3. The difference is that in steps (4)-4.3, the mass ratio of the perfluoroether rubber after surface modification treatment with coupling agent to tetraethyl orthosilicate is 100:15; and the mass fraction of nano-sized silica in the formed modified perfluoroether rubber is 4.5wt%.

[0092] Example 9

[0093] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3. The difference is that in steps (4)-4.3, the mass ratio of the perfluoroether rubber after surface modification treatment with coupling agent to tetraethyl orthosilicate is 100:5; and the mass fraction of nano-sized silica in the formed modified perfluoroether rubber is 1.5wt%.

[0094] Example 10

[0095] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3, except that an equimolar amount of aluminum isopropoxide is used to replace tetraethyl orthosilicate in step (4)-4.2.

[0096] Example 11

[0097] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3, except that the amount of coupling agent used in step (3) is 5 wt% of the mass of the activated perfluoroether rubber.

[0098] Example 12

[0099] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3, except that the amount of coupling agent used in step (3) is 8 wt% of the mass of the activated perfluoroether rubber.

[0100] Example 13

[0101] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3, except that the mass ratio of the matrix material and the modified perfluoroether rubber in step (5) is 95:5.

[0102] Example 14

[0103] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3, except that the mass ratio of the matrix material and the modified perfluoroether rubber in step (5) is 9:1.

[0104] Example 15

[0105] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3, except that the mass ratio of the matrix material and the modified perfluoroether rubber in step (5) is 8:2.

[0106] Example 16

[0107] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3, except that the mass ratio of the matrix material and the modified perfluoroether rubber in step (5) is 7:3.

[0108] Example 17

[0109] This embodiment provides a method for preparing a perfluoroether rubber composite material, the specific steps and parameters of which are as follows:

[0110] (1) The perfluoroether rubber was treated in a liquid nitrogen environment at -85℃ for 60 minutes and then pulverized by a high-speed ball mill until the particle size of the perfluoroether rubber was 5μm-30μm. In this embodiment, the perfluoroether rubber was a waste perfluoroether rubber product.

[0111] (2) The pulverized perfluoroether rubber was activated by plasma under the conditions of argon plasma flow rate of 30 sccm, chamber pressure of 30 Pa, and power of 100 W for 15 min.

[0112] (3) The activated perfluoroether rubber and γ-aminopropyltriethoxysilane (APTES) coupling agent were stirred at 400 rpm for 2 h at 60 °C to obtain a mixture, wherein the amount of coupling agent was 3 wt% of the mass of the activated perfluoroether rubber.

[0113] (4) The surface-modified perfluoroether rubber after coupling agent surface treatment is processed by sol-gel method to obtain modified perfluoroether rubber, specifically including the following steps:

[0114] 4.1 The perfluoroether rubber after surface modification with coupling agent was immersed in anhydrous ethanol and ultrasonically cleaned for 40 minutes at 300W power.

[0115] 4.2 Preparation of nano silica precursor sol: Tetraethyl orthosilicate, anhydrous ethanol, deionized water and hydrochloric acid were mixed in a molar ratio of 1:4:1.5:0.2 and stirred at 400 rpm for 4 hours at 60°C to form a uniform and transparent sol.

[0116] 4.3 The perfluoroether rubber after surface modification with coupling agent was immersed in sol and impregnated for 6 hours under stirring conditions of 30℃ and 200rpm. The mass ratio of the perfluoroether rubber after surface modification with coupling agent to tetraethyl orthosilicate was 100:10.

[0117] 4.4 Remove the impregnated granules, let them stand at room temperature for 36 hours, and then dry them using a gradient temperature increase: dry at 60℃ for 1 hour and at 120℃ for 1 hour.

[0118] 4.5 Finally, under nitrogen protection, the mixture is heat-treated at 250℃ for 3 hours to form a dense silica coating layer with a thickness of 150-250nm.

[0119] The mass fraction of nano-sized silica is 3.0 wt% based on the total amount of modified perfluoroether rubber.

[0120] (5) According to the mass ratio of the matrix material and the modified perfluoroether rubber being 85:15, the matrix material polyetheretherketone (brand name: 450G) and the mixture are mixed in a twin-screw extruder and extruded through the twin-screw extruder. The twin-screw extruder has a screw length-to-diameter ratio of 40, and the extrusion temperature is set to 350℃ (feed) → 365℃ (middle section) → 380℃ (end), the screw speed is 120 rpm, and the mixing time is 8 min to obtain the extrudate.

