Multidimensional filler synergistically modified thermoplastic polyester elastomer compositions, methods of making and use

Abstract

Multi-dimensional filler synergistically modified thermoplastic polyester elastomer composition, preparation method and application relate to the technical field of functional composite materials, and comprise the following components by mass percentage: 1-3% of molybdenum disulfide-graphene oxide hybrid material, 3-5% of carbon fiber micro powder, 0.1-1% of inorganic nano particles, 0.1-0.5% of antioxidant and the balance of thermoplastic polyester elastomer. The thermoplastic polyester elastomer composition modified by multi-dimensional fillers has high strength and high elasticity, and has high temperature resistance and thermal conductivity, and has a long service life under the conditions of high temperature and frequent swing.

Description

Technical Field

[0001] This invention relates to the field of functional composite materials technology, and in particular to thermoplastic polyester elastomer compositions modified by multidimensional fillers, their preparation methods, and applications. Background Technology

[0002] Thermoplastic polyester elastomers (TPEEs) consist of rigid, crystalline, high-melting-point aromatic polyester segments and soft, amorphous, low-glass-transition-temperature aliphatic polyester or polyether segments linked by chemical bonds. TPEEs perfectly combine the high elasticity of rubber products, the high strength of engineering plastics, and the easy processability of thermoplastics. Due to the polarity, rigidity, and crystallinity of the rigid polyester segments, TPEEs possess excellent thermal properties and resistance to oils and solvents. Because the soft polyether segments have a low glass transition temperature, the material also exhibits excellent anti-aging properties and mechanical properties.

[0003] TPEE combines excellent melt stability, thermoplasticity, and good processability, allowing for the use of various thermoplastic processing techniques such as extrusion, blow molding, injection molding, melt casting, and rotational molding to obtain products with superior performance. Thermoplastic polyester elastomers combine the advantages of both plastics and rubber materials, exhibiting excellent properties such as high toughness, high strength, abrasion resistance, cold resistance, oil resistance, aging resistance, and biodegradability. Thermoplastic polyester elastomer products possess high strength, good airtightness, and abrasion resistance, leading to their widespread application in numerous fields.

[0004] Thermoplastic polyester elastomers (TPEs) possess excellent flexural fatigue properties and a relatively wide operating temperature range, making them a preferred material for bearing dust cover seals. However, under conditions of frequent oscillation and high temperatures, the mechanical properties of TPEs decrease, consequently reducing their service durability. Furthermore, bearing dust covers generate friction during bearing operation; therefore, materials used for bearing dust covers must possess certain friction-reducing and wear-resistant properties. Summary of the Invention

[0005] The purpose of this invention is to provide a thermoplastic polyester elastomer composition modified by multidimensional fillers, its preparation method and application. The thermoplastic polyester elastomer composition modified by multidimensional fillers has high strength and high elasticity, as well as high temperature resistance and thermal conductivity, and has a long service life under high temperature, frequent oscillation and other conditions.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: The first objective of the present invention is to provide a thermoplastic polyester elastomer composition with multidimensional filler synergistic modification, comprising the following components by mass percentage: 1-3% molybdenum disulfide-graphene oxide hybrid material, 3-5% carbon fiber powder, 0.1-1% inorganic nanoparticles, 0.1-0.5% antioxidant, and the remainder thermoplastic polyester elastomer.

[0007] Preferably, the molybdenum disulfide-graphene oxide hybrid material is prepared by a hydrothermal method. Both molybdenum disulfide and graphene have certain lubricity, but their tribological properties differ under different environments. Graphene not only has good lubricity but also excellent mechanical properties and thermal conductivity. When the two materials are combined and added to polyester elastomer, the friction reduction and wear resistance of the composite material are improved, while the strength and thermal conductivity of the composite material are also improved.

[0008] Preferably, the carbon fiber powder is a micron-sized carbon fiber powder with a particle size of 300-500 mesh. The carbon fiber powder is first acidified and oxidized, and then modified with a silane coupling agent to improve the compatibility between the carbon fiber powder and the polymer matrix material (thermoplastic polyester elastomer). Carbon fiber has high strength, high modulus, high heat resistance, and high thermal conductivity. The addition of carbon fiber powder can improve the strength and thermal conductivity of thermoplastic polyester elastomer.

