Flame-retardant wear-resistant hydrogenated butadiene-acrylonitrile rubber composite material and preparation method thereof

Abstract

The invention relates to the technical field of rubber materials, and discloses a flame-retardant wear-resistant hydrogenated butadiene-acrylonitrile rubber composite material and a preparation method thereof. The preparation method comprises the following steps: uniformly mixing hydrogenated butadiene-acrylonitrile rubber, stearic acid and aramid pulp, adding zinc oxide, the anti-aging agent and the composite filler, uniformly mixing, heating, adding the vulcanizing agent and the assistant cross-linking agent, heating, mixing and vulcanizing to obtain a hydrogenated butadiene-acrylonitrile rubber composite material; the hydrogenated butadiene-acrylonitrile rubber composite material comprises the following raw materials in parts by mass: 80-100 parts of hydrogenated butadiene-acrylonitrile rubber, 1-2 parts of stearic acid, 5-10 parts of aramid pulp, 5-10 parts of zinc oxide, 2-4 parts of an anti-aging agent, 50-65 parts of a composite filler, 2-4 parts of a vulcanizing agent and 1-2 parts of an assistant crosslinking agent, the composite filler is prepared from the following raw materials in parts by mass: 20 to 25 parts of zinc methacrylate modified polytetrafluoroethylene micro powder, 10 to 15 parts of silicone oil modified polytetrafluoroethylene micro powder and 20 to 25 parts of flame-retardant modified carbon nanotubes.

Description

Technical Field

[0001] The invention relates to the technical field of rubber materials and discloses a flame-retardant and wear-resistant hydrogenated nitrile rubber composite material and a preparation method thereof. Background Art

[0002] Nitrile rubber is obtained by emulsion polymerization of acrylonitrile and butadiene, and hydrogenated nitrile rubber is a special rubber obtained by hydrogenating and saturating nitrile rubber. It has excellent oil resistance, weather resistance, heat resistance, and chemical stability and is widely used in the fields of automobiles, aerospace, oil and gas development, etc. However, hydrogenated nitrile rubber itself has poor flame retardancy and poses a large fire safety hazard. In addition, the wear resistance of hydrogenated nitrile rubber is insufficient, resulting in a short service life of the product. In the prior art, performance is often improved by adding flame retardants or inorganic fillers, but it is often difficult to achieve excellent flame retardancy and wear resistance at the same time due to problems such as compatibility and dispersibility, and it may have a negative impact on other properties of the rubber. Therefore, it is of great significance to study a flame retardant and wear-resistant hydrogenated nitrile rubber composite material and its preparation method. Summary of the Invention

[0003] The object of the present invention is to provide a flame retardant and wear-resistant hydrogenated nitrile rubber composite material and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions: A method for preparing a flame-retardant and wear-resistant hydrogenated nitrile rubber composite material, comprising the following steps: uniformly mixing hydrogenated nitrile rubber, stearic acid, and aramid pulp, adding zinc oxide, an antioxidant, and a composite filler, uniformly mixing, heating and adding a vulcanizing agent and a cross-linking agent, heating and mixing, and vulcanizing to obtain a hydrogenated nitrile rubber composite material; the composite filler comprises zinc methacrylate modified polytetrafluoroethylene micropowder, silicone oil modified polytetrafluoroethylene micropowder, and flame-retardant modified carbon nanotubes.

[0005] More optimally, the hydrogenated nitrile rubber composite material includes the following raw materials, calculated by mass: 80 to 100 parts of hydrogenated nitrile rubber, 1 to 2 parts of stearic acid, 5 to 10 parts of aramid pulp, 5 to 10 parts of zinc oxide, 2 to 4 parts of antioxidant, 50 to 65 parts of composite filler, 2 to 4 parts of vulcanizing agent, and 1 to 2 parts of cross-linking agent.

[0006] More optimally, the composite filler includes the following raw materials, calculated by mass: 20 to 25 parts of zinc methacrylate modified polytetrafluoroethylene powder, 10 to 15 parts of silicone oil modified polytetrafluoroethylene powder, and 20 to 25 parts of flame retardant modified carbon nanotubes.

[0007] More optimally, the preparation of the silicone oil-modified polytetrafluoroethylene micropowder comprises the following steps: S1: taking polytetrafluoroethylene micropowder and 3-(2,3-epoxypropoxy)propyltrimethoxysilane, stirring them evenly, placing them in an irradiation box, and irradiating them with a high-energy electron beam to obtain irradiated modified polytetrafluoroethylene micropowder;

[0008] S2: Take irradiated modified polytetrafluoroethylene powder, add it to ethylene glycol and stir evenly, add polyvinyl pyrrolidone and disperse it evenly, hydrothermally react at 140-150°C for 4-5 hours, remove the solvent, wash and dry to obtain carboxyl modified polytetrafluoroethylene powder;

[0009] S3: Take carboxyl-modified polytetrafluoroethylene powder and hydroxyl-terminated methyl vinyl silicone oil, add them to acetone and stir evenly, add dimethylimidazole, react at 150-160°C for 8-12 hours, remove the solvent and dry to obtain silicone oil-modified polytetrafluoroethylene powder.

