Perfluoroether rubber composite material and preparation method thereof

Abstract

The invention relates to the technical field of perfluoroether rubber, in particular to a perfluoroether rubber composite material and a preparation method thereof. The perfluoroether rubber composite material provided by the invention comprises modified perfluoroether rubber and a matrix material, a method for obtaining the modified perfluoroether rubber comprises the step of sequentially carrying out plasma activation and surface modification treatment on the perfluoroether rubber, and the surface modification method comprises at least one of coupling agent modification and nanofiller coating. The perfluoroether rubber is treated to obtain the modified perfluoroether rubber, so that the interface energy of the perfluoroether rubber is reduced, and the compatibility of the perfluoroether rubber and a matrix material is effectively improved; uniform nanoscale coarse structures and active sites are formed on the surface of the perfluoroether rubber through plasma activation, and the activated perfluoroether rubber is subjected to surface modification through coupling agent surface modification or nano filler coating, so that the processing stability and the mechanical property of the perfluoroether rubber composite material are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of perfluoroether rubber, and in particular to a perfluoroether rubber composite material and a preparation method thereof. Background Art

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

[0003] With the rise of the semiconductor industry, perfluoroether rubber, as a key material in semiconductor equipment, has a performance that is directly related to the reliability, yield rate and equipment life of semiconductor equipment. However, the current performance of perfluoroether rubber cannot meet the above requirements, resulting in great processing difficulties and unstable mechanical properties of the material.

[0004] Furthermore, while perfluoroether rubber's exceptional chemical stability imparts excellent properties, it also presents challenges in its post-waste recycling. Currently used treatment methods, such as solvent dissolution and high-temperature incineration, suffer from low resource utilization and high energy consumption, and their actual recycling rates fall short of meeting sustainable development requirements. This current treatment process not only wastes resources but also falls short of green environmental protection principles. Summary of the Invention

[0005] Therefore, in order to solve 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 and a preparation method and application thereof.

[0006] At the same time, in order to solve the defect in the prior art that waste perfluoroether rubber cannot be fully recycled and utilized, the present invention provides a perfluoroether rubber composite material and its preparation method and application.

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

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

[0009] In some embodiments, the matrix material comprises a high molecular polymer. Preferably, the high molecular polymer has properties such as strong mechanical properties, 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, the plasma includes argon plasma and oxygen plasma, and the flow ratio of the argon plasma to the oxygen plasma 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-100 nm.

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

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

[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 base material are configured as follows: when the base material is polytetrafluoroethylene, the coupling agent is a fluorinated silane coupling agent; when the base material is polyetheretherketone, the coupling agent is an aminosilane coupling agent; when the base material is polyphenylene sulfide, the coupling agent is a titanate coupling agent.

[0017] In some embodiments, the fluorine-containing silane coupling agent includes at least one of perfluoroalkyltrimethoxysilane, perfluoroalkylethoxysilane, fluorine-containing aromatic silane and partially fluorinated alkylsilane; more preferably, the aminosilane coupling agent includes at least one of γ-aminopropyltriethoxysilane, bisaminosilane, 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 a modified perfluoroether rubber and a matrix material, and performing 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 method for preparing the perfluoroether rubber composite material further includes a post-treatment step, wherein the post-treatment includes annealing and heat treatment, wherein the annealing temperature is 250°C-280°C and the time is 2h-4h, and the heat treatment temperature is 290°C-310°C and the time is 8h-12h. The present invention controls the annealing temperature to 250-280°C and sets the annealing time to 2-4h to release internal stress and improve dimensional stability. At the same time, a secondary heat treatment step is provided, and the secondary heat treatment temperature is controlled to 290-310°C and the heat treatment time is 8-12h to improve chemical corrosion resistance and thermal stability.

