Modified composite conductive fluororubber as well as preparation method and application thereof

Abstract

The invention provides modified composite conductive fluororubber as well as a preparation method and application thereof, and the modified composite conductive fluororubber is prepared from fluororubber, 3, 4-ethylenedioxythiophenol, a single-walled carbon nanotube, metal oxide powder, carbon black, a silane coupling agent, an anti-aging agent, a plasticizer, stearic acid, sulfur and an accelerant according to the mass ratio of the fluororubber, the 3, 4-ethylenedioxythiophenol, the single-walled carbon nanotube, the metal oxide powder, the carbon black, the silane coupling agent, the anti-aging agent, the plasticizer, the stearic acid, the sulfur and the accelerant. The conductive fluororubber material with low volume resistivity, good tensile strength and elongation at break can be obtained, and the conductive fluororubber material shows excellent toughness characteristic. At present, the device is mainly applied to a liquid crystal semiconductor drying procedure and can effectively lead out static electricity in a product production process and reduce damage of the static electricity to products. The conductive fluororubber material disclosed by the invention has a wide application prospect, can meet the requirements on conductivity and mechanical properties, and provides reliable protection and performance expression.

Description

Technical Field

[0001] This application belongs to the field of materials science and technology, and in particular relates to a composite conductive fluororubber modified with 3,4-ethylenedioxythiophenol and single-walled carbon nanotubes, its preparation method and application. Background Technology

[0002] Composite conductive rubber materials are functional composite materials made by filling a rubber matrix with conductive fillers. These conductive fillers can be conductive particles, fibers, or additives, possessing excellent conductivity and forming a conductive network within the material. Utilizing the conductivity of composite conductive rubber materials, the following protective effects can be provided: Composite conductive rubber materials can effectively dissipate static electricity, preventing static accumulation and charge instability. In scenarios requiring protection against electrostatic interference or static-induced sparks, the use of conductive rubber materials can protect equipment and personnel safety. Composite conductive rubber materials can effectively shield electromagnetic radiation and block external electromagnetic waves from interfering with equipment, circuits, or electronic components. This material is widely used in electronic and communication equipment, ensuring stable equipment operation and reducing the impact of electromagnetic interference on other equipment. Conductive rubber materials have chemical corrosion resistance, protecting equipment or components from chemical corrosion. This is crucial for equipment used in chemical industries or environments exposed to chemical corrosion. Conductive fluororubber is a type of fluororubber material with conductive properties, formed by filling a fluororubber matrix with conductive particles, fibers, or additives to create a conductive network.

[0003] However, the insufficient conductivity and poor mechanical properties of existing conductive rubbers can lead to problems such as poor contact of equipment parts, poor sealing, and easy wear or breakage of materials during use, thereby affecting the normal operation and service life of the equipment. Summary of the Invention

[0004] This application is made in view of the above-mentioned issues, and its purpose is to provide a composite conductive fluororubber modified with 3,4-ethylenedioxythiophenol and single-walled carbon nanotubes, its preparation method and application, in order to solve the problems of insufficient conductivity and mechanical properties in the prior art.

[0005] The first aspect of this application provides a modified composite conductive fluororubber, comprising the following raw materials in parts by weight: 100-120 parts of fluororubber, 1-5 parts of 3,4-ethylenedioxythiophenol, 0.4-0.8 parts of single-walled carbon nanotubes, 2.0-9.0 parts of metal oxide powder, 23-25 ​​parts of carbon black, 2-3 parts of silane coupling agent, 3.0-4.0 parts of antioxidant, 3.5-5 parts of plasticizer, 2-4 parts of stearic acid, 0.3-1 part of sulfur, and 0.8-2.3 parts of accelerator.

[0006] In any embodiment, the metal oxide powder is one or more of titanium dioxide, tin dioxide, aluminum oxide, and zinc oxide.

[0007] In any embodiment, the carbon black is one or more of furnace black, acetylene black, and silica.

[0008] In any embodiment, the silane coupling agent is one or more of Si75, A-174, KH570, Si69, Si266, KH550, KH560, and Si75C.

[0009] In any embodiment, the antioxidant is one or more of antioxidant MBI, antioxidant 2246, antioxidant E, antioxidant RD, antioxidant 4020, antioxidant DD, antioxidant T501, and antioxidant 4010.