[0010] More optimally, the radiation-modified polytetrafluoroethylene powder comprises the following raw materials, in parts by mass: 10 to 15 parts of polytetrafluoroethylene powder, 0.2 to 0.5 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane;

[0011] The carboxyl modified polytetrafluoroethylene powder comprises the following raw materials, calculated by weight: 10 to 15 parts of irradiated modified polytetrafluoroethylene powder, 80 to 100 parts of ethylene glycol, and 0.5 to 1 part of polyvinyl pyrrolidone;

[0012] The silicone oil modified polytetrafluoroethylene powder comprises the following raw materials, calculated by mass: 10 to 15 parts of carboxyl modified polytetrafluoroethylene powder, 4 to 6 parts of hydroxyl terminated methyl vinyl silicone oil, 80 to 100 parts of acetone, and 0.2 to 0.5 parts of dimethylimidazole.

[0013] More optimally, the preparation of the flame-retardant modified carbon nanotubes includes the following steps: Step 1: mixing biphenyl aminophosphoric acid ester, sodium hydroxide and acetone under nitrogen protection, stirring at a constant temperature of 5 to 10° C. in an ice-water bath, adding cyanuric chloride, stirring and reacting for 2 to 3 hours, and removing the solvent to obtain phosphate-modified cyanuric chloride;

[0014] Step 2: Add carbon nanotubes to a mixed solution of water and ethanol, heat to 60-70°C, add aminosilane coupling agent and vinylsilane coupling agent, stir and react for 5-6 hours, remove the solvent, wash, and dry to obtain modified carbon nanotubes containing amino groups and double bonds;

[0015] Step 3: Mix the modified carbon nanotubes, sodium hydroxide and acetone under nitrogen protection, stir at a constant temperature of 5-10°C in an ice water bath, add phosphate-modified cyanuric chloride, stir and react for 2-3 hours, remove the solvent, and obtain flame-retardant modified carbon nanotubes.

[0016] More optimally, the phosphate-modified cyanuric chloride comprises the following raw materials, calculated by weight: 15 to 25 parts of biphenylphosphoramidate, 3 to 5 parts of sodium hydroxide, 100 to 150 parts of acetone, and 8 to 10 parts of cyanuric chloride;

[0017] The modified carbon nanotubes include the following raw materials, calculated by weight: 10 to 15 parts of carbon nanotubes, 1 to 2 parts of aminosilane coupling agent, and 1 to 2 parts of vinylsilane coupling agent;

[0018] The flame retardant modified carbon nanotubes include the following raw materials, calculated by mass: 10 to 15 parts of modified carbon nanotubes, 3 to 5 parts of sodium hydroxide, 100 to 150 parts of acetone, and 3 to 6 parts of phosphate-modified cyanuric chloride.

[0019] More optimally, the preparation of the zinc methacrylate modified polytetrafluoroethylene micropowder comprises the following steps: taking polytetrafluoroethylene micropowder and zinc methacrylate, stirring for 2 to 5 minutes, and obtaining the zinc methacrylate modified polytetrafluoroethylene micropowder.

[0020] More optimally, the zinc methacrylate modified polytetrafluoroethylene powder comprises the following raw materials, calculated by mass: 10 to 15 parts of polytetrafluoroethylene powder and 1 to 2 parts of zinc methacrylate.

[0021] Compared with the prior art, the present invention achieves the following beneficial effects: adding a composite filler, specifically a composition of zinc methacrylate modified polytetrafluoroethylene micropowder, silicone oil modified polytetrafluoroethylene micropowder, and flame retardant modified carbon nanotubes;

[0022] Polytetrafluoroethylene powder can improve the basic physical properties, flame retardancy, and wear resistance of rubber, but its surface energy is low and its compatibility with other materials is very poor. This solution uses zinc methacrylate to modify the surface of polytetrafluoroethylene powder. The zinc ions can participate in the rubber cross-linking reaction, acting as a bridge and increasing the compatibility between polytetrafluoroethylene powder and rubber.

[0023] Silicone oil-modified polytetrafluoroethylene micropowder contains siloxane chain segments, and its flexibility and low interfacial energy can improve the wear resistance and heat resistance of rubber materials. At the same time, due to compatibility issues, silicone oil-modified polytetrafluoroethylene micropowder will migrate to the surface of the rubber material, acting as a physical barrier and improving the wear resistance of the surface. The present invention uses vinyl-containing silicone oil, which can produce a cross-linking reaction with hydrogenated nitrile rubber, so that one end of the silicone oil-modified polytetrafluoroethylene micropowder is fixed in the rubber material, and its bonding force with the rubber matrix is ​​not too weak, so that it will fall off from the surface under the action of friction and shear force, and accelerate wear. The amount of silicone oil-modified polytetrafluoroethylene micropowder added needs to be controlled. Too little addition will result in no obvious performance improvement, and too much addition will cause an oil film to form on the surface or the polytetrafluoroethylene micropowder to fall off easily, which will in turn reduce the wear resistance.