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

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

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

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

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

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

[0026] In some embodiments, a sol-gel method is used to coat an intermediate or modified perfluoroether rubber with a nanofiller, specifically comprising the following steps: immersing the intermediate or modified perfluoroether rubber in a sol under stirring for 2-6 hours, with a stirring speed of 200-400 rpm and an immersion temperature of 30°C-50°C. After immersion, the intermediate or modified perfluoroether rubber is aged and dried, and then heat-treated in an inert atmosphere for 2-3 hours at a heat treatment temperature of 250-300°C. Preferably, the preparation method of the sol comprises stirring the above materials at 40-60°C and 400-600 rpm for 2-4 hours according to a molar ratio of ethyl 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 ethyl orthosilicate, anhydrous ethanol, deionized water and hydrochloric acid in a molar ratio of 1:4-6:1.5-2.5:0.05-0.2, stirring at 40°C-60°C and 400rpm-600rpm for 2h-4h to form a uniform and transparent sol ; (3) Immerse the cleaned perfluoroether rubber particles in the sol and immerse them at 30℃-50℃ and 200rpm-400rpm stirring conditions for 2h-6h; (4) Take out the immersed particles, first let them stand and age at room temperature for 24h-48h, and then use gradient temperature drying: drying at 60℃ for 1 hour and drying at 120℃ for 1 hour; (5) Finally, heat treat at 250℃-300℃ for 2h-3h 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, an ultrasonic dispersion method is used to coat an intermediate or modified perfluoroether rubber with a nanofiller, specifically comprising the following steps: ultrasonically treating the intermediate or modified perfluoroether rubber in a sol at a power of 300W-600W for 30-60 minutes, with the temperature controlled at 30°C-50°C. The ultrasonic treatment of the present invention can optimize the dispersion state and loading effect of the nano-silica. High-frequency oscillation can effectively break up the agglomerates of the nano-silica precursor, resulting in a monodisperse state in the sol. The microfluidic effect generated by the ultrasound can enhance the penetration of the silica sol into the micropores and etched structures on the FFKM surface, thereby improving the bonding strength of the coating.

[0029] In some embodiments, the perfluoroether rubber is obtained by low-temperature treatment and crushing of perfluoroether rubber, the low-temperature treatment temperature is -196°C to -50°C, the treatment time is 30min-60min, the particle size of the crushed perfluoroether rubber is 5μm-50μm, and the perfluoroether rubber is waste perfluoroether rubber. Perfluoroether rubber has high elasticity at room temperature and consumes a lot of energy to crush. However, the heat generated by high-speed shearing can cause local fusion and form irregular particles. The present invention utilizes low-temperature crushing technology to cool the perfluoroether rubber to below its glass transition temperature (Tg≈-10°C), so that the material changes from a highly elastic state to a brittle state. At this time, the molecular chain activity is reduced and it is easier to break under external force, thereby obtaining microparticles with uniform particle size (5μm-50μm), improving the subsequent mixing uniformity with the matrix (such as PTFE / PEEK). When the particle size of the microparticles is higher than 50μm, the interfacial stress concentration is caused due to the excessive size of the particles, which reduces the mechanical properties of the composite material (such as tensile strength and elongation at break), and is easy to settle during processing and uneven dispersion. When the particle size of the microparticles is lower than 5μm, the specific surface area of ​​the microparticles increases, and the van der Waals force is enhanced, which can cause the problem of easy agglomeration, resulting in reduced processing fluidity, difficulty in melt blending, and defects in the final product.

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

[0031] 1. The present invention provides a perfluoroether rubber composite material, comprising a modified perfluoroether rubber and a matrix material, wherein the method for obtaining the modified perfluoroether rubber comprises sequentially performing plasma activation and surface modification treatments on the perfluoroether rubber, wherein the surface modification method comprises at least one of coupling agent modification and nanofiller coating. The present invention obtains the modified perfluoroether rubber after performing plasma activation and surface modification treatments on the perfluoroether rubber, thereby reducing the interfacial energy of the perfluoroether rubber and effectively improving the compatibility between the perfluoroether rubber and the matrix material. Specifically, the present invention forms a uniform nanoscale rough structure and active sites on the surface of the perfluoroether rubber by a plasma activation method, and then uses coupling agent surface modification or nanofiller coating to perform surface modification on the activated perfluoroether rubber, thereby improving the dispersibility of the perfluoroether rubber in the matrix material and improving the processing stability and mechanical properties of the perfluoroether rubber material.

[0032] 2. The present invention provides a perfluoroether rubber composite material, wherein the matrix material is polytetrafluoroethylene, and the coupling agent is a fluorine-containing silane coupling agent; the matrix material is polyetheretherketone, and the coupling agent is an aminosilane coupling agent; the matrix material is polyphenylene sulfide, and the coupling agent is a titanate coupling agent. When the matrix material is polytetrafluoroethylene, a fluorine-containing silane coupling agent is used as the coupling agent, and the fluorine segment of the coupling agent is similar to the chemical structure of polytetrafluoroethylene, which can more effectively reduce the interfacial energy difference and improve the dispersibility; when the matrix material is polyetheretherketone, an aminosilane coupling agent is used as the coupling agent, and the amino group (-NH) in the coupling agent forms a hydrogen bond with the ketone group of polyetheretherketone, which can enhance the interfacial bonding and effectively reduce the interfacial energy; when the matrix material is polyphenylene sulfide, a titanate coupling agent is used as the coupling agent, and the chelating effect of the coupling agent bonds with the sulfide group of polyphenylene sulfide, reducing interfacial defects and effectively reducing the interfacial energy.

