A butyl rubber type TPV material and a method for preparing the same

Abstract

The application discloses a butyl rubber type TPV material and a preparation method thereof, and belongs to the technical field of polymer materials.The butyl rubber type TPV material is prepared from the following raw materials in parts by weight: polypropylene 10-60 parts, butyl rubber 80-110 parts, hydrogenated butyl nitrile rubber 5-10 parts, stannous chloride 0.5-2 parts, vulcanizing agent 5-10 parts, anti-aging agent 0.6-1.2 parts, talc 20-30 parts and paraffin oil 10-20 parts.The TPV material has excellent temperature resistance, oil resistance and high air tightness, and has good deformation recovery performance and good thermoplastic processing performance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a butyl rubber type TPV material and its preparation method. Background Technology

[0002] TPV (Thermoplastic Vulcanizate) is a type of plasticizable elastomer material. Its composition mainly includes a cross-linked elastomer as the dispersed phase and a thermoplastic polymer as the continuous phase. Therefore, it combines the advantages of both rubber and plastic, and has the advantages of convenient molding and processing, material recyclability, and excellent comprehensive performance.

[0003] Currently, commercially available TPV materials all use polyolefin plastics as the continuous phase and EPDM rubber and nitrile rubber as the dispersed phases. Their oil resistance, airtightness, abrasion resistance, and heat resistance are insufficient to meet increasingly demanding technical requirements. Furthermore, the vulcanization systems used in TPV preparation can be broadly categorized into sulfur vulcanization systems, peroxide vulcanization systems, phenolic resin vulcanization systems, and sulfur-carrier vulcanization systems. Existing technologies mostly employ sulfur vulcanization and peroxide vulcanization systems for crosslinking vulcanization. However, TPV materials prepared using sulfur vulcanization systems exhibit significant color changes and a pungent odor; TPV prepared using peroxide vulcanization systems readily counteracts anti-aging agents, accelerating material aging.

[0004] Patent CN106939100A discloses a dynamically vulcanized flame-retardant acrylate TPV material. This TPV material is made from the following raw materials in parts by weight: 20-50 parts polypropylene, 20-60 parts EPDM rubber, 5-15 parts thermoplastic polyurethane elastomer, 15-30 parts flame retardant, 0.5-1.5 parts flow modifier, 0.2-0.6 parts crosslinking agent, 0.2-0.8 parts heat stabilizer, and 0.2-0.8 parts ultraviolet absorber. This dynamically vulcanized flame-retardant acrylate TPV material exhibits excellent flame retardancy, antibacterial properties, and good processability, making it easy to process and mold. This technology solves the problem of poor plasticity in flame-retardant TPVs. However, the dispersed phase used in this technology is EPDM rubber, which is a saturated rubber and not self-reinforcing, and has a low methyl content on the side, significantly reducing the TPV's shock absorption performance and damping properties, and also worsening its airtightness.

[0005] Patent CN110698755A discloses a thermoplastic acrylate TPV material, which is made from raw materials comprising the following parts by weight: 20-65 parts acrylate rubber; 10-50 parts polar thermoplastic elastomer; 1-3 parts vulcanization system; 10-30 parts plasticizing system; 10-30 parts filler system; 0.5-1 part anti-aging system; and 2-6 parts heat-stabilizing system. This thermoplastic acrylate TPV material exhibits excellent oil resistance, temperature resistance, and water resistance, and can be produced using thermoplastic processes such as injection molding, extrusion, and blow molding. It can be used in the manufacture of various oil-resistant seals, pipes, and oil-resistant cables. This technology solves the problems of existing oil-resistant rubbers being unable to undergo thermoplastic processing and existing TPVs having poor oil resistance. However, this technology uses a vulcanization system containing sulfur compounds and organic peroxides, failing to overcome the defects brought about by such vulcanizing agents. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a butyl rubber-based TPV material and its preparation method. The TPV material exhibits excellent heat resistance, oil resistance, and high air tightness, while also possessing good deformation recovery properties and good thermoplastic processing performance.