[0024] The flame-retardant modified carbon nanotubes contain phosphorus and nitrogen elements, which play a synergistic flame retardant role. At the same time, they contain double bonds, which can improve the dispersion of flame retardants and carbon nanotubes in rubber, improve the problems of flame retardant migration and poor compatibility between inorganic fillers and rubber matrix, and finally produce a hydrogenated nitrile rubber composite material with both flame retardancy and wear resistance. DETAILED DESCRIPTION

[0025] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0026] It should be noted that there is no special restriction on the purchase manufacturers of all raw materials involved in the present invention, and illustratively include: ethanol (CAS: 64-17-5); vinyl silane coupling agent (CAS: 2768-02-7); hydrogenated nitrile rubber (Z-2020L, Zeon); stearic acid (CAS: 57-11-4); aramid pulp Zinc oxide (Jiyesheng 4203); antioxidant (rubber antioxidant 4010NA, CAS: 101-72-4); vulcanizing agent (DCP, CAS: 80-43-3); cross-linking agent TAIC (CAS: 1025-15-6); polytetrafluoroethylene powder (L-5, 5μm, Daikin Fluorochemical); zinc methacrylate (CAS: 13189-00-9); 3-(2,3-epoxypropoxy)propyltrimethoxysilane (CAS: 2530-83-8); polyvinylpyrrolidone (Jiyesheng 2528); hydroxyl-terminated methyl vinyl silicone oil (IOTA 1203V); biphenylamidophosphorate (CAS: 2015-56-7); carbon nanotubes (Yami MWCNT-N-03); aminosilane coupling agent (CAS: 919-30-2); hydroxyl-terminated silicone oil (IOTA 8866);

[0027] Unless otherwise specified, the following are parts by mass and mass ratios;

[0028] Example 1: S1: Take 12 parts of polytetrafluoroethylene powder and 2 parts of zinc methacrylate, stir for 5 minutes, and obtain zinc methacrylate modified polytetrafluoroethylene powder;

[0029] S2: Take 10 parts of polytetrafluoroethylene micropowder and 0.4 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, stir them evenly, place them in an irradiation box, and irradiate them with a high-energy electron beam to obtain irradiated modified polytetrafluoroethylene micropowder; the irradiation dose is 20 Mrad; the irradiation source is a high-energy electron beam;

[0030] Take 12 parts of irradiated modified polytetrafluoroethylene powder, add it to 100 parts of ethylene glycol and stir evenly, add 0.8 parts of polyvinyl pyrrolidone, disperse it evenly, hydrothermally react at 150°C for 5 hours, remove the solvent, wash and dry to obtain carboxyl modified polytetrafluoroethylene powder;

[0031] Take 12 parts of carboxyl-modified polytetrafluoroethylene powder and 5 parts of hydroxyl-terminated methyl vinyl silicone oil, add them to 100 parts of acetone and stir evenly, add 0.4 parts of dimethylimidazole, react at 160°C for 12 hours, remove the solvent and dry to obtain silicone oil-modified polytetrafluoroethylene powder;

[0032] S3: 25 parts of biphenylphosphamidate, 4 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice-water bath. 10 parts of cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain phosphate-modified cyanuric chloride.

[0033] Take 10 parts of carbon nanotubes and add them to 100 parts of water and ethanol in a volume ratio of 3:7, raise the temperature to 60°C, add 1 part of aminosilane coupling agent and 1 part of vinylsilane coupling agent, stir and react for 6 hours, remove the solvent, wash and dry to obtain modified carbon nanotubes containing amino groups and double bonds;

[0034] 12 parts of modified carbon nanotubes, 4 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice water bath. 5 parts of phosphate-modified cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain flame-retardant modified carbon nanotubes.

[0035] S4: Take 25 parts of zinc methacrylate modified polytetrafluoroethylene powder, 10 parts of silicone oil modified polytetrafluoroethylene powder, and 25 parts of flame retardant modified carbon nanotubes and mix them evenly to obtain a composite filler:

[0036] S5: 80 parts of hydrogenated nitrile rubber, 1 part of stearic acid, and 6 parts of aramid pulp were mixed for 5 minutes, 6 parts of zinc oxide, 3 parts of antioxidant, and 60 parts of composite fillers were added, and the mixture was mixed for 5 minutes. The mixture was heated to 90°C, 3 parts of vulcanizing agent DCP and 1 part of co-crosslinking agent TAIC were added, the mixture was heated to 100°C, and the mixture was mixed for 15 minutes. The mixture was vulcanized at a temperature of 150°C and a pressure of 5 MPa for 15 minutes, and then vulcanized at a temperature of 170°C for 3 hours to obtain a hydrogenated nitrile rubber composite material.