[0033] 3. The present invention provides a method for preparing a perfluoroether rubber composite material, comprising mixing a modified perfluoroether rubber with a matrix material and subjecting the mixture to a densification reaction to obtain the perfluoroether rubber composite material. The present invention combines the modified perfluoroether rubber with the matrix material to form the perfluoroether rubber composite material, with simple steps and stable processing performance.

[0034] 4. The present invention provides a method for preparing a perfluoroether rubber composite material, wherein the method for preparing the modified perfluoroether rubber comprises the following steps: S1, subjecting the perfluoroether rubber to plasma treatment to obtain an intermediate; S2, subjecting the intermediate and a coupling agent to heat treatment to obtain a modified perfluoroether rubber; and S3, coating the modified perfluoroether rubber obtained in step S2 with a nanofiller using a sol-gel method or an ultrasonic dispersion method. The present invention sequentially utilizes plasma treatment, coupling agent modification, and nanofiller coating to obtain a modified perfluoroether rubber. First, plasma treatment introduces free radical active sites and polar groups onto the perfluoroether rubber surface, increasing its surface energy and interfacial reactivity. Next, 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 molecules is compatible with the matrix material, thereby reducing the interfacial energy difference and achieving a uniform interface transition through chemical bond bridging. Finally, nanofiller coating is used to construct a uniform nanoreinforcement layer on the rubber surface, which not only improves interfacial compatibility but also enhances the mechanical properties of the composite material through the rigidity enhancement and stress dispersion effects of the nanoparticles. This organic combination of processes synergistically improves interfacial compatibility from three dimensions: physical morphology, chemical bonding, and nanoreinforcement, enabling the modified perfluoroether rubber to be uniformly dispersed in the matrix material, significantly improving the processing stability and mechanical properties of the composite material. This multi-stage modification process achieves efficient composite and performance improvement of perfluoroether rubber and matrix materials through the synergistic mechanism of "surface activation-interface optimization-nanoreinforcement."

[0035] 5. The present invention provides a method for preparing a perfluoroether rubber composite material, comprising plasma modification of the perfluoroether rubber. The plasma comprises at least one of argon, oxygen, and ammonia. The plasma modification power is 100W-250W, the modification treatment time is 5-15 minutes, and the plasma flow rate during the plasma modification process is 30 sccm-60 sccm. Adjustment of plasma parameters significantly affects the modification effect of the perfluoroether rubber. Researchers of the present invention have found that appropriately increasing the power (e.g., 200W) and extending the treatment time (10 minutes) can enhance surface etching and the introduction of chemical groups, increasing the bonding strength between the material and the substrate by more than 50%. However, excessively high power (>250W) or prolonged treatment time (>15 minutes) can damage the rubber structure and reduce chemical resistance by 30%. The choice of gas type is particularly critical: mixing oxygen and ammonia can unexpectedly generate nitrogen-oxygen complex groups, significantly enhancing interfacial reactivity, but can also accelerate the material's hygrothermal aging due to the byproducts. In addition, a gas flow rate that is too low (<30sccm) may form "patch-like" defects due to uneven plasma distribution, while the turbulent effect at a specific flow rate (such as 40sccm) may give the material superhydrophobic properties (contact angle >150°). Therefore, after treatment with a plasma including at least one of argon, oxygen and ammonia, a plasma modification power of 100W-250W, a modification treatment time of 5min-15min, and a plasma flow rate of 30sccm-60sccm, the surface of the perfluoroether rubber can be effectively modified and its chemical properties are enhanced. DETAILED DESCRIPTION

[0036] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0037] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0038] The perfluoroether rubber products discarded in the embodiments and comparative examples of the present invention mainly come from: sealing rings retired in high-clean working conditions such as semiconductor production lines, such as O-rings, valve seals, etc.; unqualified products produced by manufacturers of perfluoroether rubber products are mainly rubber rings that are judged to have defects or wire diameters that do not meet the requirements during terminal inspection and have only appearance problems.