[0007] To achieve the above objectives, according to one aspect of the present invention, a butyl rubber type TPV material is provided, wherein the raw materials comprise, by weight, 10-60 parts of polypropylene, 80-110 parts of butyl rubber, 5-10 parts of hydrogenated nitrile rubber, 0.5-2 parts of stannous chloride, 5-10 parts of vulcanizing agent, 0.6-1.2 parts of anti-aging agent, 20-30 parts of talc, and 10-20 parts of paraffin oil.

[0008] In some embodiments, the polypropylene is random copolymer polypropylene, and the melt mass flow rate (MFR) of the polypropylene under test conditions of 230°C and 2.16 kg load is 7.0-8.0 g / 10 min.

[0009] In some embodiments, the butyl rubber is brominated butyl rubber and / or chlorinated butyl rubber.

[0010] In some embodiments, the vulcanizing agent is a phenolic resin vulcanizing agent.

[0011] In some embodiments, the anti-aging agent is a compound of phenolic antioxidants and phosphite antioxidants, with a compounding ratio of 1.5-2:3.

[0012] According to another aspect of the present invention, a method for preparing the above-mentioned butyl rubber type TPV material is also provided, comprising the following steps: (1) The polypropylene and anti-aging agent are added to the torque rheometer and mixed in proportion, and then butyl rubber, hydrogenated nitrile rubber, paraffin oil and talc are added and mixed evenly to obtain a rubber-plastic premix. (2) After cooling the rubber-plastic premix, add it to an open mixing mill, add the stannous chloride and vulcanizing agent at room temperature, mix evenly, take it out and cut it into strips, send it into a twin-screw extruder for dynamic vulcanization, and extrude to obtain semi-finished TPV material; (3) The semi-finished TPV material is placed on a flat vulcanizing machine for preheating, pressure holding and cooling, dehydration and drying, and vacuum sealing to obtain the butyl rubber type TPV material.

[0013] According to the preparation method of the present invention, in some embodiments, in step (1), the rotational speed of the torque rheometer is 60-65 rpm / min and the temperature is 180-185℃.

[0014] According to the preparation method of the present invention, in some embodiments, in step (2), the dynamic vulcanization conditions are: vulcanization temperature of 185-187℃ and extruder screw speed of 100-120rpm.

[0015] According to the preparation method of the present invention, in some embodiments, in step (3), the preheating temperature is 180-182°C and the preheating time is 10-15 min.

[0016] According to the preparation method of the present invention, in some embodiments, in step (3), the holding pressure is 10-12 MPa and the holding time is 3-5 min.

[0017] Compared with the prior art, the beneficial effects of the present invention are: (1) The present invention uses polypropylene as the continuous phase of TPV material, which can significantly improve the thermal properties, wear resistance, oil resistance and barrier properties of TPV material; uses butyl rubber and hydrogenated nitrile rubber as the dispersed phase of TPV material, which can significantly enhance the air tightness and shock absorption of TPV material and improve its damping properties; uses phenolic resin vulcanization system, which overcomes the defects caused by sulfur-containing compounds and organic peroxide vulcanizing agents, and significantly improves the oil resistance and barrier properties of TPV material; the present invention further controls the composition and content of raw materials, so that the butyl rubber type TPV material has excellent thermal properties, wear resistance, oil resistance and air tightness, and at the same time has good processability and deformation recovery. The molded TPV products can be used in harsh environments such as high sealing, oil contact and friction.

[0018] (2) The preparation method of the present invention can further improve the tensile strength and elastic modulus of the TPV material and reduce permanent compression deformation by controlling the dynamic vulcanization conditions, especially by controlling the vulcanization temperature and the screw speed of the extruder within a specific range, thereby ensuring that the TPV material has good processability and deformation recovery. Detailed Implementation

[0019] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0020] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0021] In this document, when describing embodiments or examples, it should be understood that it is not intended to limit the invention to those embodiments or examples. Rather, all alternatives, modifications, and equivalents of the methods and materials described herein are covered within the scope defined by the claims.

[0022] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0023] In this invention, dynamic vulcanization, as opposed to "static" vulcanization, refers to the process during which the mixture is subjected to shear forces.

[0024] This invention provides a butyl rubber type TPV material, the raw materials of which include: polypropylene, butyl rubber, hydrogenated nitrile rubber, stannous chloride, vulcanizing agent, anti-aging agent, talc powder and paraffin oil.