[0010] In any embodiment, the plasticizer is diethylhexanoate (DOP), octanoate (DINP), decanoate (DIDP), phthalocyanine blue plasticizer (Pc blue plasticizer), phosphate ester plasticizer (TBEP, TBP, TEHP), silicone oil plasticizer (PDMS), fatty acid ester plasticizer (such as Cetyl Palmitate, Stearates), or coal tar plasticizer (CTBN).

[0011] In any embodiment, the accelerator is one or more of accelerator DM, accelerator TMTD, accelerator TMTM, accelerator CZ, accelerator MBT, accelerator CBS, and accelerator TMT.

[0012] A second aspect of this application also provides a method for preparing a modified composite conductive fluororubber, comprising the following steps:

[0013] (1) Raw material preparation: The weight parts of the raw materials added are as follows: 100-120 parts of fluororubber, 1-5 parts of 3,4-ethylenedioxythiophenol, 0.4-0.8 parts of single-walled carbon nanotubes, 2.0-9.0 parts of metal oxide powder, 23-25 ​​parts of carbon black, 2-3 parts of silane coupling agent, 3.0-4.0 parts of antioxidant, 3.5-5 parts of plasticizer, 2-4 parts of stearic acid, 1-4 parts of antioxidant, 0.3-1 part of sulfur, and 0.8-2.3 parts of accelerator;

[0014] (2) Pretreatment: The fluororubber raw material is chopped into appropriate blocks to remove impurities and improve plasticity. Then it is mixed evenly with appropriate amounts of plasticizer, antioxidant, accelerator, etc.

[0015] (3) Feeding: The pretreated fluororubber raw material and other additives in (1) are fed into the rubber mixing machine together;

[0016] (4) Mixing: Through the high temperature and high shear of the mixing machine, the fluororubber raw material is continuously heated, cut, and extruded to ensure uniform mixing with the additives. During this process, vulcanizing agents and other auxiliary agents can be gradually added as needed;

[0017] (5) Plasticizing: The mixed rubber is plasticized at appropriate temperature and time.

[0018] In any embodiment, the plasticizing is completed by extrusion and calendering; specifically, the internal mixer speed is 50-700 r / min, the initial temperature of the internal mixer is 45-50℃, the temperature is increased to 70-90℃ at a rate of 3℃ / min, stirring is continued for 5-20 min, vacuum is drawn, and the negative pressure is maintained at 0.8-1.2MPa to produce sheets, which are then placed in a cooler to cool. Once the temperature of the sheets is below 40℃ after cooling, the masterbatch is obtained.

[0019] In any embodiment, the plasticizing process is subjected to vulcanization treatment for 15-25 minutes at a vulcanization temperature of 160-180°C, followed by debinding, sheeting, cooling, and standing for 2 days to obtain the finished product.

[0020] In any embodiment, the finished product obtained in step (5) is cut and shaped as follows: the plasticized conductive fluororubber is cut into blocks of appropriate size as needed, and then processed by calendering, extrusion, pressing and other processes to produce the required conductive fluororubber products.

[0021] A third aspect of this application provides the application of a modified composite conductive fluororubber in a liquid crystal semiconductor drying process.

[0022] The molded conductive fluororubber parts are installed in their respective positions within the liquid crystal semiconductor drying equipment, ensuring good contact with the semiconductor devices. Typically, these parts are placed in seals, gaskets, or other areas requiring anti-static protection.

[0023] Applications: Temperature Control: During the drying process of liquid crystal semiconductors, the temperature should be strictly controlled within the temperature resistance range of the fluororubber, typically between 100℃ and 150℃, to ensure that the material does not undergo thermal degradation. Humidity Control: Due to the low hygroscopicity of fluororubber, it can be used in low-humidity environments. However, to ensure the drying effect of the semiconductor, the humidity during the drying process is usually controlled below 1%. Electrostatic Protection: During application, ensure good contact between the conductive fluororubber and the semiconductor equipment to exert its antistatic effect.