[0039] Example 1

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

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

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

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

[0044] (4) According to the mass ratio of base material to modified perfluoroether rubber of 85:15, the base material polyetheretherketone (brand: 450G) and the mixed material were mixed in a twin-screw extruder and extruded through the twin-screw extruder, wherein the screw aspect ratio of the twin-screw extruder was 40, the extrusion temperature was set at 350°C (feed) → 365°C (middle section) → 380°C (end), the screw speed was 120 rpm, and the mixing time was 8 min to obtain an extrudate;

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

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

[0047] The formed composite material was sequentially annealed, cooled, and heat-treated to obtain a perfluoroether rubber composite material. The annealing temperature was 280°C for 2 hours. After annealing, the composite material was cooled to 180°C at a rate not exceeding 5°C / min and held at that temperature for 0.5 hours. The composite material was then heat-treated at 300°C for 10 hours.

[0048] Example 2

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

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

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

[0052] (3) treating the plasma-modified perfluoroether rubber by a sol-gel method to obtain a modified perfluoroether rubber, specifically comprising the following steps:

[0053] 3.1 Immerse the plasma-modified perfluoroelastomer in anhydrous ethanol and ultrasonically clean it at 300W power for 40 minutes;

[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 Immerse the cleaned perfluoroelastomer in the sol at 40°C and 300 rpm for 4 hours. The mass ratio of perfluoroelastomer to tetraethyl orthosilicate is 100:10.

[0056] 3.4 Take out the impregnated particles, let them stand at room temperature for 36 hours, and then dry them at a gradient temperature: 60℃ for 1 hour and 120℃ for 1 hour;

[0057] 3.5 Finally, heat treatment was performed at 280°C for 2.5 hours under nitrogen protection to form a dense silica coating layer with a thickness of 150-250 nm to obtain a modified perfluoroether rubber;

[0058] Based on the total amount of the modified perfluoroether rubber, the mass fraction of the nano-scale silicon dioxide is 3.0 wt %.

[0059] (4) According to the mass ratio of base material to mixed material of 85:15, the base material polyetheretherketone (brand: 450G) and modified perfluoroether rubber were mixed in a twin-screw extruder and extruded through the twin-screw extruder, wherein the screw aspect ratio of the twin-screw extruder was 40, the extrusion temperature was set at 350°C (feed) → 365°C (middle section) → 380°C (end), the screw speed was 120 rpm, and the mixing time was 8 min to obtain an extrudate;

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

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

[0062] The formed composite material was sequentially annealed, cooled, and heat-treated to obtain a perfluoroether rubber composite material. The annealing temperature was 280°C for 2 hours. After annealing, the composite material was cooled to 180°C at a rate not exceeding 5°C / min and held at that temperature for 0.5 hours. The composite material was then heat-treated at 300°C for 10 hours.

[0063] Example 3

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

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

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

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

[0068] (4) treating the perfluoroether rubber after the surface modification treatment with the coupling agent by a sol-gel method to obtain a modified perfluoroether rubber, specifically comprising the following steps:

[0069] 4.1 Immerse the perfluoroelastomer after surface modification with coupling agent in anhydrous ethanol and ultrasonically clean it at 300W power for 40 minutes;

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

[0071] 4.3 Immerse the perfluoroether rubber after the coupling agent surface modification treatment in the sol and immerse it at 40°C and 300 rpm for 4 hours. The mass ratio of the perfluoroether rubber after the coupling agent surface modification treatment to ethyl orthosilicate is 100:10.

[0072] 4.4 Take out the impregnated particles, let them stand at room temperature for 36 hours, and then dry them at a gradient temperature: 60℃ for 1 hour and 120℃ for 1 hour;

[0073] 4.5 Finally, heat treatment was performed at 280°C for 2.5 hours under nitrogen protection to form a dense silica coating with a thickness of 150-250 nm;

[0074] Based on the total amount of the modified perfluoroether rubber, the mass fraction of the nano-scale silicon dioxide is 3.0 wt %.

[0075] (5) According to the mass ratio of base material to modified perfluoroether rubber of 85:15, the base material polyetheretherketone (brand: 450G) and the mixed material were mixed in a twin-screw extruder and extruded through the twin-screw extruder, wherein the screw aspect ratio of the twin-screw extruder was 40, the extrusion temperature was set at 350°C (feed) → 365°C (middle section) → 380°C (end), the screw speed was 120 rpm, and the mixing time was 8 min to obtain an extrudate;

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

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

[0078] The formed composite material was sequentially annealed, cooled, and heat-treated to obtain a perfluoroether rubber composite material. The annealing temperature was 280°C for 2 hours. After annealing, the composite material was cooled to 180°C at a rate not exceeding 5°C / min and held at that temperature for 0.5 hours. The composite material was then heat-treated at 300°C for 10 hours.