[0025] In this invention, the polypropylene comprises 10-60 parts by weight, preferably 30-60 parts, and more preferably 40-60 parts. In some embodiments, the polypropylene is a random copolymer polypropylene. In some embodiments, the melt flow rate (MFR) of the polypropylene under test conditions of 230°C and 2.16 kg load is 7.0-8.0 g / 10 min. This invention uses polypropylene as the continuous phase of the TPV material, which can significantly improve the thermal properties, frictional properties, oil resistance, and barrier properties of the TPV material.

[0026] In this invention, the butyl rubber comprises 80-110 parts by weight, preferably 90-110 parts. In some embodiments, the butyl rubber is brominated butyl rubber and / or chlorinated butyl rubber. In this invention, the butyl rubber serves as the dispersed phase of the TPV material, which can significantly enhance the airtightness and shock absorption of the TPV material, thereby improving its damping performance.

[0027] In this invention, the hydrogenated nitrile butadiene rubber comprises 5-10 parts by weight. It is understood that the weight percentage can be any specific value among 5, 6, 7, 8, 9, and 10 parts, or any value within the range of 5-10 parts. In this invention, the hydrogenated nitrile butadiene rubber, together with butyl rubber, serves as the dispersed phase of the TPV material. The two work synergistically to improve the airtightness and shock absorption of the TPV material, thereby improving its damping properties, while simultaneously ensuring the mechanical properties and oil resistance of the TPV material. Without the addition of hydrogenated nitrile butadiene rubber, the reinforcing properties of the TPV material will decrease, and its oil resistance will also be reduced.

[0028] In this invention, the stannous chloride is present in an amount of 0.5-2 parts by weight. It is understood that the weight percentage can be any specific value from 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.1 parts, 1.7 parts, 1.8 parts, 1.9 parts, or 2.0 parts, or any value within the range of 0.5-2 parts. In this invention, the stannous chloride acts as an accelerator to accelerate the coordination and crosslinking of the dispersed butyl rubber and hydrogenated nitrile rubber, thus accelerating vulcanization.

[0029] In this invention, the vulcanizing agent is 5-10 parts by weight. It is understood that the weight percentage can be any specific value among 5, 6, 7, 8, 9, and 10 parts, or any value within the range of 5-10 parts. In some embodiments, the vulcanizing agent is a phenolic resin vulcanizing agent. This invention uses a phenolic resin vulcanization system, overcoming the defects caused by sulfur-containing compounds and organic peroxide vulcanizing agents, and significantly improving the oil resistance and barrier properties of TPV materials.

[0030] In this invention, the anti-aging agent is present in an amount of 0.6-1.2 parts by weight. It is understood that the weight percentage can be any specific value selected from 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, and 1.2 parts, or any value within the range of 0.6-1.2 parts. In some embodiments, the anti-aging agent is a compound of phenolic antioxidants and phosphite antioxidants, with a compounding ratio of 1.5-2:3. Preferably, the anti-aging agent is a compound of antioxidant 1010 and antioxidant 168, with a compounding ratio of 2:3.

[0031] In this invention, the talc powder is present in an amount of 20-30 parts by weight. It is understood that the weight percentage can be any specific value from 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 parts, or any value within the range of 20-30 parts. This invention does not impose a specific limitation on the mesh size of the talc powder; talc powder with a conventional mesh size in the art can be used. In this invention, the talc powder serves as a filler to further improve the strength of the TPV material.

[0032] In this invention, the paraffin oil is 10-20 parts by weight. It can be understood that the weight can be any specific value among 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 parts, or any value within the range of 10-20 parts.

[0033] The inventors of this invention have discovered that by selecting specific dispersible and continuous phase materials, the butyl rubber type TPV material can possess excellent thermal properties, frictional properties, oil resistance, and airtightness, while also exhibiting good processability and deformation recovery. The molded TPV products can be used in harsh environments such as high sealing, oil contact, and friction.