[0024] The beneficial effects of this invention are as follows: The conductive fluororubber used in this invention functions as a composite conductive rubber material, including dissipating static electricity, shielding electromagnetic radiation, and protecting against electro-corrosion. It effectively prevents the accumulation and instability of static electricity, reducing the dangers of electrostatic interference and sparks. Simultaneously, the conductive fluororubber material can shield external electromagnetic radiation, ensuring stable equipment operation, and possesses chemical corrosion resistance, protecting equipment from chemical corrosion. Conductive fluororubber plays a crucial role in electrostatic protection, electromagnetic protection, and electro-corrosion protection, and is widely used in various fields to reduce or eliminate the hazards caused by electromagnetic interference, radiation, and static electricity. By modifying the fluororubber, its conductivity is improved while maintaining its excellent mechanical properties, further enhancing its practicality and reliability. The high-conductivity preparation method provided by this invention facilitates the large-scale mass production of conductive fluororubber. Attached Figure Description

[0025] Figure 1 This is a product image of the modified composite conductive fluororubber of this application. Detailed Implementation

[0026] The following detailed description, with appropriate reference to the accompanying drawings, discloses embodiments of the 3,4-ethylenedioxythiophenol and single-walled carbon nanotube modified composite conductive fluororubber, their preparation methods, and applications. However, unnecessary details may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0027] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0028] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0029] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0030] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0031] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0032] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0033] A composite conductive fluororubber modified with 3,4-ethylenedioxythiophenol and single-walled carbon nanotubes comprises the following components by weight: 100-120 parts fluororubber, 1-5 parts 3,4-ethylenedioxythiophenol, 0.4-0.8 parts single-walled carbon nanotubes, 2.0-9.0 parts metal oxide powder, 23-25 ​​parts carbon black, 2-3 parts silane coupling agent, 3.0-4.0 parts antioxidant, 3.5-5 parts plasticizer, 2-4 parts stearic acid, 0.3-1 part sulfur, and 0.8-2.3 parts accelerator.

[0034] Conductive fluororubber functions as a composite conductive rubber material, including dissipating static electricity, shielding electromagnetic radiation, and protecting against electrostatic corrosion. It effectively prevents the accumulation and instability of static electricity, reducing the dangers of electrostatic interference and sparks. Simultaneously, conductive fluororubber materials can shield external electromagnetic radiation, ensuring stable equipment operation, and possess chemical corrosion resistance, protecting equipment from chemical corrosion. Conductive fluororubber materials play a crucial role in electrostatic protection, electromagnetic protection, and electrostatic corrosion protection, and are widely used in various fields to reduce or eliminate the hazards caused by electromagnetic interference, radiation, and static electricity.

[0035] Adding 3,4-ethylenedioxythiophenol to fluororubber significantly improves its overall performance. Firstly, the conductivity of 3,4-ethylenedioxythiophenol significantly enhances the conductivity of fluororubber, making it suitable for antistatic applications. Secondly, the anti-corrosion properties of 3,4-ethylenedioxythiophenol, combined with the inherent chemical resistance of fluororubber, result in superior performance of this composite material in corrosive environments. Furthermore, 3,4-ethylenedioxythiophenol improves the mechanical properties of fluororubber, enhancing its durability under high stress and pressure. Simultaneously, the thermal stability of 3,4-ethylenedioxythiophenol improves the stability of fluororubber at high temperatures, extending its service life. Finally, the flame-retardant properties of 3,4-ethylenedioxythiophenol make this composite material excellent for fire-resistant applications. Therefore, the composite material of fluororubber and 3,4-ethylenedioxythiophenol has wider and more effective applications in antistatic, anti-corrosion, high-strength, and fire-resistant properties, making it suitable for various fields such as electronics, chemicals, and aerospace.

[0036] Adding single-walled carbon nanotubes to fluororubber can significantly improve the overall properties of the material, including enhanced electrical conductivity, mechanical strength, thermal stability, and chemical resistance. These improvements make this modified fluororubber more promising for applications in demanding fields such as electronics, antistatic agents, chemicals, and aerospace.

[0037] This invention utilizes modification of fluororubber to improve its electrical conductivity. The goal of this technology is to address the insufficient conductivity issues in existing technologies. Simultaneously, this method maintains the excellent mechanical properties of conductive fluororubber, further enhancing its practicality and reliability. Adding 3,4-ethylenedioxythiophenol to fluororubber can improve the material's conductivity, corrosion resistance, mechanical properties, and thermal stability, as well as enhance its flame retardancy. This makes the application of fluororubber in antistatic, anti-corrosion, high-strength, and fire-retardant applications more widespread and effective. Adding single-walled carbon nanotubes can significantly improve the conductivity, mechanical strength, thermal stability, and chemical resistance of fluororubber. Furthermore, this invention provides a method for preparing highly conductive fluororubber, facilitating its large-scale production.