[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 those in Example 3, except that an equal mass of polyphenylene sulfide (brand: DIC Corporation FZ-210) is used to replace the polyetheretherketone 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 those in Example 3, except that the same mass of polytetrafluoroethylene (brand: DuPont PTFE 7A) replaces the polyetheretherketone in step (5). The specific steps are as follows:

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

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

[0085] The formed mixture was sintered at 390°C for 6 hours, then cooled to 280°C at a rate of 3°C / min for annealing for 2 hours, then slowly cooled to 180°C for 0.5 hours, and finally heat treated at 300°C for 10 hours under nitrogen protection. This process achieved a SiO2-PEEK interfacial shear strength of 35 MPa and an 8°C increase in heat deformation temperature, resulting in a perfluoroether rubber composite.

[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 those in Example 4, except that an equal mass of titanate coupling agent (model: KR-TTS, manufacturer: Kenrich Petrochemicals) was used instead of 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 those in Example 5, except that an equal mass of perfluoroalkyltrimethoxysilane is used to replace the 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 those in Example 3, except that the mass ratio of the perfluoroether rubber after surface modification with a coupling agent and ethyl orthosilicate in steps (4)-4.3 is 100:15; and the mass fraction of nano-scale silica in the modified perfluoroether rubber is 4.5 wt%.

[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 those in Example 3, except that the mass ratio of the perfluoroether rubber after surface modification with a coupling agent and ethyl orthosilicate in steps (4)-4.3 is 100:5; and the mass fraction of nano-scale silica in the modified perfluoroether rubber is 1.5 wt%.

[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 those in Example 3, except that an equimolar amount of aluminum isopropoxide is used to replace the 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 those 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 those 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 those in Example 3, except that in step (5), the mass ratio of the base material to the modified perfluoroether rubber 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 those in Example 3, except that in step (5), the mass ratio of the base material to the modified perfluoroether rubber 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 those in Example 3, except that in step (5), the mass ratio of the base material to the modified perfluoroether rubber 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 those in Example 3, except that in step (5), the mass ratio of the base material to the modified perfluoroether rubber is 7:3.

[0108] Example 17

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

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

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

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

[0113] (4) treating the perfluoroether rubber after the surface modification treatment with the coupling agent by a sol-gel method to obtain a modified perfluoroether rubber, specifically comprising the following steps:

[0114] 4.1 Immerse the perfluoroelastomer after surface modification with coupling agent in anhydrous ethanol and ultrasonically clean it at 300W power for 40 minutes;

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

[0116] 4.3 Immerse the perfluoroether rubber after the coupling agent surface modification treatment in the sol and immerse it at 30°C and 200 rpm for 6 hours. The mass ratio of the perfluoroether rubber after the coupling agent surface modification treatment to ethyl orthosilicate is 100:10.

[0117] 4.4 Take out the impregnated particles, let them stand at room temperature for 36 hours, and then dry them at a gradient temperature: 60℃ for 1 hour and 120℃ for 1 hour;

[0118] 4.5 Finally, heat treatment was performed at 250°C for 3 hours under nitrogen protection to form a dense silica coating with a thickness of 150-250 nm;

[0119] Calculated based on the total amount of the modified perfluoroether rubber, the mass fraction of the nano-scale silicon dioxide is 3.0 wt %.

[0120] (5) According to the mass ratio of base material to modified perfluoroether rubber of 85:15, the base material polyetheretherketone (brand: 450G) and the mixed material were mixed in a twin-screw extruder and extruded through the twin-screw extruder, wherein the screw aspect ratio of the twin-screw extruder was 40, the extrusion temperature was set at 350°C (feed) → 365°C (middle section) → 380°C (end), the screw speed was 120 rpm, and the mixing time was 8 min to obtain an extrudate;

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

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

[0123] The formed composite material was sequentially annealed, cooled, and heat-treated to obtain a perfluoroether rubber composite material. The annealing temperature was 250°C for 4 hours. After annealing, the composite material was cooled to 180°C at a rate not exceeding 5°C / min and held at that temperature for 0.5 hours. The composite material was then heat-treated at 290°C for 12 hours.