[0121] The extrudate was cooled with water and then pelletized to obtain 2mm composite particles;

[0122] The composite particles were injection molded at 300℃, with the mold temperature at 160℃, the pressure at 10MPa, and the holding time at 5min.

[0123] The molded composite material was subjected to annealing, cooling, and heat treatment sequentially to obtain a perfluoroether rubber composite material. The annealing temperature was 250℃ and the annealing time was 4 hours. After annealing, the temperature was cooled to 180℃ at a rate not exceeding 5℃ / min and held for 0.5 hours. Subsequently, heat treatment was performed at a temperature of 290℃ for 12 hours.

[0124] Example 18

[0125] This embodiment provides a method for preparing a perfluoroether rubber composite material, the specific steps and parameters of which are as follows:

[0126] (1) The perfluoroether rubber was treated in a liquid nitrogen environment at -120℃ for 30 minutes and then pulverized by a high-speed ball mill until the particle size of the perfluoroether rubber was 5μm-20μm. In this embodiment, the perfluoroether rubber was a waste perfluoroether rubber product.

[0127] (2) The pulverized perfluoroether rubber was activated by plasma under the conditions of argon plasma flow rate of 60 sccm, chamber pressure of 30 Pa, and power of 250 W for 5 min.

[0128] (3) The activated perfluoroether rubber and γ-aminopropyltriethoxysilane (APTES) coupling agent were stirred at 200 rpm for 4 h at 80 °C to obtain a mixture, wherein the amount of coupling agent was 3 wt% of the mass of the activated perfluoroether rubber.

[0129] (4) The surface-modified perfluoroether rubber after coupling agent surface treatment is processed by sol-gel method to obtain modified perfluoroether rubber, specifically including the following steps:

[0130] 4.1 The perfluoroether rubber after surface modification with coupling agent was immersed in anhydrous ethanol and ultrasonically cleaned for 40 minutes at 300W power.

[0131] 4.2 Preparation of nano silica precursor sol: Tetraethyl orthosilicate, anhydrous ethanol, deionized water and hydrochloric acid were mixed in a molar ratio of 1:6:2.5:0.05 and stirred at 600 rpm for 2 hours at 40°C to form a uniform and transparent sol.

[0132] 4.3 The perfluoroether rubber after surface modification with coupling agent was immersed in sol and impregnated for 6 hours under stirring conditions of 30℃ and 200rpm. The mass ratio of the perfluoroether rubber after surface modification with coupling agent to tetraethyl orthosilicate was 100:10.

[0133] 4.4 Remove the impregnated granules, let them stand at room temperature for 36 hours, and then dry them using a gradient temperature increase: dry at 60℃ for 1 hour and at 120℃ for 1 hour.

[0134] 4.5 Finally, under nitrogen protection, the mixture is heat-treated at 300℃ for 2 hours to form a dense silica coating layer with a thickness of 150-250nm.

[0135] The mass fraction of nano-sized silica is 3.0 wt% based on the total amount of modified perfluoroether rubber.

[0136] (5) According to the mass ratio of the matrix material and the modified perfluoroether rubber being 85:15, the matrix material polyetheretherketone (brand name: 450G) and the mixture are mixed in a twin-screw extruder and extruded through the twin-screw extruder. The twin-screw extruder has a screw length-to-diameter ratio of 40, and the extrusion temperature is set to 350℃ (feed) → 365℃ (middle section) → 380℃ (end), the screw speed is 120 rpm, and the mixing time is 8 min to obtain the extrudate.

[0137] The extrudate was cooled with water and then pelletized to obtain 2mm composite particles;

[0138] The composite particles were injection molded at 300℃, with the mold temperature at 160℃, the pressure at 10MPa, and the holding time at 5min.

[0139] The molded composite material was subjected to annealing, cooling, and heat treatment sequentially to obtain a perfluoroether rubber composite material. The annealing temperature was 280℃ and the annealing time was 2 hours. After annealing, the temperature was cooled to 180℃ at a rate not exceeding 5℃ / min and held for 0.5 hours. Subsequently, heat treatment was performed at a temperature of 310℃ for 8 hours.