[0038] Adding too much 3,4-ethylenedioxythiophenol may lead to an overly dense material, preventing electrons from flowing freely and thus reducing conductivity; conversely, adding too little may increase porosity in the material, also affecting electron transport and reducing conductivity. Therefore, strictly and precisely controlling the amount of 3,4-ethylenedioxythiophenol added is crucial for maintaining the conductivity of conductive fluororubber.

[0039] The amount of single-walled carbon nanotubes (SUVs) added significantly affects the conductivity of conductive fluororubber. Adding more SUVs may enhance the interactions between nanotubes, forming more conductive channels and thus improving conductivity. However, excessive addition may cause nanotubes to aggregate and accumulate, forming non-conductive clumps and reducing conductivity. Conversely, adding too few SUVs may restrict the formation of conductive channels, thereby reducing conductivity.

[0040] The single-walled carbon nanotubes are prepared by the following method: First, 1-5 g of ferric chloride, 50-200 mL of benzyl alcohol, 1-6 mL of thiophene, and 200-500 μL of water are mixed in a specific ratio. Next, the mixture is heated with ethylene reducing gas at 1000-8000 sccm and argon gas at 4000 sccm to maintain suitable temperature and pressure. The mixed gas flows into the furnace tube and is introduced into a high-temperature furnace at 1180-1200℃ at a flow rate of 120-150 μL / min. Samples are taken every 30 minutes to prevent prolonged deposition in the high-temperature zone, which would reduce quality. The formation temperature is typically between 1150-1250℃. The deposition temperature should be maintained at 500-850℃. Subsequent operations include calcining the crude product in air at 1400-1600℃ for 1-2 hours to remove surface amorphous carbon and improve the graphitization level. During this process, oxygen in the air oxidizes the amorphous carbon into carbon dioxide or carbon monoxide, which is then released. Then, under the same high-temperature conditions, the product is calcined at a carbon dioxide flow rate of 1000-1500 sccm for 1-2 hours to produce metallic iron and carbon dioxide, the latter of which can be recycled during the purification process. Finally, the crude product is immersed in a 3-5M hydrochloric acid or sulfuric acid solution and stirred at 50-70℃ for 5-10 hours to effectively remove iron impurities. Considering the stability of iron oxide, the initial carbon monoxide reduction promotes the metal removal efficiency.

[0041] The single-walled carbon nanotubes were prepared as follows: First, 2 g of ferric chloride, 50 mL of benzyl alcohol, 1 mL of thiophene, and 200 μL of water were mixed. Then, a mixture of ethylene (8000 sccm) and argon (4000 sccm) was introduced into a high-temperature furnace at 1180 °C, with a flow rate of 120 μL / min, and samples were taken every 30 min. Subsequently, the product was calcined in air at 1400 °C for 2 h to remove amorphous carbon, and then calcined again at 1500 sccm of carbon dioxide for 2 h to generate metallic iron and carbon dioxide. Finally, the product was immersed in a 3M hydrochloric acid or sulfuric acid solution and stirred at 50 °C for 10 h to remove iron impurities.

[0042] The single-walled carbon nanotubes prepared by the above method have a conductivity of 0.001085 Ω*cm under a test condition of 10 MPa, and the conductivity of the single-walled carbon nanotube conductive paste is 3904 S / cm, which is 11.5% higher than that of commercially available OCSiAl.

[0043] In a further improvement, the metal oxide powder is one or more of titanium dioxide, tin dioxide, aluminum oxide, and zinc oxide.

[0044] Further improvements are made, wherein the carbon black is one or more of furnace black, acetylene black, and silica.

[0045] In a further improvement, the silane coupling agent is one or more of Si75, A-174, KH570, Si69, Si266, KH550, KH560, and Si75C.

[0046] Further improvements are made, wherein the antioxidant is one or more of antioxidants MBI, antioxidant 2246, antioxidant E, antioxidant RD, antioxidant 4020, antioxidant DD, antioxidant T501, and antioxidant 4010.