[0037] Example 2: S1: Take 10 parts of polytetrafluoroethylene powder and 1 part of zinc methacrylate, stir for 5 minutes, and obtain zinc methacrylate modified polytetrafluoroethylene powder;

[0038] S2: Take 10 parts of polytetrafluoroethylene micropowder and 0.2 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, stir them evenly, place them in an irradiation box, and irradiate them with a high-energy electron beam to obtain irradiated modified polytetrafluoroethylene micropowder; the irradiation dose is 20 Mrad; the irradiation source is a high-energy electron beam;

[0039] Take 10 parts of irradiated modified polytetrafluoroethylene powder, add it to 100 parts of ethylene glycol and stir evenly, add 0.5 parts of polyvinyl pyrrolidone, disperse it evenly, hydrothermally react at 150°C for 5 hours, remove the solvent, wash and dry to obtain carboxyl modified polytetrafluoroethylene powder;

[0040] Take 10 parts of carboxyl-modified polytetrafluoroethylene powder and 4 parts of hydroxyl-terminated methyl vinyl silicone oil, add them to 100 parts of acetone and stir evenly, add 0.2 parts of dimethylimidazole, react at 160°C for 12 hours, remove the solvent and dry to obtain silicone oil-modified polytetrafluoroethylene powder;

[0041] S3: 25 parts of biphenylphosphamidate, 5 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice-water bath. 10 parts of cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain phosphate-modified cyanuric chloride.

[0042] Take 15 parts of carbon nanotubes and add 100 parts of water and ethanol in a volume ratio of 3:7, raise the temperature to 60°C, add 1 part of aminosilane coupling agent and 1 part of vinylsilane coupling agent, stir and react for 6 hours, remove the solvent, wash and dry to obtain modified carbon nanotubes containing amino groups and double bonds;

[0043] 15 parts of modified carbon nanotubes, 5 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice water bath. 6 parts of phosphate-modified cyanuric chloride were added and stirred for 3 hours. The solvent was removed to obtain flame-retardant modified carbon nanotubes.

[0044] S4: Take 20 parts of zinc methacrylate modified polytetrafluoroethylene powder, 15 parts of silicone oil modified polytetrafluoroethylene powder, and 25 parts of flame retardant modified carbon nanotubes and mix them evenly to obtain a composite filler:

[0045] S5: 80 parts of hydrogenated nitrile rubber, 1 part of stearic acid, and 6 parts of aramid pulp were mixed for 5 minutes, 6 parts of zinc oxide, 3 parts of antioxidant, and 60 parts of composite fillers were added, and the mixture was mixed for 5 minutes. The mixture was heated to 90°C, 3 parts of vulcanizing agent DCP and 1 part of co-crosslinking agent TAIC were added, the mixture was heated to 100°C, and the mixture was mixed for 15 minutes. The mixture was vulcanized at a temperature of 150°C and a pressure of 5 MPa for 15 minutes, and then vulcanized at a temperature of 170°C for 3 hours to obtain a hydrogenated nitrile rubber composite material.

[0046] Example 3: S1: Take 15 parts of polytetrafluoroethylene powder and 2 parts of zinc methacrylate, stir for 5 minutes, and obtain zinc methacrylate modified polytetrafluoroethylene powder;

[0047] S2: Take 15 parts of polytetrafluoroethylene micropowder and 0.5 parts of 3-(2,3-epoxypropyloxy)propyltrimethoxysilane, stir them evenly, place them in an irradiation box, and irradiate them with a high-energy electron beam to obtain irradiated modified polytetrafluoroethylene micropowder; the irradiation dose is 20 Mrad; the irradiation source is a high-energy electron beam;

[0048] Take 15 parts of irradiated modified polytetrafluoroethylene powder, add it to 100 parts of ethylene glycol and stir evenly, add 1 part of polyvinyl pyrrolidone, disperse it evenly, hydrothermally react at 150°C for 5 hours, remove the solvent, wash and dry to obtain carboxyl modified polytetrafluoroethylene powder;

[0049] Take 15 parts of carboxyl-modified polytetrafluoroethylene powder and 6 parts of hydroxyl-terminated methyl vinyl silicone oil, add them to 100 parts of acetone and stir evenly, add 0.5 parts of dimethylimidazole, react at 160°C for 12 hours, remove the solvent and dry to obtain silicone oil-modified polytetrafluoroethylene powder;

[0050] S3: 15 parts of biphenylphosphamidate, 3 parts of sodium hydroxide, and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice-water bath. 8 parts of cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain phosphate-modified cyanuric chloride.

[0051] Take 10 parts of carbon nanotubes and add them to 100 parts of water and ethanol in a volume ratio of 3:7, raise the temperature to 60°C, add 1 part of aminosilane coupling agent and 1 part of vinylsilane coupling agent, stir and react for 6 hours, remove the solvent, wash and dry to obtain modified carbon nanotubes containing amino groups and double bonds;

[0052] 10 parts of modified carbon nanotubes, 3 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice water bath. 6 parts of phosphate-modified cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain flame-retardant modified carbon nanotubes.