[0034] According to another aspect of the present invention, a method for preparing the above-mentioned butyl rubber type TPV material is also provided, comprising the following steps: (1) The polypropylene and anti-aging agent are added to the torque rheometer and mixed in proportion, and then butyl rubber, hydrogenated nitrile rubber, paraffin oil and talc are added and mixed evenly to obtain a rubber-plastic premix. (2) After cooling the rubber-plastic premix, add it to an open mixing mill, add the stannous chloride and vulcanizing agent at room temperature, mix evenly, take it out and cut it into strips, send it into a twin-screw extruder for dynamic vulcanization, and extrude to obtain semi-finished TPV material; (3) The semi-finished TPV material is placed on a flat vulcanizing machine for preheating, pressure holding and cooling, dehydration and drying, and vacuum sealing to obtain the butyl rubber type TPV material.

[0035] In this invention, in step (1), the polypropylene and anti-aging agent are added to a torque rheometer in proportion and mixed, followed by the addition of butyl rubber, hydrogenated nitrile rubber, paraffin oil, and talc powder, and mixed evenly to obtain a rubber-plastic premix. In some embodiments, in step (1), the rotational speed of the torque rheometer is 60-65 rpm / min. It can be understood that the rotational speed can be any specific value among 60 rpm / min, 61 rpm / min, 62 rpm / min, 63 rpm / min, 64 rpm / min, and 65 rpm / min, or any value within the range of 60-65 rpm / min. In some embodiments, in step (1), the temperature of the torque rheometer is 180-185℃. It can be understood that the temperature can be any specific value among 180℃, 181℃, 182℃, 183℃, 184℃, and 185℃, or any value within the range of 180-185℃. In some embodiments, in step (1), the time for mixing the polypropylene and the anti-aging agent in the torque rheometer is 2-5 minutes. It can be understood that the time can be any specific value among 2 minutes, 3 minutes, 4 minutes, and 5 minutes, or any value within the range of 2-5 minutes.

[0036] In this invention, in step (2), the rubber-plastic premix is ​​cooled and added to an open-type mixer. Stannous chloride and a vulcanizing agent are added at room temperature. After mixing evenly, the mixture is taken out, cut into strips, and fed into a twin-screw extruder for dynamic vulcanization. The resulting material is a semi-finished TPV material. In some embodiments, in step (2), the dynamic vulcanization conditions are: a vulcanization temperature of 185-187℃, which can be understood as any specific value among 185℃, 186℃, and 187℃, or any value within the range of 185-187℃; and an extruder screw speed of 100-120 rpm, which can be understood as any specific value among 100 rpm, 110 rpm, and 120 rpm, or any value within the range of 100-120 rpm. The inventors of this invention have discovered that controlling the dynamic vulcanization conditions, particularly controlling the vulcanization temperature and the extruder screw speed within the specified range, can further improve the tensile strength and elastic modulus of the TPV material, reduce permanent compression deformation, and thus ensure that the TPV material has good processability and resistance to deformation recovery.

[0037] In this invention, in step (3), the semi-finished TPV material is placed on a flat vulcanizing machine for preheating, pressure holding, cooling, dehydration and drying, and vacuum sealing to obtain the butyl rubber type TPV material. In some embodiments, in step (3), the preheating temperature is 180-182℃ and the preheating time is 10-15min. It can be understood that the time can be any specific value among 10min, 11min, 12min, 13min, 14min, and 15min, or any value within the range of 10-15min. In some embodiments, in step (3), the pressure holding pressure is 10-12MPa and the pressure holding time is 3-5min. In some embodiments, in step (3), the dehydration and drying temperature is 156-158℃.

[0038] The present invention will be described in detail below through embodiments. It should be understood that the following embodiments are only used to further explain and illustrate the content of the present invention by way of example, and are not intended to limit the present invention.