[0047] Further improvements include the following plasticizers: diethylhexanoate (DOP), octanoate (DINP), decanoate (DIDP), phthalocyanine blue plasticizer (Pc blue plasticizer), phosphate ester plasticizers (TBEP, TBP, TEHP), silicone oil plasticizers (PDMS), fatty acid ester plasticizers (such as Cetyl Palmitate, Stearates), and coal tar-based plasticizers (CTBN).

[0048] A further improvement is provided: a method for preparing a composite conductive fluororubber modified with 3,4-ethylenedioxythiophenol and single-walled carbon nanotubes, characterized in that the accelerator is one or more of accelerators DM, TMTD, TMTM, CZ, MBT, CBS, and TMT.

[0049] A method for preparing a composite conductive fluororubber modified with 3,4-ethylenedioxythiophenol and single-walled carbon nanotubes, the process comprising the following steps:

[0050] 1) Pretreatment: Chop 100-120 parts by weight of fluororubber raw material into appropriate blocks, remove impurities and improve plasticity. Then mix it evenly with an appropriate amount of antioxidant 3.0-4.0 parts by weight, plasticizer 3.5-5 parts by weight, and accelerator 0.8-2.3 parts by weight.

[0051] 2) Feeding: The pretreated fluororubber raw rubber, 1-5 parts by weight of 3,4-ethylenedioxythiasol, 0.4-0.8 parts by weight of single-walled carbon nanotubes, 2.0-9.0 parts by weight of metal oxide powder, 23-25 ​​parts by weight of carbon black, 2-3 parts by weight of silane coupling agent, 2-4 parts by weight of stearic acid, 1-4 parts by weight of antioxidant, and 0.3-1 parts by weight of sulfur are fed into the rubber mixing machine.

[0052] 3) Mixing: Through the high temperature and high shear of the mixing machine, the fluororubber raw material is continuously heated, cut, and extruded to ensure uniform mixing with the additives. During this process, vulcanizing agents and other auxiliary agents can be gradually added as needed.

[0053] 4) Plasticizing: The mixed rubber is plasticized at 150℃ for 1 hour. During this process, the rubber molecular chains are stretched, broken, and reorganized, giving it elasticity and processability. This is usually accomplished through extrusion, calendering, etc. The internal mixer speed is 60 r / min, the initial temperature of the internal mixer is 50℃, and the temperature is increased to 80℃ at a rate of 3℃ / min. Stirring continues for 10 minutes, vacuum is applied, and the negative pressure is maintained at 1MPa before sheeting. The sheet is then placed in a cooler to cool. Once the temperature of the sheet is below 40℃, the masterbatch is obtained. Throughout the plasticizing process, parameters such as temperature, time, and shear force need to be strictly controlled to ensure the modification of the rubber molecular chains and the processing effect. Simultaneously, subsequent vulcanization or other treatments are carried out to obtain the final conductive fluororubber product. The vulcanization time is 20 minutes, the vulcanization temperature is 170℃, the rubber is discharged, sheeted, cooled, and left to stand for 2 days to obtain the finished product.

[0054] Cutting and molding: The plasticized conductive fluororubber is cut into blocks of appropriate size as needed, and then processed through calendering, extrusion, pressing and other processes to produce the required conductive fluororubber products.

[0055] Example

[0056] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0057] Example 1:

[0058] The present invention adopts the following technical solution: 100 parts by weight of fluororubber, 0.4 parts by weight of single-walled carbon nanotubes, 5 parts by weight of 3,4-ethylenedioxythiophenol, 2.0 parts by weight of zinc oxide powder, 23 parts by weight of silica, 2 parts by weight of Si75 silane coupling agent, 3.0 parts by weight of antioxidant RD and antioxidant DD, 3.5 parts by weight of coal tar plasticizer (CTBN), 2 parts by weight of stearic acid, 0.3 parts by weight of sulfur, and 0.8 parts by weight of accelerator DM.

[0059] The preparation process is as follows:

[0060] Pretreatment: The fluororubber raw material is chopped into appropriate blocks to remove impurities and improve plasticity. Then it is mixed evenly with appropriate amounts of plasticizer, antioxidant, and accelerator.

[0061] Feeding: The pretreated fluororubber raw material and other additives are fed into the rubber mixing machine.