[0053] S4: Take 25 parts of zinc methacrylate modified polytetrafluoroethylene powder, 15 parts of silicone oil modified polytetrafluoroethylene powder, and 20 parts of flame retardant modified carbon nanotubes and mix them evenly to obtain a composite filler:

[0054] S5: 80 parts of hydrogenated nitrile rubber, 1 part of stearic acid, and 6 parts of aramid pulp were mixed for 5 minutes, 6 parts of zinc oxide, 3 parts of antioxidant, and 60 parts of composite fillers were added, and the mixture was mixed for 5 minutes. The mixture was heated to 90°C, 3 parts of vulcanizing agent DCP and 1 part of co-crosslinking agent TAIC were added, the mixture was heated to 100°C, and the mixture was mixed for 15 minutes. The mixture was vulcanized at a temperature of 150°C and a pressure of 5 MPa for 15 minutes, and then vulcanized at a temperature of 170°C for 3 hours to obtain a hydrogenated nitrile rubber composite material.

[0055] Comparative Example 1 (the amount of the composite filler raw material added was changed, and the remaining steps were the same as those in Example 1): S1: 12 parts of polytetrafluoroethylene powder and 2 parts of zinc methacrylate were taken and stirred for 5 minutes to obtain zinc methacrylate-modified polytetrafluoroethylene powder;

[0056] S2: Take 10 parts of polytetrafluoroethylene micropowder and 0.4 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, stir them evenly, place them in an irradiation box, and irradiate them with a high-energy electron beam to obtain irradiated modified polytetrafluoroethylene micropowder; the irradiation dose is 20 Mrad; the irradiation source is a high-energy electron beam;

[0057] Take 12 parts of irradiated modified polytetrafluoroethylene powder, add it to 100 parts of ethylene glycol and stir evenly, add 0.8 parts of polyvinyl pyrrolidone, disperse it evenly, hydrothermally react at 150°C for 5 hours, remove the solvent, wash and dry to obtain carboxyl modified polytetrafluoroethylene powder;

[0058] Take 12 parts of carboxyl-modified polytetrafluoroethylene powder and 5 parts of hydroxyl-terminated methyl vinyl silicone oil, add them to 100 parts of acetone and stir evenly, add 0.4 parts of dimethylimidazole, react at 160°C for 12 hours, remove the solvent and dry to obtain silicone oil-modified polytetrafluoroethylene powder;

[0059] S3: 25 parts of biphenylphosphamidate, 4 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice-water bath. 10 parts of cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain phosphate-modified cyanuric chloride.

[0060] Take 10 parts of carbon nanotubes and add them to 100 parts of water and ethanol in a volume ratio of 3:7, raise the temperature to 60°C, add 1 part of aminosilane coupling agent and 1 part of vinylsilane coupling agent, stir and react for 6 hours, remove the solvent, wash and dry to obtain modified carbon nanotubes containing amino groups and double bonds;

[0061] 12 parts of modified carbon nanotubes, 4 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice water bath. 5 parts of phosphate-modified cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain flame-retardant modified carbon nanotubes.

[0062] S4: Take 15 parts of zinc methacrylate modified polytetrafluoroethylene powder, 20 parts of silicone oil modified polytetrafluoroethylene powder, and 25 parts of flame retardant modified carbon nanotubes and mix them evenly to obtain a composite filler:

[0063] S5: 80 parts of hydrogenated nitrile rubber, 1 part of stearic acid, and 6 parts of aramid pulp were mixed for 5 minutes, 6 parts of zinc oxide, 3 parts of antioxidant, and 60 parts of composite fillers were added, and the mixture was mixed for 5 minutes. The mixture was heated to 90°C, 3 parts of vulcanizing agent DCP and 1 part of co-crosslinking agent TAIC were added, the mixture was heated to 100°C, and the mixture was mixed for 15 minutes. The mixture was vulcanized at a temperature of 150°C and a pressure of 5 MPa for 15 minutes, and then vulcanized at a temperature of 170°C for 3 hours to obtain a hydrogenated nitrile rubber composite material.

[0064] Comparative Example 2 (changing the amount of composite filler raw material added, the remaining method steps are consistent with Example 1): S1: taking 12 parts of polytetrafluoroethylene powder and 2 parts of zinc methacrylate, stirring for 5 minutes to obtain zinc methacrylate modified polytetrafluoroethylene powder;

[0065] S2: Take 10 parts of polytetrafluoroethylene micropowder and 0.4 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, stir them evenly, place them in an irradiation box, and irradiate them with a high-energy electron beam to obtain irradiated modified polytetrafluoroethylene micropowder; the irradiation dose is 20 Mrad; the irradiation source is a high-energy electron beam;

[0066] Take 12 parts of irradiated modified polytetrafluoroethylene powder, add it to 100 parts of ethylene glycol and stir evenly, add 0.8 parts of polyvinyl pyrrolidone, disperse it evenly, hydrothermally react at 150°C for 5 hours, remove the solvent, wash and dry to obtain carboxyl modified polytetrafluoroethylene powder;

[0067] Take 12 parts of carboxyl-modified polytetrafluoroethylene powder and 5 parts of hydroxyl-terminated methyl vinyl silicone oil, add them to 100 parts of acetone and stir evenly, add 0.4 parts of dimethylimidazole, react at 160°C for 12 hours, remove the solvent and dry to obtain silicone oil-modified polytetrafluoroethylene powder;

[0068] S3: 25 parts of biphenylphosphamidate, 4 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice-water bath. 10 parts of cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain phosphate-modified cyanuric chloride.