[0039] The chemical additives used in the embodiments and comparative examples of this invention are all commercially available, and the specific information is as follows: Polypropylene: Grade W331, with a melt flow rate (MFR) of 7.0 g / 10 min under test conditions of 230℃ and 2.16 kg load; manufacturer: Singapore Polyolefins; Chlorinated butyl rubber: Grade 1204; manufacturer: Lanxess Chemical GmbH, Germany; Chlorinated butyl rubber: Grade 1068; manufacturer: ExxonMobil; Brominated butyl rubber: Grade 2030; manufacturer: Lanxess Chemical GmbH, Germany; Stannous chloride: Langfang Pengcai Fine Chemical Co., Ltd.; Phenolic resin vulcanizing agent: RT42 10. Manufacturer: Shandong Shengquan New Material Co., Ltd.; Anti-aging agent: a compound of antioxidant 1010 and antioxidant 168, with a compounding ratio of 2:3; Talc powder: 1200 mesh, manufacturer: Changzhou Deshuo Chemical Technology Co., Ltd.; Paraffin oil: manufacturer: Hengshui Aoda Chemical Rubber Co., Ltd.; Sulfur: manufacturer: Chongqing Zhichuang Chemical Co., Ltd.; Accelerator BZ: manufacturer: Jinan Hongteng Weiye New Material Co., Ltd.; Accelerator BM: manufacturer: Jinan Hongteng Weiye New Material Co., Ltd.; Zinc oxide: manufacturer: Hengshui Lianke Rubber & Plastics Trading Co., Ltd.

[0040] Example 1 The butyl rubber type TPV material described in this embodiment comprises the following raw materials by weight: 54 parts polypropylene, 100 parts chlorinated butyl rubber, 8 parts hydrogenated nitrile rubber, 2 parts stannous chloride, 10 parts phenolic resin vulcanizing agent, 0.8 parts anti-aging agent, 20 parts talc powder, and 10 parts paraffin oil.

[0041] The preparation method of the butyl rubber type TPV material includes the following steps: (1) Add the polypropylene and anti-aging agent to the torque rheometer and mix for 2 minutes. The speed of the torque rheometer is 60 rpm / min and the temperature is 180℃. Then add chlorinated butyl rubber, hydrogenated nitrile rubber, paraffin oil and talc powder and mix evenly to obtain rubber-plastic premix. (2) After cooling the rubber-plastic premix, add it to an open mixing mill, add the stannous chloride and phenolic resin vulcanizing agent at room temperature, mix evenly, take it out and cut it into strips, and send it into a twin-screw extruder for dynamic vulcanization. The vulcanization temperature is 185°C, the screw speed of the extruder is 100 rpm, and the semi-finished TPV material is obtained by extrusion. (3) The semi-finished TPV material is placed on a flat vulcanizing machine and preheated at 180°C for 10 minutes, then held under pressure for 3 minutes and cooled, dehydrated and dried, and vacuum sealed to obtain the butyl rubber type TPV material.

[0042] Example 2 The butyl rubber type TPV material described in this embodiment comprises the following raw materials by weight: 10 parts polypropylene, 80 parts brominated butyl rubber, 5 parts hydrogenated nitrile rubber, 0.5 parts stannous chloride, 5 parts phenolic resin vulcanizing agent, 0.6 parts anti-aging agent, 20 parts talc powder, and 10 parts paraffin oil.

[0043] The preparation method of the butyl rubber type TPV material includes the following steps: (1) Add the polypropylene and anti-aging agent to the torque rheometer and mix for 2 minutes. The torque rheometer is 65 rpm / min and the temperature is 185℃. Then add brominated butyl rubber, hydrogenated nitrile rubber, paraffin oil and talc powder and mix evenly to obtain rubber-plastic premix. (2) After cooling the rubber-plastic premix, add it to an open mixing mill, add the stannous chloride and phenolic resin vulcanizing agent at room temperature, mix evenly, take it out and cut it into strips, and send it into a twin-screw extruder for dynamic vulcanization. The vulcanization temperature is 187°C and the screw speed of the extruder is 120 rpm. The semi-finished TPV material is obtained by extrusion. (3) The semi-finished TPV material is placed on a flat vulcanizing machine and preheated at 182°C for 10 minutes, then held under pressure for 5 minutes and cooled, dehydrated and dried, and vacuum sealed to obtain the butyl rubber type TPV material.

[0044] Example 3 The butyl rubber type TPV material described in this embodiment comprises the following raw materials by weight: 60 parts polypropylene, 110 parts chlorinated butyl rubber, 10 parts hydrogenated nitrile rubber, 2 parts stannous chloride, 10 parts phenolic resin vulcanizing agent, 1.2 parts anti-aging agent, 30 parts talc powder, and 20 parts paraffin oil.