[0062] Mixing: Through the high temperature and high shear of the mixing machine, the fluororubber raw material is continuously heated, cut, and extruded to ensure uniform mixing with additives. During this process, vulcanizing agents and other auxiliary agents can be gradually added as needed.

[0063] Plasticizing: The mixed rubber is plasticized at 150℃ for 1 hour. During this process, the rubber molecular chains are stretched, broken, and reorganized, giving it elasticity and processability. This is usually accomplished through extrusion, calendering, and other methods. The internal mixer speed is 60 r / min, the initial temperature of the internal mixer is 50℃, and the temperature is increased to 80℃ at a rate of 3℃ / min. Stirring continues for 10 minutes, vacuum is applied, and the negative pressure is maintained at 1 MPa before sheeting. The sheet is then placed in a cooler to cool. Once the temperature of the sheet is below 40℃, the masterbatch is obtained. Throughout the plasticizing process, parameters such as temperature, time, and shear force need to be strictly controlled to ensure the modification of the rubber molecular chains and the processing effect. Simultaneously, subsequent vulcanization or other treatments are carried out to obtain the final conductive fluororubber product. The vulcanization time is 20 minutes, the vulcanization temperature is 170℃, the rubber is discharged, sheeted, cooled, and allowed to stand for 2 days to obtain the finished product.

[0064] Cutting and molding: The plasticized conductive fluororubber is cut into blocks of appropriate size as needed, and then processed through calendering, extrusion, pressing and other processes to produce the required conductive fluororubber products.

[0065] Example 2:

[0066] The present invention adopts the following technical solution: 100 parts by weight of fluororubber, 0.6 parts by weight of single-walled carbon nanotubes, 5 parts by weight of 3,4-ethylenedioxythiophenol, 2.0 parts by weight of titanium dioxide powder, 23 parts by weight of acetylene black, 2 parts by weight of Si69 silane coupling agent, 3.0 parts by weight of antioxidant MBI and antioxidant 2246, 3.5 parts by weight of diethylhexanoate (DOP), 2 parts by weight of stearic acid, 0.3 parts by weight of sulfur, and 0.8 parts by weight of accelerator CZ.

[0067] The preparation process is as follows:

[0068] Pretreatment: The fluororubber raw material is chopped into appropriate blocks to remove impurities and improve plasticity. Then it is mixed evenly with appropriate amounts of plasticizers, antioxidants, accelerators, etc.

[0069] Feeding: The pretreated fluororubber raw material is fed into the rubber mixing machine along with other additives (such as fillers, vulcanizing agents, etc.).

[0070] Mixing: Through the high temperature and high shear of the mixing machine, the fluororubber raw material is continuously heated, cut, and extruded to ensure uniform mixing with additives. During this process, vulcanizing agents and other auxiliary agents can be gradually added as needed.

[0071] Plasticizing: The mixed rubber is plasticized at 150℃ for 1 hour. During this process, the rubber molecular chains are stretched, broken, and reorganized, giving it elasticity and processability. This is usually accomplished through extrusion, calendering, and other methods. The internal mixer speed is 60 r / min, the initial temperature of the internal mixer is 50℃, and the temperature is increased to 80℃ at a rate of 3℃ / min. Stirring continues for 10 minutes, vacuum is applied, and the negative pressure is maintained at 1 MPa before sheeting. The sheet is then placed in a cooler to cool. Once the temperature of the sheet is below 40℃, the masterbatch is obtained. Throughout the plasticizing process, parameters such as temperature, time, and shear force need to be strictly controlled to ensure the modification of the rubber molecular chains and the processing effect. Simultaneously, subsequent vulcanization or other treatments are carried out to obtain the final conductive fluororubber product. The vulcanization time is 20 minutes, the vulcanization temperature is 170℃, the rubber is discharged, sheeted, cooled, and allowed to stand for 2 days to obtain the finished product.

[0072] Cutting and molding: The plasticized conductive fluororubber is cut into blocks of appropriate size as needed, and then processed through calendering, extrusion, pressing and other processes to produce the required conductive fluororubber products.