[0140] Example 19

[0141] This embodiment provides a method for preparing a perfluoroether rubber composite material, the specific steps and parameters of which are as follows:

[0142] (1) The perfluoroether rubber was treated in a liquid nitrogen environment at -196℃ for 45 minutes and then pulverized by a high-speed ball mill until the particle size of the perfluoroether rubber was 20μm-50μm. In this embodiment, the perfluoroether rubber was a waste perfluoroether rubber product.

[0143] (2) The pulverized perfluoroether rubber was activated by plasma under the conditions of argon plasma flow rate of 50 sccm, chamber pressure of 30 Pa, and power of 180 W for 10 min.

[0144] (3) The activated perfluoroether rubber and γ-aminopropyltriethoxysilane (APTES) coupling agent were stirred at 350 rpm for 4 h at 70 °C to obtain a mixture, wherein the amount of coupling agent was 3 wt% of the mass of the activated perfluoroether rubber.

[0145] (4) The surface-modified perfluoroether rubber after coupling agent surface treatment is processed by sol-gel method to obtain modified perfluoroether rubber, specifically including the following steps:

[0146] 4.1 The perfluoroether rubber after surface modification with coupling agent was immersed in anhydrous ethanol and ultrasonically cleaned for 40 minutes at 300W power.

[0147] 4.2 Preparation of nano-silica precursor sol: Tetraethyl orthosilicate, anhydrous ethanol, deionized water and hydrochloric acid were mixed in a molar ratio of 1:5:2:0.1 and stirred at 500 rpm for 3 hours at 50°C to form a uniform and transparent sol. Specifically, tetraethyl orthosilicate (TEOS) hydrolyzes under acidic conditions to generate silicic acid monomers, which then form a three-dimensional network structure of silica sol through a condensation reaction.

[0148] 4.3 The perfluoroether rubber after surface modification with coupling agent was immersed in sol and ultrasonically treated at 400W power for 50min. The temperature was controlled at 40℃ during the treatment. The mass ratio of the perfluoroether rubber after surface modification with coupling agent to tetraethyl orthosilicate was 100:10.

[0149] The mass fraction of nano-sized silica is 3.0 wt% based on the total amount of modified perfluoroether rubber.

[0150] (5) According to the mass ratio of the matrix material and the modified perfluoroether rubber being 85:15, the matrix material polyetheretherketone (brand name: 450G) and the mixture are mixed in a twin-screw extruder and extruded through the twin-screw extruder. The twin-screw extruder has a screw length-to-diameter ratio of 40, and the extrusion temperature is set to 350℃ (feed) → 365℃ (middle section) → 380℃ (end), the screw speed is 120 rpm, and the mixing time is 8 min to obtain the extrudate.

[0151] The extrudate was cooled with water and then pelletized to obtain 2mm composite particles;

[0152] The composite particles were injection molded at 300℃, with the mold temperature at 160℃, the pressure at 10MPa, and the holding time at 5min.

[0153] The molded composite material was subjected to annealing, cooling, and heat treatment sequentially to obtain a perfluoroether rubber composite material. The annealing temperature was 280℃ and the annealing time was 2h. After annealing, the temperature was cooled to 180℃ at a rate not exceeding 5℃ / min and held for 0.5h. Subsequently, heat treatment was performed at a temperature of 300℃ for 10h.

[0154] Example 20

[0155] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3. The difference is that in step (2), the plasma includes argon plasma and oxygen plasma, and the flow rate ratio of argon plasma to oxygen plasma is 50:2.

[0156] Example 21

[0157] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3. The difference is that in step (2), the plasma includes argon plasma and oxygen plasma, and the flow ratio of argon plasma to oxygen plasma is 30:5.

[0158] Example 22

[0159] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3. The difference is that in step (2), the plasma includes argon plasma and oxygen plasma, and the flow rate ratio of argon plasma to oxygen plasma is 100:1.

[0160] Example 23

[0161] This embodiment provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 3, except that oxygen plasma is used instead of argon plasma in step (2).

[0162] Comparative Example 1

[0163] This comparative example provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 1, except that the perfluoroether rubber composite material does not contain modified perfluoroether rubber. The specific preparation method is as follows:

[0164] The matrix material is extruded through a twin-screw extruder with a screw length-to-diameter ratio of 40. The extrusion temperature is set to 350℃ (feed) → 365℃ (middle section) → 380℃ (end section), the screw speed is 120 rpm, and the mixing time is 8 min to obtain the extrudate.