[0045] The preparation method of the butyl rubber type TPV material includes the following steps: (1) Add the polypropylene and anti-aging agent to the torque rheometer and mix for 5 min. The speed of the torque rheometer is 62 rpm / min and the temperature is 182℃. Then add chlorinated butyl rubber, hydrogenated nitrile rubber, paraffin oil and talc powder and mix evenly to obtain rubber-plastic premix. (2) After cooling the rubber-plastic premix, add it to an open mixing mill, add the stannous chloride and phenolic resin vulcanizing agent at room temperature, mix evenly, take it out and cut it into strips, and send it into a twin-screw extruder for dynamic vulcanization. The vulcanization temperature is 186°C and the screw speed of the extruder is 110 rpm. The semi-finished TPV material is obtained by extrusion. (3) The semi-finished TPV material is placed on a flat vulcanizing machine and preheated at 181°C for 12 minutes, then held under pressure for 3 minutes and cooled, dehydrated and dried, and vacuum sealed to obtain the butyl rubber type TPV material.

[0046] Comparative Example 1 The raw material composition and preparation method of the butyl rubber type TPV material described in this comparative example are the same as those in Example 1, except that the dynamic vulcanization temperature in step (2) is 180°C.

[0047] Comparative Example 2 The raw material composition and preparation method of the butyl rubber type TPV material described in this comparative example are the same as those in Example 1, except that the dynamic vulcanization temperature in step (2) is 190°C.

[0048] Comparative Example 3 The raw material composition and preparation method of the butyl rubber type TPV material described in this comparative example are the same as those in Example 1, except that the extruder screw speed in step (2) is 150 rpm.

[0049] Comparative Example 4 The raw material composition and preparation method of the butyl rubber type TPV material described in this comparative example are the same as those in Example 1, except that the extruder screw speed in step (2) is 200 rpm.

[0050] Comparative Example 5 The raw material composition and preparation method of the butyl rubber type TPV material described in this comparative example are the same as those in Example 1, except that 10 parts of phenolic resin vulcanizing agent and 2 parts of stannous chloride are replaced with 2 parts of sulfur, 0.5 parts of accelerator BZ, 1 part of accelerator BM and 5 parts of zinc oxide.

[0051] Performance testing The butyl rubber type TPV materials described in Examples 1-3 and Comparative Examples 1-5 were tested for performance according to the following methods, and the specific results are shown in Table 1.

[0052] (1) Tensile strength: Tested using an electronic tensile testing machine according to GB-T528-2009 standard, with a tensile rate of 500 mm / min.

[0053] (2) Permanent compression set: TPV samples were prepared according to GB-T7759.1-2015 and tested using a rubber compression setter. The final result was the average value.

[0054] (3) Elastic modulus: Samples were prepared and tested according to the requirements of HG / T3321-2012. The average value of the three test results was taken.

[0055] (4) Elongation at break: Samples were prepared according to the requirements of GB6037-1985 and tested using a tensile testing machine at a tensile rate of 450 mm / min.

[0056] (5) Heat distortion temperature: Tested according to GB / 3512-2014, aging temperature 100℃, time 72h.

[0057] (6) Abrasion resistance index: DIN abrasion performance test is adopted, with a stroke of 40m.

[0058] (7) Oil resistance: The oil immersion method was used for testing, as follows: The cut sample was immersed in 46# hydraulic oil for 72 hours at room temperature. After immersion, its tensile strength and elongation at break were measured.

[0059] Table 1. Performance data of butyl rubber-type TPV materials described in Examples 1-3 and Comparative Examples 1-5. .