[0069] Take 10 parts of carbon nanotubes and add them to 100 parts of water and ethanol in a volume ratio of 3:7, raise the temperature to 60°C, add 1 part of aminosilane coupling agent and 1 part of vinylsilane coupling agent, stir and react for 6 hours, remove the solvent, wash and dry to obtain modified carbon nanotubes containing amino groups and double bonds;

[0070] 12 parts of modified carbon nanotubes, 4 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice water bath. 5 parts of phosphate-modified cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain flame-retardant modified carbon nanotubes.

[0071] S4: Take 30 parts of zinc methacrylate modified polytetrafluoroethylene powder, 5 parts of silicone oil modified polytetrafluoroethylene powder, and 25 parts of flame retardant modified carbon nanotubes and mix them evenly to obtain a composite filler:

[0072] S5: 80 parts of hydrogenated nitrile rubber, 1 part of stearic acid, and 6 parts of aramid pulp were mixed for 5 minutes, 6 parts of zinc oxide, 3 parts of antioxidant, and 60 parts of composite fillers were added, and the mixture was mixed for 5 minutes. The mixture was heated to 90°C, 3 parts of vulcanizing agent DCP and 1 part of co-crosslinking agent TAIC were added, the mixture was heated to 100°C, and the mixture was mixed for 15 minutes. The mixture was vulcanized at a temperature of 150°C and a pressure of 5 MPa for 15 minutes, and then vulcanized at a temperature of 170°C for 3 hours to obtain a hydrogenated nitrile rubber composite material.

[0073] Comparative Example 3 (no double bond is introduced into the modified carbon nanotubes, and the remaining steps are the same as those in Example 1): S1: 12 parts of polytetrafluoroethylene powder and 2 parts of zinc methacrylate are taken and stirred for 5 minutes to obtain zinc methacrylate-modified polytetrafluoroethylene powder;

[0074] S2: Take 10 parts of polytetrafluoroethylene micropowder and 0.4 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, stir them evenly, place them in an irradiation box, and irradiate them with a high-energy electron beam to obtain irradiated modified polytetrafluoroethylene micropowder; the irradiation dose is 20 Mrad; the irradiation source is a high-energy electron beam;

[0075] Take 12 parts of irradiated modified polytetrafluoroethylene powder, add it to 100 parts of ethylene glycol and stir evenly, add 0.8 parts of polyvinyl pyrrolidone, disperse it evenly, hydrothermally react at 150°C for 5 hours, remove the solvent, wash and dry to obtain carboxyl modified polytetrafluoroethylene powder;

[0076] Take 12 parts of carboxyl-modified polytetrafluoroethylene powder and 5 parts of hydroxyl-terminated methyl vinyl silicone oil, add them to 100 parts of acetone and stir evenly, add 0.4 parts of dimethylimidazole, react at 160°C for 12 hours, remove the solvent and dry to obtain silicone oil-modified polytetrafluoroethylene powder;

[0077] S3: 25 parts of biphenylphosphamidate, 4 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice-water bath. 10 parts of cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain phosphate-modified cyanuric chloride.

[0078] Take 10 parts of carbon nanotubes and add them to 100 parts of water and ethanol in a volume ratio of 3:7, raise the temperature to 60°C, add 2 parts of aminosilane coupling agent, stir and react for 6 hours, remove the solvent, wash and dry to obtain modified carbon nanotubes containing amino groups;

[0079] 12 parts of modified carbon nanotubes, 4 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice water bath. 5 parts of phosphate-modified cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain flame-retardant modified carbon nanotubes.

[0080] S4: Take 25 parts of zinc methacrylate modified polytetrafluoroethylene powder, 10 parts of silicone oil modified polytetrafluoroethylene powder, and 25 parts of flame retardant modified carbon nanotubes and mix them evenly to obtain a composite filler:

[0081] S5: 80 parts of hydrogenated nitrile rubber, 1 part of stearic acid, and 6 parts of aramid pulp were mixed for 5 minutes, 6 parts of zinc oxide, 3 parts of antioxidant, and 60 parts of composite fillers were added, and the mixture was mixed for 5 minutes. The mixture was heated to 90°C, 3 parts of vulcanizing agent DCP and 1 part of co-crosslinking agent TAIC were added, the mixture was heated to 100°C, and the mixture was mixed for 15 minutes. The mixture was vulcanized at a temperature of 150°C and a pressure of 5 MPa for 15 minutes, and then vulcanized at a temperature of 170°C for 3 hours to obtain a hydrogenated nitrile rubber composite material.