[0165] The extrudate was cooled with water and then pelletized to obtain 2mm composite particles;

[0166] The composite particles were injection molded at 300℃, with the mold temperature at 160℃, the pressure at 10MPa, and the holding time at 5min.

[0167] The molded composite material was subjected to annealing and heat treatment in sequence to obtain a perfluoroether rubber composite material. The annealing temperature was 280℃ and the annealing time was 2h. The heat treatment temperature was 300℃ and the heat treatment time was 10h.

[0168] Comparative Example 2

[0169] This comparative example provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 1, except that an equal mass of unmodified perfluoroether rubber is used to replace the modified perfluoroether rubber in step (5). The specific steps are as follows:

[0170] According to the mass ratio of matrix material to perfluoroether rubber of 85:15, the matrix material is polyetheretherketone (brand name: 450G) and perfluoroether rubber are mixed and extruded through a twin-screw extruder. The twin-screw extruder has a screw length-to-diameter ratio of 40, and the extrusion temperature is set to 350℃ (feed) → 365℃ (middle section) → 380℃ (end), the screw speed is 120 rpm, and the mixing time is 8 min to obtain the extrudate.

[0171] The extrudate was cooled with water and then pelletized to obtain 2mm composite particles;

[0172] The composite particles were injection molded at 300℃, with the mold temperature at 160℃, the pressure at 10MPa, and the holding time at 5min.

[0173] The molded composite material was subjected to annealing and heat treatment in sequence to obtain a perfluoroether rubber composite material. The annealing temperature was 280℃ and the annealing time was 2h. The heat treatment temperature was 300℃ and the heat treatment time was 10h.

[0174] Comparative Example 3

[0175] This comparative example provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 5, except that it does not contain modified perfluoroether rubber. The specific steps are as follows:

[0176] Polytetrafluoroethylene (brand: DuPont) TM Place PTFE 7A into a high-energy mixer and mix at 600 rpm for 30 minutes;

[0177] Subsequently, the mixture was molded at a molding temperature of 350℃, a pressure of 15MPa, and a holding time of 10min.

[0178] After sintering the shaped mixture at 390℃ for 6 hours, it was first cooled to 280℃ at 3℃ / min and annealed for 2 hours, then slowly cooled to 180℃ and held for 0.5 hours, and finally heat-treated at 300℃ for 10 hours under nitrogen protection throughout the process to obtain a perfluoroether rubber composite material.

[0179] Comparative Example 4

[0180] This comparative example provides a method for preparing a perfluoroether rubber composite material. The specific steps and parameters are the same as in Example 5, except that an equal mass of unmodified perfluoroether rubber is used to replace the modified perfluoroether rubber in step (4). The specific steps are as follows:

[0181] According to the matrix material (polytetrafluoroethylene grade: DuPont) TM The mass ratio of PTFE 7A and perfluoroether rubber is 9:1. The matrix material and perfluoroether rubber are mixed in a high-energy mixer at 600 rpm for 30 minutes to obtain the mixture.

[0182] Subsequently, the mixture was molded at a molding temperature of 350℃, a pressure of 15MPa, and a holding time of 10min.

[0183] After sintering the shaped mixture at 390℃ for 6 hours, it was first cooled to 280℃ at 3℃ / min and annealed for 2 hours, then slowly cooled to 180℃ and held for 0.5 hours, and finally heat-treated at 300℃ for 10 hours under nitrogen protection throughout the process to obtain a perfluoroether rubber composite material.

[0184] Comparative Example 5

[0185] This comparative example provides a method for preparing a perfluoroether rubber composite material, the specific steps and parameters of which are as follows:

[0186] (1) The perfluoroether rubber was treated in a liquid nitrogen environment at -196℃ for 45 minutes and then pulverized by a high-speed ball mill until the particle size of the perfluoroether rubber was 20-50μm. In this embodiment, the perfluoroether rubber was a waste perfluoroether rubber product.

[0187] (2) The pulverized perfluoroether rubber was subjected to plasma activation under the conditions of oxygen flow rate of 50 sccm, chamber pressure of 30 Pa, and power of 180 W for 10 min to obtain modified perfluoroether rubber.

[0188] (4) According to the mass ratio of the matrix material and the modified perfluoroether rubber being 85:15, the matrix material polyetheretherketone (brand: 450G) and the mixture are mixed in a twin-screw extruder and extruded through the twin-screw extruder. The twin-screw extruder has a screw length-to-diameter ratio of 40, and the extrusion temperature is set to 350℃ (feed) → 365℃ (middle section) → 380℃ (end), the screw speed is 120 rpm, and the mixing time is 8 min to obtain the extrudate.