[0060] As shown in Table 1, the butyl rubber-type TPV materials described in Examples 1-3 of this invention exhibit high elongation at break and tensile strength, indicating excellent comprehensive mechanical properties. The materials also have high elastic modulus and low permanent compression set, demonstrating excellent airtightness and resistance to deformation recovery. Furthermore, the TPV materials in Examples 1-3 maintain high elongation at break and tensile strength after oil immersion, indicating excellent oil resistance. Simultaneously, their heat distortion temperature and abrasion resistance index are high, indicating good heat resistance and abrasion resistance. However, as shown in Examples 1 and Comparative Example 1, the TPV material in Comparative Example 1 has a lower dynamic vulcanization temperature during preparation, resulting in reduced tensile strength and elastic modulus, increased permanent compression set, and decreased elongation at break, heat distortion temperature, and abrasion resistance index. This indicates a decline in the material's mechanical properties, airtightness, oil resistance, heat resistance, and abrasion resistance. As shown in Examples 1 and 2, the dynamic vulcanization temperature during the preparation of the TPV material in Comparative Example 2 was too high, resulting in decreased tensile strength and elastic modulus, increased permanent compression deformation, and decreased heat distortion temperature and abrasion resistance index. This indicates a decrease in the material's mechanical properties, airtightness, oil resistance, heat resistance, and abrasion resistance. Similarly, as shown in Examples 1 and 3-4, the extruder screw speed during the preparation of the TPV material in Comparative Examples 3-4 was too high, resulting in increased permanent compression deformation, decreased elastic modulus, elongation at break, heat distortion temperature, and abrasion resistance index. This indicates a decrease in the material's airtightness, oil resistance, heat resistance, and abrasion resistance. Finally, as shown in Examples 1 and 5, the use of different vulcanization systems in the raw material composition of the TPV material in Comparative Example 5 resulted in decreased tensile strength and elastic modulus, increased permanent compression deformation, increased elongation at break, and decreased heat distortion temperature and abrasion resistance index. This indicates a decrease in the material's mechanical properties, airtightness, oil resistance, heat resistance, and abrasion resistance.

[0061] Therefore, by selecting specific dispersed and continuous phase materials and further controlling the dynamic vulcanization conditions, especially by controlling the vulcanization temperature and extruder screw speed within a specific range, the present invention can make the butyl rubber type TPV material have excellent thermal properties, wear resistance, oil resistance and air tightness, while also having good processability and deformation recovery. The molded TPV products can be used in harsh environments such as high sealing, oil contact and friction.

[0062] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A butyl rubber-based TPV material, characterized in that, The raw materials, by weight, include: 10-60 parts polypropylene, 80-110 parts butyl rubber, 5-10 parts hydrogenated nitrile rubber, 0.5-2 parts stannous chloride, 5-10 parts vulcanizing agent, 0.6-1.2 parts anti-aging agent, 20-30 parts talc, and 10-20 parts paraffin oil. The butyl rubber is brominated butyl rubber and / or chlorinated butyl rubber; The vulcanizing agent is a phenolic resin vulcanizing agent; The preparation method of the butyl rubber type TPV material includes the following steps: (1) The polypropylene and anti-aging agent are added to the torque rheometer and mixed in proportion, and then butyl rubber, hydrogenated nitrile rubber, paraffin oil and talc are added and mixed evenly to obtain a rubber-plastic premix. (2) After cooling the rubber-plastic premix, add it to an open mixing mill, add the stannous chloride and vulcanizing agent at room temperature, mix evenly, take it out and cut it into strips, send it into a twin-screw extruder for dynamic vulcanization, and extrude to obtain semi-finished TPV material; (3) The semi-finished TPV material is placed on a flat vulcanizing machine for preheating, pressure holding and cooling, dehydration and drying, and vacuum sealing to obtain the butyl rubber type TPV material. In step (2), the dynamic vulcanization conditions are: vulcanization temperature of 185-187℃ and extruder screw speed of 100-120rpm.

2. The butyl rubber type TPV material according to claim 1, characterized in that, The polypropylene is a random copolymer polypropylene, and the melt flow rate (MFR) of the polypropylene under test conditions of 230℃ and 2.16kg load is 7.0-8.0g / 10min.

3. The butyl rubber type TPV material according to claim 1, characterized in that, The anti-aging agent is a compound of phenolic antioxidants and phosphite antioxidants, with a compounding ratio of 1.5-2:

3.

4. The butyl rubber type TPV material according to claim 1, characterized in that, In step (1), the torque rheometer has a rotational speed of 60-65 rpm / min and a temperature of 180-185℃.

5. The butyl rubber type TPV material according to claim 1, characterized in that, In step (3), the preheating temperature is 180-182℃ and the preheating time is 10-15min.

6. The butyl rubber type TPV material according to claim 1, characterized in that, In step (3), the pressure holding pressure is 10-12 MPa and the pressure holding time is 3-5 min.