[0073] Example 3:

[0074] The present invention adopts the following technical solution: 120 parts by weight of fluororubber, 0.8 parts by weight of single-walled carbon nanotubes, 5 parts by weight of 3,4-ethylenedioxythiophenol, 9.0 parts by weight of tin dioxide powder, 25 parts by weight of furnace black, 3 parts by weight of KH570 silane coupling agent, 4.0 parts by weight of antioxidant E and antioxidant RD, 5 parts by weight of octanoic acid ester (DINP), 4 parts by weight of stearic acid, 1 part by weight of sulfur, and 2.3 parts by weight of accelerator TMTD.

[0075] The preparation process is as follows:

[0076] Pretreatment: The fluororubber raw material is chopped into appropriate blocks to remove impurities and improve plasticity. Then it is mixed evenly with appropriate amounts of plasticizers, antioxidants, accelerators, etc.

[0077] Feeding: The pretreated fluororubber raw material is fed into the rubber mixing machine along with other additives (such as fillers, vulcanizing agents, etc.).

[0078] Mixing: Through the high temperature and high shear of the mixing machine, the fluororubber raw material is continuously heated, cut, and extruded to ensure uniform mixing with additives. During this process, vulcanizing agents and other auxiliary agents can be gradually added as needed.

[0079] Plasticizing: The mixed rubber is plasticized at 150℃ for 1 hour. During this process, the rubber molecular chains are stretched, broken, and reorganized, giving it elasticity and processability. This is usually accomplished through extrusion, calendering, and other methods. The internal mixer speed is 60 r / min, the initial temperature of the internal mixer is 50℃, and the temperature is increased to 80℃ at a rate of 3℃ / min. Stirring continues for 10 minutes, vacuum is applied, and the negative pressure is maintained at 1 MPa before sheeting. The sheet is then placed in a cooler to cool. Once the temperature of the sheet is below 40℃, the masterbatch is obtained. Throughout the plasticizing process, parameters such as temperature, time, and shear force need to be strictly controlled to ensure the modification of the rubber molecular chains and the processing effect. Simultaneously, subsequent vulcanization or other treatments are carried out to obtain the final conductive fluororubber product. The vulcanization time is 20 minutes, the vulcanization temperature is 170℃, the rubber is discharged, sheeted, cooled, and allowed to stand for 2 days to obtain the finished product.

[0080] Cutting and molding: The plasticized conductive fluororubber is cut into blocks of appropriate size as needed, and then processed through calendering, extrusion, pressing and other processes to produce the required conductive fluororubber products.

[0081] Comparative Example 1:

[0082] The only difference between this scheme and Example 2 is the addition of 0.2g of single-walled carbon nanotubes.

[0083] Comparative Example 2:

[0084] The only difference between this scheme and Example 2 is the addition of 0.8g of single-walled carbon nanotubes.

[0085] Comparative Example 3:

[0086] The only difference between this scheme and Example 2 is that it does not add single-walled carbon nanotubes.

[0087] Comparative Example 4:

[0088] The only difference between this scheme and Example 2 is that 3,4-ethylenedioxythiophenol is not added.

[0089] Comparative Example 5:

[0090] The only difference between this scheme and Example 2 is the addition of 10 parts of 3,4-ethylenedioxythiophenol.

[0091] Comparative Example 6:

[0092] The only difference between this scheme and Example 2 is that it does not add single-walled carbon nanotubes and 3,4-ethylenedioxythiophenol.

[0093] Performance test results of conductive rubber prepared in the examples and comparative examples:

[0094] Table 1

[0095]

[0096] Table 2

[0097]

[0098]

[0099] Adding single-walled carbon nanotubes (SWCNTs) to rubber affects its electrical conductivity and tensile properties; both excessive and insufficient addition will degrade these properties. Specifically, too little SWCNTs cannot form a complete conductive network and fully exert their reinforcing effect, while excessive addition will lead to agglomeration, uneven dispersion, and processing difficulties, affecting the tensile and electrical properties of the rubber. Therefore, it is necessary to experimentally determine the optimal amount of SWCNTs to achieve the most ideal electrical conductivity and tensile properties. Adding 3,4-ethylenedioxythiophenol (PANI) to rubber also significantly impacts its electrical conductivity and tensile properties. Excessive addition will cause agglomeration and processing difficulties, thus reducing electrical conductivity and affecting tensile properties; insufficient addition will result in an incomplete conductive network and insignificant reinforcing effect, similarly affecting electrical conductivity and tensile properties.