[0189] The extrudate was cooled with water and then pelletized to obtain 2mm composite particles;

[0190] The composite particles were injection molded at 300℃, with the mold temperature at 160℃, the pressure at 10MPa, and the holding time at 5min.

[0191] The molded composite material was subjected to annealing, cooling, and heat treatment sequentially to obtain a perfluoroether rubber composite material. The annealing temperature was 280℃ and the annealing time was 2h. After annealing, the temperature was cooled to 180℃ at a rate not exceeding 5℃ / min and held for 0.5h. Subsequently, heat treatment was performed at a temperature of 300℃ for 10h.

[0192] Experimental Example

[0193] The mechanical properties of the perfluoroether rubber composites prepared in Examples 1-23 and Comparative Examples 1-5 were tested, and the test results are shown in Table 1. The testing methods for the mechanical properties are as follows:

[0194] The tensile strength and elongation at break were tested according to ASTM D638 standard.

[0195] The method for testing compression set is in accordance with ASTM D395 standard, with specific conditions of 200℃ for 70h;

[0196] The heat distortion temperature was tested according to ASTM D638 standard, where the temperature was 290℃ and the load pressure was 1.8MPa.

[0197] The method for testing chemical corrosion resistance involves immersing the sample in a 98wt% sulfuric acid solution at room temperature for 24 hours. The mass change rate of the sample before and after immersion is determined by the mass change of the sample before and after immersion. That is, the mass change rate of chemical corrosion resistance = (x1-x2) / x1×100%, where x1 is the mass of the sample before immersion and x2 is the mass of the sample after immersion.

[0198] Table 1 Performance test results of perfluoroether rubber composites

[0199]

[0200]

[0201]

[0202] Because perfluoroether rubber has poor compatibility with the high-performance polymers it is bonded to, it not only affects the flowability of the composite material but also leads to poor mechanical properties. When using polyetheretherketone (PEEK) as the matrix material, compared to Comparative Examples 1-2, the perfluoroether rubber composite materials prepared in Examples 1-3 and 8-23 of this invention exhibit better tensile strength, elongation at break, compression set, and heat distortion temperature than both matrix materials without and with perfluoroether rubber. When using polytetrafluoroethylene (PTFE) as the matrix material, compared to Comparative Examples 3-4, the perfluoroether rubber composite materials prepared in Examples 5 and 7 of this invention exhibit better tensile strength, elongation at break, and compression set than both matrix materials without and with perfluoroether rubber. This demonstrates that by using modified perfluoroether rubber, this invention achieves better compatibility with the matrix material, resulting in composite materials that exhibit better overall mechanical properties.

[0203] Depending on the modification method, the resulting composite materials exhibit different effects on various mechanical properties. Compared to Comparative Example 5, Example 1 of this invention uses plasma treatment and coupling agent modification to modify perfluoroether rubber, resulting in a composite material with good tensile strength, compression set, and heat distortion temperature. Example 2 of this invention uses plasma treatment and nanofiller coating modification, resulting in a composite material with good elongation at break, exhibiting better durability and stability. Example 3 uses plasma, coupling agent modification, and nanofiller coating in sequence to form a composite material that exhibits good performance in tensile strength, elongation at break, compression set, chemical corrosion resistance, and heat distortion temperature.

[0204] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A perfluoroether rubber composite material, characterized in that, Including modified perfluoroether rubber and matrix materials, The method for obtaining the modified perfluoroether rubber includes sequentially subjecting the perfluoroether rubber to plasma activation and surface modification treatments. The surface modification method includes at least one of coupling agent modification and nanofiller coating. The matrix material includes at least one of polytetrafluoroethylene, polyetheretherketone, or polyphenylene sulfide. The coupling agent includes at least one of silane coupling agents or titanate coupling agents. The nanofiller includes at least one of silicon dioxide or aluminum oxide.

2. The perfluoroether rubber composite material according to claim 1, characterized in that, The modified perfluoroether rubber content is 5wt%-30wt% based on the mass of the perfluoroether rubber composite material; and / or, The plasma includes argon plasma.

3. The perfluoroether rubber composite material according to claim 2, characterized in that, The plasma also includes oxygen plasma, and the flow rate ratio of argon plasma to oxygen plasma in the plasma is 30-100:1-5.