[0082] Comparative Example 4 (the preparation method of silicone oil-modified polytetrafluoroethylene powder was changed, and the remaining steps were the same as those in Example 1): S1: 12 parts of polytetrafluoroethylene powder and 2 parts of zinc methacrylate were taken and stirred for 5 minutes to obtain zinc methacrylate-modified polytetrafluoroethylene powder;

[0083] S2: Take 10 parts of polytetrafluoroethylene micropowder and 0.4 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, stir them evenly, place them in an irradiation box, and irradiate them with a high-energy electron beam to obtain irradiated modified polytetrafluoroethylene micropowder; the irradiation dose is 20 Mrad; the irradiation source is a high-energy electron beam;

[0084] Take 12 parts of irradiated modified polytetrafluoroethylene powder, add it to 100 parts of ethylene glycol and stir evenly, add 0.8 parts of polyvinyl pyrrolidone, disperse it evenly, hydrothermally react at 150°C for 5 hours, remove the solvent, wash and dry to obtain carboxyl modified polytetrafluoroethylene powder;

[0085] Take 12 parts of carboxyl-modified polytetrafluoroethylene powder and 5 parts of hydroxyl-terminated silicone oil, add them to 100 parts of acetone and stir evenly, add 0.4 parts of dimethylimidazole, react at 160°C for 12 hours, remove the solvent and dry to obtain silicone oil-modified polytetrafluoroethylene powder;

[0086] S3: 25 parts of biphenylphosphamidate, 4 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice-water bath. 10 parts of cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain phosphate-modified cyanuric chloride.

[0087] Take 10 parts of carbon nanotubes and add them to 100 parts of water and ethanol in a volume ratio of 3:7, raise the temperature to 60°C, add 1 part of aminosilane coupling agent and 1 part of vinylsilane coupling agent, stir and react for 6 hours, remove the solvent, wash and dry to obtain modified carbon nanotubes containing amino groups and double bonds;

[0088] 12 parts of modified carbon nanotubes, 4 parts of sodium hydroxide and 100 parts of acetone were mixed under nitrogen protection, and stirred at a constant temperature of 5°C in an ice water bath. 5 parts of phosphate-modified cyanuric chloride were added, and the mixture was stirred for 3 hours. The solvent was removed to obtain flame-retardant modified carbon nanotubes.

[0089] S4: Take 25 parts of zinc methacrylate modified polytetrafluoroethylene powder, 10 parts of silicone oil modified polytetrafluoroethylene powder, and 25 parts of flame retardant modified carbon nanotubes and mix them evenly to obtain a composite filler:

[0090] S5: 80 parts of hydrogenated nitrile rubber, 1 part of stearic acid, and 6 parts of aramid pulp were mixed for 5 minutes, 6 parts of zinc oxide and 3 parts of antioxidant were added, the temperature was raised to 100°C, and mixed for 15 minutes. The mixture was vulcanized at a temperature of 150°C and a pressure of 5 MPa for 15 minutes, and then vulcanized at a temperature of 170°C for 3 hours to obtain a hydrogenated nitrile rubber composite material.

[0091] Performance test: Take the hydrogenated nitrile rubber composite materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4; (1) refer to GB / T9867-Method A to test the wear resistance; (2) refer to GB / T2406.2 to test the flame retardancy; see Table 1 for details;

[0092] Table 1:

[0093]

[0094] Conclusion: Comparative Examples 1 and 2 changed the addition amount of the composite filler raw material and the addition ratio of silicone oil modified polytetrafluoroethylene micropowder and zinc methacrylate modified polytetrafluoroethylene micropowder, and the performance was not as good as that of the embodiment. It can be seen that controlling the addition amount is of great significance; Comparative Example 3 did not introduce double bonds into the flame retardant modified carbon nanotubes, and the compatibility with the rubber matrix deteriorated, resulting in a decrease in the overall flame retardancy; Comparative Example 4 changed the preparation method of silicone oil modified polytetrafluoroethylene micropowder and used hydroxy silicone oil, which resulted in a decrease in performance due to the lack of double bonds; In summary, the hydrogenated nitrile rubber composite material prepared by the present invention has good flame retardancy and wear resistance.

[0095] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing a flame retardant and wear-resistant hydrogenated nitrile rubber composite material, characterized in that: The following steps are involved: The hydrogenated nitrile rubber, stearic acid and aramid pulp are mixed evenly, zinc oxide, an antioxidant and a composite filler are added, mixed evenly, the temperature is increased and a vulcanizing agent and a cross-linking agent are added, the temperature is increased and mixed, and vulcanization is performed to obtain a hydrogenated nitrile rubber composite material; The composite filler comprises zinc methacrylate modified polytetrafluoroethylene micropowder, silicone oil modified polytetrafluoroethylene micropowder and flame retardant modified carbon nanotubes.

2. The method for preparing a flame retardant and wear-resistant hydrogenated nitrile rubber composite material according to claim 1, wherein: The hydrogenated nitrile rubber composite material comprises the following raw materials, calculated by mass: 80 to 100 parts of hydrogenated nitrile rubber, 1 to 2 parts of stearic acid, 5 to 10 parts of aramid pulp, 5 to 10 parts of zinc oxide, 2 to 4 parts of antioxidant, 50 to 65 parts of composite filler, 2 to 4 parts of vulcanizing agent, and 1 to 2 parts of auxiliary cross-linking agent.

3. The method for preparing a flame retardant and wear-resistant hydrogenated nitrile rubber composite material according to claim 1, wherein: The composite filler comprises the following raw materials, calculated by mass: 20 to 25 parts of zinc methacrylate modified polytetrafluoroethylene powder, 10 to 15 parts of silicone oil modified polytetrafluoroethylene powder, and 20 to 25 parts of flame retardant modified carbon nanotubes.