[0100] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A modified composite conductive fluoroelastomer characterized in that, The raw material composition comprises the following weight parts: fluoro rubber 100-120 parts, 3,4-ethylenedioxythiophene 1-5 parts, single-walled carbon nanotube 0.4-0.8 parts, metal oxide powder 2.0-9.0 parts, carbon black 23-25 parts, silane coupling agent 2-3 parts, antioxidant 3.0-4.0 parts, plasticizer 3.5-5 parts, stearic acid 2-4 parts, sulfur 0.3-1 part, accelerator 0.8-2.3 parts.

2. The modified composite conductive fluororubber according to claim 1, wherein The metal oxide powder is one or several of titanium dioxide, tin dioxide, aluminum oxide, zinc oxide.

3. The modified composite conductive fluororubber of claim 1, wherein The carbon black is one or several of furnace black, acetylene black, white carbon black.

4. The modified composite conductive fluororubber of claim 1, wherein The silane coupling agent is one or several of Si75, A-174, KH570, Si69, Si266, KH550, KH560, Si75C.

5. The modified composite conductive fluororubber of claim 1, wherein The antioxidant is one or several of antioxidant MBI, antioxidant 2246, antioxidant E, antioxidant RD, antioxidant 4020 antioxidant DD, antioxidant T501, antioxidant 4010.

6. The modified composite conductive fluororubber of claim 1 wherein, The plasticizer is diethylhexyl adipate (DOP), octyl adipate (DINP), decanoate (DIDP), phthalocyanine blue plasticizer (Pc blue plasticizer), phosphate plasticizer (TBEP, TBP, TEHP), silicone oil plasticizer (PDMS), fatty acid ester plasticizer (such as Cetyl Palmitate, Stearates), coal tar plasticizer (CTBN).

7. The modified composite conductive fluororubber of claim 1 wherein, The accelerator is one or several of accelerator DM, accelerator TMTD, accelerator TMTM, accelerator CZ, accelerator MBT, accelerator CBS, accelerator TMT.

8. A preparation method of modified composite conductive fluoro rubber, comprising the following steps: (1) raw material preparation: the addition weight parts of raw materials are as follows: fluoro rubber 100-120 parts, 3,4-ethylenedioxythiophene 1-5 parts, single-walled carbon nanotube 0.4-0.8 parts, metal oxide powder 2.0-9.0 parts, carbon black 23-25 parts, silane coupling agent 2-3 parts, antioxidant 3.0-4.0 parts, plasticizer 3.5-5 parts, stearic acid 2-4 parts, antioxidant 1-4 parts, sulfur 0.3-1 part, accelerator 0.8-2.3 parts; (2) pretreatment: the fluoro rubber raw rubber is cut into appropriate blocks, impurities are removed, and plasticity is improved. Then it is mixed uniformly with appropriate amount of plasticizer, antioxidant, accelerator and the like. (3) feeding: the pretreated fluoro rubber raw rubber and other additives in (1) are fed into a rubber mixing machine together; (4) mixing: through the high temperature and high shear action of the mixing machine, the fluoro rubber raw rubber is continuously heated, cut and extruded to mix uniformly with the additives. In this process, vulcanizing agent and other auxiliary agents can be gradually added as needed; (5) plasticizing: the mixed rubber is plasticized under appropriate temperature and time.

9. The modified composite conductive fluororubber of claim 8, wherein The plastication is completed by extrusion and calendering; specifically, the speed of the internal mixer is 50-700 r / min, the initial feeding temperature of the internal mixer is 45-50 DEG C, the temperature is increased at a speed of 3 DEG C / min to 70-90 DEG C, then the stirring is continued for 5-20 min, vacuum is extracted, the negative pressure is maintained at 0.8-1.2 MPa, the sheet is discharged, then the sheet is placed in a cooling machine for cooling, the temperature of the sheet after cooling is lower than 40 DEG C, the masterbatch is obtained, and subsequent vulcanization treatment is carried out, the vulcanization time is 15-25 min, the vulcanization temperature is 160-180 DEG C, the rubber is discharged, the sheet is discharged, cooled, and placed for 2 days, and the finished product is prepared.

10. Use of the conductive fluororubber obtained according to the method for preparing the modified composite conductive fluororubber according to any one of claims 1-7 or according to any one of claims 8-9 in a liquid crystal semiconductor drying procedure.

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