4. The perfluoroether rubber composite material according to claim 2, characterized in that, The particle size of the nanofiller is 10nm-100nm.

5. The perfluoroether rubber composite material according to claim 2, characterized in that, The coupling agent content is 3wt%-8wt% based on the mass of the modified perfluoroether rubber; and / or, The coating amount of the nanofiller is 1 wt%-5 wt% based on the mass of the modified perfluoroether rubber.

6. The perfluoroether rubber composite material according to claim 4, characterized in that, The silane coupling agent includes any one of fluorinated silane coupling agents and aminosilane coupling agents; The coupling agent and the matrix material are configured as follows: When the matrix material is polytetrafluoroethylene, the coupling agent is a fluorinated silane coupling agent; When the matrix material is polyetheretherketone, the coupling agent is an aminosilane coupling agent; When the matrix material is polyphenylene sulfide, the coupling agent is a titanate coupling agent; The fluorinated silane coupling agent includes at least one of perfluoroalkyltrimethoxysilane, perfluoroalkylethoxysilane, fluorinated aromatic silane, and partially fluorinated alkylsilane; the aminosilane coupling agent includes at least one of γ-aminopropyltriethoxysilane, diaminosilane, phenylaminosilane, and long-chain alkylaminosilane.

7. A method for preparing a perfluoroether rubber composite material as described in any one of claims 1-6, characterized in that, Includes the following steps, The modified perfluoroether rubber and the matrix material are mixed and subjected to a densification reaction; Perfluoroether rubber composite materials are obtained through molding processes; The densification reaction includes at least one of melting or sintering.

8. The method for preparing the perfluoroether rubber composite material according to claim 7, characterized in that, It also includes post-processing steps, which include annealing and heat treatment. The annealing temperature is 250℃-280℃ and the time is 2 h-4 h. The heat treatment temperature is 290℃-310℃ and the time is 8 h-12 h.

9. The method for preparing the perfluoroether rubber composite material according to claim 8, characterized in that, The preparation method of the modified perfluoroether rubber includes the following steps: S1, Perfluoroether rubber is subjected to plasma activation treatment to obtain an intermediate; S2, the intermediate and coupling agent obtained in step S1 are heat-treated to obtain modified perfluoroether rubber; or, the nanofiller is coated with the intermediate obtained in step S1 by sol-gel method or ultrasonic dispersion method.

10. The method for preparing the perfluoroether rubber composite material according to claim 8, characterized in that, The preparation method of the modified perfluoroether rubber includes the following steps: S1, the perfluoroether rubber is subjected to plasma treatment to obtain an intermediate; S2, the intermediate and coupling agent are subjected to heat treatment to obtain the modified perfluoroether rubber; S3, the modified perfluoroether rubber obtained in step S2 is coated with nanofillers using sol-gel method or ultrasonic dispersion method.

11. The method for preparing the perfluoroether rubber composite material according to claim 9 or 10, characterized in that, The steps of obtaining an intermediate by plasma treatment of perfluoroether rubber include: the plasma modification power is 100W-300W, the modification treatment time is 1min-10min, the internal pressure of the plasma modification treatment is 5Pa-50Pa, and the plasma flow rate is 30 sccm-110 sccm.

12. The method for preparing the perfluoroether rubber composite material according to claim 9 or 10, characterized in that, The specific steps of heat treatment of the intermediate and coupling agent include: under stirring, the heat treatment temperature is 60℃-80℃, the stirring speed is 200rpm-400rpm, and the treatment time is 2h-4h.

13. The method for preparing the perfluoroether rubber composite material according to claim 9 or 10, characterized in that, The sol-gel method is used to coat intermediates or modified perfluoroether rubber with nanofillers. The specific steps include: immersing the intermediates or modified perfluoroether rubber in a sol for 2-6 hours under stirring conditions, with a stirring speed of 200-400 rpm and an immersion temperature of 30℃-50℃; after immersion, aging and drying, followed by heat treatment in an inert atmosphere for 2-3 hours at a temperature of 250℃-300℃. The intermediate or modified perfluoroether rubber is coated with nanofillers using the ultrasonic dispersion method. Specifically, the following steps are included: ultrasonically treating the intermediate or modified perfluoroether rubber in a sol at a power of 300W-600W for 30min-60min, with the temperature controlled at 30℃-50℃.

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