4. The method for preparing a flame retardant and wear resistant hydrogenated nitrile rubber composite material according to claim 1, wherein: The preparation of the silicone oil modified polytetrafluoroethylene micropowder comprises the following steps: S1: Take polytetrafluoroethylene micropowder and 3-(2,3-epoxypropoxy)propyltrimethoxysilane, stir them evenly, place them in an irradiation box, and irradiate them with a high-energy electron beam to obtain irradiation-modified polytetrafluoroethylene micropowder; S2: Take irradiated modified polytetrafluoroethylene powder, add it to ethylene glycol and stir evenly, add polyvinyl pyrrolidone and disperse it evenly, hydrothermally react at 140-150°C for 4-5 hours, remove the solvent, wash and dry to obtain carboxyl modified polytetrafluoroethylene powder; S3: Take carboxyl-modified polytetrafluoroethylene powder and hydroxyl-terminated methyl vinyl silicone oil, add them to acetone and stir evenly, add dimethylimidazole, react at 150-160°C for 8-12 hours, remove the solvent and dry to obtain silicone oil-modified polytetrafluoroethylene powder.

5. The method for preparing a flame retardant and wear-resistant hydrogenated nitrile rubber composite material according to claim 4, characterized in that: The radiation-modified polytetrafluoroethylene powder comprises the following raw materials, in parts by mass: 10 to 15 parts of polytetrafluoroethylene powder, 0.2 to 0.5 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane; The carboxyl modified polytetrafluoroethylene powder comprises the following raw materials, calculated by weight: 10 to 15 parts of irradiated modified polytetrafluoroethylene powder, 80 to 100 parts of ethylene glycol, and 0.5 to 1 part of polyvinyl pyrrolidone; The silicone oil modified polytetrafluoroethylene powder comprises the following raw materials, calculated by mass: 10 to 15 parts of carboxyl modified polytetrafluoroethylene powder, 4 to 6 parts of hydroxyl terminated methyl vinyl silicone oil, 80 to 100 parts of acetone, and 0.2 to 0.5 parts of dimethylimidazole.

6. The method for preparing a flame retardant and wear resistant hydrogenated nitrile rubber composite material according to claim 1, wherein: The preparation of the flame retardant modified carbon nanotubes comprises the following steps:

1. Mix biphenylphosphoramidate, sodium hydroxide and acetone under nitrogen protection, stir at a constant temperature of 5-10°C in an ice-water bath, add cyanuric chloride, stir and react for 2-3 hours, remove the solvent to obtain phosphate-modified cyanuric chloride; Step 2: Add carbon nanotubes to a mixed solution of water and ethanol, heat to 60-70°C, add aminosilane coupling agent and vinylsilane coupling agent, stir and react for 5-6 hours, remove the solvent, wash, and dry to obtain modified carbon nanotubes containing amino groups and double bonds; Step 3: Mix the modified carbon nanotubes, sodium hydroxide and acetone under nitrogen protection, stir at a constant temperature of 5-10°C in an ice water bath, add phosphate-modified cyanuric chloride, stir and react for 2-3 hours, remove the solvent, and obtain flame-retardant modified carbon nanotubes.

7. The method for preparing a flame retardant and wear resistant hydrogenated nitrile rubber composite material according to claim 6, characterized in that: The phosphate-modified cyanuric chloride comprises the following raw materials, calculated by mass: 15 to 25 parts of biphenylphosphamidate, 3 to 5 parts of sodium hydroxide, 100 to 150 parts of acetone, and 8 to 10 parts of cyanuric chloride; The modified carbon nanotubes include the following raw materials, calculated by weight: 10 to 15 parts of carbon nanotubes, 1 to 2 parts of aminosilane coupling agent, and 1 to 2 parts of vinylsilane coupling agent; The flame retardant modified carbon nanotubes include the following raw materials, calculated by mass: 10 to 15 parts of modified carbon nanotubes, 3 to 5 parts of sodium hydroxide, 100 to 150 parts of acetone, and 3 to 6 parts of phosphate-modified cyanuric chloride.

8. The method for preparing a flame retardant and wear resistant hydrogenated nitrile rubber composite material according to claim 1, wherein: The preparation of the zinc methacrylate modified polytetrafluoroethylene micropowder comprises the following steps: Take polytetrafluoroethylene micropowder and zinc methacrylate, stir for 2 to 5 minutes, and obtain zinc methacrylate modified polytetrafluoroethylene micropowder.

9. The method for preparing a flame retardant and wear resistant hydrogenated nitrile rubber composite material according to claim 8, characterized in that: The zinc methacrylate modified polytetrafluoroethylene powder comprises the following raw materials, calculated by mass: 10 to 15 parts of polytetrafluoroethylene powder and 1 to 2 parts of zinc methacrylate.

10. A hydrogenated nitrile rubber composite material prepared according to the method for preparing a flame retardant and wear resistant hydrogenated nitrile rubber composite material according to any one of claims 1 to 9.

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