[0124] Example 18

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

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

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

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

[0129] (4) treating the perfluoroether rubber after the surface modification treatment with the coupling agent by a sol-gel method to obtain a modified perfluoroether rubber, specifically comprising the following steps:

[0130] 4.1 Immerse the perfluoroelastomer after surface modification with coupling agent in anhydrous ethanol and ultrasonically clean it at 300W power for 40 minutes;

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

[0132] 4.3 Immerse the perfluoroether rubber after the coupling agent surface modification treatment in the sol and immerse it at 30°C and 200 rpm for 6 hours. The mass ratio of the perfluoroether rubber after the coupling agent surface modification treatment to ethyl orthosilicate is 100:10.

[0133] 4.4 Take out the impregnated particles, let them stand at room temperature for 36 hours, and then dry them at a gradient temperature: 60℃ for 1 hour and 120℃ for 1 hour;

[0134] 4.5 Finally, heat treatment was performed at 300°C for 2 hours under nitrogen protection to form a dense silica coating with a thickness of 150-250 nm;

[0135] Calculated based on the total amount of the modified perfluoroether rubber, the mass fraction of the nano-scale silicon dioxide is 3.0 wt %.

[0136] (5) According to the mass ratio of base material to modified perfluoroether rubber of 85:15, the base material polyetheretherketone (brand: 450G) and the mixed material were mixed in a twin-screw extruder and extruded through the twin-screw extruder, wherein the screw aspect ratio of the twin-screw extruder was 40, the extrusion temperature was set at 350°C (feed) → 365°C (middle section) → 380°C (end), the screw speed was 120 rpm, and the mixing time was 8 min to obtain an extrudate;

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

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

[0139] The formed composite material was subjected to annealing, cooling, and heat treatment in sequence to obtain a perfluoroether rubber composite material. The annealing temperature was 280°C for 2 hours. After annealing, the composite material was cooled to 180°C at a rate not exceeding 5°C / min and held at that temperature for 0.5 hours. The composite material was then heat treated at 310°C for 8 hours.

[0140] Example 19

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

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

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

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

[0145] (4) treating the perfluoroether rubber after the surface modification treatment with the coupling agent by a sol-gel method to obtain a modified perfluoroether rubber, specifically comprising the following steps:

[0146] 4.1 Immerse the perfluoroelastomer after surface modification with coupling agent in anhydrous ethanol and ultrasonically clean it at 300W power for 40 minutes;

[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 at 50°C for 3 hours to form a uniform and transparent sol. Specifically, tetraethyl orthosilicate (TEOS) was hydrolyzed under acidic conditions to generate silicic acid monomers, which then formed a three-dimensional network structure of silica sol through polycondensation.

[0148] 4.3 Immerse the perfluoroether rubber after the coupling agent surface modification treatment in the sol and ultrasonically treat it at a power of 400 W for 50 min. The temperature during the treatment is controlled at 40°C. The mass ratio of the perfluoroether rubber after the coupling agent surface modification treatment to ethyl orthosilicate is 100:10.

[0149] Based on the total amount of the modified perfluoroether rubber, the mass fraction of the nano-scale silicon dioxide is 3.0 wt %.

[0150] (5) According to the mass ratio of base material to modified perfluoroether rubber of 85:15, the base material polyetheretherketone (brand: 450G) and the mixed material were mixed in a twin-screw extruder and extruded through the twin-screw extruder, wherein the screw aspect ratio of the twin-screw extruder was 40, the extrusion temperature was set at 350°C (feed) → 365°C (middle section) → 380°C (end), the screw speed was 120 rpm, and the mixing time was 8 min to obtain an extrudate;

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

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

[0153] The formed composite material was sequentially annealed, cooled, and heat-treated to obtain a perfluoroether rubber composite material. The annealing temperature was 280°C for 2 hours. After annealing, the composite material was cooled to 180°C at a rate not exceeding 5°C / min and held at that temperature for 0.5 hours. The composite material was then heat-treated at 300°C for 10 hours.

[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 those in Example 3, except that the plasma in step (2) includes argon plasma and oxygen plasma, and the flow 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 those in Example 3, except that the plasma in step (2) 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 those in Example 3, except that the plasma in step (2) includes argon plasma and oxygen plasma, and the flow 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 those in Example 3, except that oxygen plasma is used instead of the 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 those 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 was extruded through a twin-screw extruder, wherein the screw aspect ratio of the twin-screw extruder was 40, the extrusion temperature was set at 350°C (feed) → 365°C (middle section) → 380°C (end section), the screw speed was 120 rpm, and the mixing time was 8 min to obtain an extrudate;

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

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

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

[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 those in Example 1, except that unmodified perfluoroether rubber of the same mass is used to replace the modified perfluoroether rubber in step (5). The specific steps are as follows:

[0170] According to the mass ratio of base material to perfluoroether rubber of 85:15, the base material polyetheretherketone (brand: 450G) and perfluoroether rubber were mixed and extruded through a twin-screw extruder, wherein the screw aspect ratio of the twin-screw extruder was 40, the extrusion temperature was set at 350°C (feed) → 365°C (middle section) → 380°C (end), the screw speed was 120 rpm, and the mixing time was 8 min to obtain an extrudate;

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

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

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

[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 those in Example 5, except that the modified perfluoroether rubber is not included. The specific steps are as follows:

[0176] Polytetrafluoroethylene (brand: DuPont TM PTFE 7A) was placed in a high-energy mixer and mixed at 600 rpm for 30 min;

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

[0178] The formed mixture was sintered at 390°C for 6 hours, cooled to 280°C at a rate of 3°C / min and annealed for 2 hours, then slowly cooled to 180°C and kept warm for 0.5 hours, and finally heat treated at 300°C 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 those 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 base material (PTFE grade: DuPont TM The mass ratio of PTFE 7A) and perfluoroether rubber is 9:1, and the base material and perfluoroether rubber are mixed in a high-energy mixer at a speed of 600 rpm for 30 min to obtain a mixture;

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

[0183] The formed mixture was sintered at 390°C for 6 hours, cooled to 280°C at a rate of 3°C / min and annealed for 2 hours, then slowly cooled to 180°C and kept warm for 0.5 hours, and finally heat treated at 300°C 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, and the specific steps and parameters are as follows:

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

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

[0188] (4) According to the mass ratio of base material to modified perfluoroether rubber of 85:15, the base material polyetheretherketone (brand: 450G) and the mixed material were mixed in a twin-screw extruder and extruded through the twin-screw extruder, wherein the screw aspect ratio of the twin-screw extruder was 40, the extrusion temperature was set at 350°C (feed) → 365°C (middle section) → 380°C (end), the screw speed was 120 rpm, and the mixing time was 8 min to obtain an extrudate;

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

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

[0191] The formed composite material was sequentially annealed, cooled, and heat-treated to obtain a perfluoroether rubber composite material. The annealing temperature was 280°C for 2 hours. After annealing, the composite material was cooled to 180°C at a rate not exceeding 5°C / min and held at that temperature for 0.5 hours. The composite material was then heat-treated at 300°C for 10 hours.

[0192] Experimental example

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

[0194] The testing methods for tensile strength and elongation at break are in accordance with ASTM D638 standard;

[0195] The compression set test method is based on the ASTM D395 standard test, with the specific conditions being 200°C and 70h.

[0196] The heat distortion temperature test method is based on the ASTM D638 standard test, where the temperature is 290°C and the load pressure is 1.8 MPa;

[0197] The chemical corrosion resistance detection method is to soak the sample in 98wt% sulfuric acid solution at room temperature for 24 hours, and determine the mass change rate of chemical corrosion resistance by the mass change of the sample before and after soaking, that is, the mass change rate of chemical corrosion resistance = (x1-x2) / x1×100%, where x1 is the mass of the sample before soaking, and x2 is the mass of the sample after soaking.

[0198] Table 1 Performance test results of perfluoroether rubber composite materials

[0199]

[0200]

[0201]

[0202] Due to the poor compatibility of perfluoroether rubber with the high-performance polymer it is combined with, not only does it affect the fluidity of the composite material, but it also leads to poor mechanical properties of the composite material. When using polyetheretherketone as the matrix material, compared with comparative examples 1-2, the perfluoroether rubber composite materials prepared in Examples 1-3 and 8-23 of the present invention are superior to the matrix materials without perfluoroether rubber and the matrix materials with perfluoroether rubber in terms of tensile strength, elongation at break, compression set, and heat deformation temperature. When using polytetrafluoroethylene as the matrix material, compared with comparative examples 3-4, the perfluoroether rubber composite materials prepared in Examples 5 and 7 of the present invention are superior to the matrix materials without perfluoroether rubber and the matrix materials with perfluoroether rubber in terms of tensile strength, elongation at break, and compression set. This demonstrates that the modified perfluoroether rubber of the present invention is more compatible with the matrix material, resulting in the composite materials exhibiting better overall mechanical properties.

[0203] According to different modification methods, the composite materials formed have different effects on different mechanical properties. Compared with Comparative Example 5, Example 1 of the present invention uses plasma treatment and coupling agent modification to modify perfluoroether rubber, and the formed composite material has good tensile strength, compression permanent set and heat deformation temperature. Example 2 of the present invention uses plasma treatment and nanofiller coating modification to form a composite material with good elongation at break and shows better durability and stability. Example 3 uses three modification methods of plasma, coupling agent modification and nanofiller coating in sequence to form a composite material with good performance in tensile strength, elongation at break, compression permanent set, chemical corrosion resistance and heat deformation temperature.

[0204] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A perfluoroether rubber composite material, characterized in that: Including modified perfluoroether rubber and base material, The method for obtaining the modified perfluoroether rubber comprises sequentially performing plasma activation and surface modification treatment on the perfluoroether rubber, The surface modification method includes at least one of coupling agent modification and nanofiller coating.

2. The perfluoroether rubber composite material according to claim 1, characterized in that Based on the mass of the perfluoroether rubber composite material, the content of the modified perfluoroether rubber is 5wt%-30wt%; and / or, The matrix material comprises a high molecular polymer; 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 matrix material includes at least one of polytetrafluoroethylene, polyetheretherketone or polyphenylene sulfide; and / or, The coupling agent includes at least one of a silane coupling agent or a titanate coupling agent; and / or, The nano filler includes at least one of silicon dioxide and aluminum oxide, and the particle size of the nano filler is 10 nm to 100 nm.

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

6. The perfluoroether rubber composite material according to claim 4, characterized in that The silane coupling agent includes any one of a fluorine-containing silane coupling agent and an amino silane coupling agent; The coupling agent and the base material are configured in the following manner: When the matrix material is polytetrafluoroethylene, the coupling agent is a fluorine-containing 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 fluorine-containing silane coupling agent includes at least one of perfluoroalkyltrimethoxysilane, perfluoroalkylethoxysilane, fluorine-containing aromatic silane and partially fluorinated alkylsilane; the aminosilane coupling agent includes at least one of γ-aminopropyltriethoxysilane, bisaminosilane, phenylaminosilane and long-chain alkylaminosilane.

7. A method for preparing the perfluoroether rubber composite material according to any one of claims 1 to 6, characterized in that: The following steps are included: The modified perfluoroether rubber and the base material are mixed to carry out a densification reaction; A perfluoroether rubber composite material is obtained through a molding process; Wherein, 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, wherein: The method further includes a post-processing step, wherein the post-processing step includes annealing and heat treatment. The annealing temperature is 250° C.-280° C. and the time is 2 h-4 h. The heat treatment temperature is 290° C.-310° C. 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 comprises the following steps: S1, subjecting perfluoroether rubber to plasma activation treatment to obtain an intermediate; S2, heat-treating the intermediate obtained in step S1 and the coupling agent to obtain a modified perfluoroether rubber; or, coating the intermediate obtained in step S1 with a nanofiller using a sol-gel method or an 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 comprises the following steps: S1, subjecting the perfluoroether rubber to plasma treatment to obtain an intermediate; S2, subjecting the intermediate and a coupling agent to heat treatment to obtain the modified perfluoroether rubber; and S3, coating the modified perfluoroether rubber obtained in step S2 with a nanofiller using a sol-gel method or an ultrasonic dispersion method.

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

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

13. The method for preparing the perfluoroether rubber composite material according to claim 9 or 10, characterized in that: The method comprises the following steps: immersing the intermediate or modified perfluoroether rubber in a sol under stirring for 2-6 hours at a stirring speed of 200-400 rpm and a immersion temperature of 30-50° C., aging and drying the intermediate or modified perfluoroether rubber in an inert atmosphere for 2-3 hours at a heat treatment temperature of 250-300° C., and immersing the intermediate or modified perfluoroether rubber in a sol under stirring for 2-6 hours at a stirring speed of 200-400 rpm and a immersion temperature of 30-50° C. After immersion, the intermediate or modified perfluoroether rubber is aged and dried, and then heat-treated in an inert atmosphere for 2-3 hours at a heat treatment temperature of 250-300° C. The method utilizes an ultrasonic dispersion method to coat an intermediate or modified perfluoroether rubber with a nanofiller, specifically comprising the following steps: ultrasonically treating the intermediate or modified perfluoroether rubber in a sol for 30-60 minutes at a power of 300W-600W and controlling the temperature at 30-50°C.

Images