[0009] Preferably, the inorganic nanoparticles are one or more of nano-silica, nano-alumina, nano-carbon dioxide, and nano-silicon nitride. The inorganic nanoparticles are modified with a silane coupling agent. The addition of inorganic nanoparticles can improve the strength and toughness of the composite material.

[0010] Preferably, the antioxidant is antioxidant 1010, and the addition of antioxidant 1010 can inhibit the oxidative decomposition of thermoplastic polyester elastomer at high temperature.

[0011] Preferably, the thermoplastic polyester elastomer possesses the elasticity of rubber, the strength of engineering plastics, and the excellent processing and molding properties of thermoplastics, making it a material highly suitable for use in bearing seals.

[0012] A second objective of this invention is to provide a method for preparing a thermoplastic polyester elastomer composition with multidimensional filler synergistic modification, comprising the following steps: Step S1: Add graphene to concentrated sulfuric acid with a mass concentration of 98% (the mass-volume ratio of graphene to concentrated sulfuric acid is 1:30 (g / mL)) to obtain a mixed solution. Place the mixed solution in an ice-water bath and stir continuously for 1 hour. Then, weigh out potassium permanganate and slowly add it to the above mixed solution (the mass ratio of graphene to potassium permanganate is 1:3). React at 35°C for 4 hours to obtain a reaction solution.

[0013] The above reaction solution was added to about 6 times the volume of deionized water. After stirring and mixing evenly under ice bath conditions, the mixture was heated to 80°C and stirred for 3 hours. Then, 30% hydrogen peroxide (the mass-volume ratio of graphene to hydrogen peroxide was 1:50 (g / mL)) was added and stirred to obtain a suspension.

[0014] The suspension was centrifuged at 1000 rad / min for 5 min, washed with 5% hydrochloric acid solution, and then washed three times with deionized water. The resulting precipitate was dispersed in deionized water to obtain a suspension of graphene oxide.

[0015] Add ammonium heptamolybdate hydrate and thioacetamide to the graphene oxide suspension (calculate the amount of ammonium heptamolybdate hydrate and thioacetamide based on the mass of molybdenum disulfide being 50% of the mass of graphene), stir until completely dissolved, and obtain a raw material mixture. Transfer the raw material mixture into a high-pressure reactor lined with polytetrafluoroethylene, react at 200°C for 24 hours, filter to obtain a black precipitate, wash three times with deionized water, and freeze-dry for later use.

[0016] Step S2: Add carbon fiber powder to a 65% (w / w) nitric acid solution, stir and reflux at 100°C for 6 hours to acidify, then add distilled water to dilute the solution. After filtration and multiple rinsing with distilled water, acid-modified carbon fiber powder is obtained. The obtained acid-modified carbon fiber powder was dispersed in anhydrous ethanol and stirred for 30 minutes until it was evenly dispersed. Glacial acetic acid was added dropwise to adjust the pH of the solution to between 3 and 4. Under stirring conditions, KH560 silane coupling agent was added at a mass ratio of 3% of the carbon fiber powder and stirred for 60 minutes. Centrifuge, wash three times with anhydrous ethanol, wash three times with water, and then dry in a vacuum drying oven at 110℃ for 6 hours to obtain carbon fiber micro powder modified with silane coupling agent.

[0017] Step S3: Disperse the inorganic nanoparticles in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid dropwise to adjust the pH of the solution to between 3 and 4. Add KH560 silane coupling agent slowly dropwise to the dispersion at a ratio of 3% by mass of inorganic nanoparticles, and stir for 60 minutes. Centrifuge, wash three times with anhydrous ethanol, then wash three times with water, and finally dry in a vacuum drying oven at 110°C for 6 hours.

[0018] Step S4: Dry the thermoplastic polyester elastomer in a vacuum drying oven at 80°C for 6 hours.

[0019] Step S5: Weigh the modified molybdenum disulfide-graphene oxide hybrid material, modified carbon fiber powder, modified inorganic nanoparticles, antioxidant 1010 and thermoplastic polyester elastomer according to the proportion and add them to a high-speed mixer. Stir at 120-150 r / min for 15-30 min to mix evenly.

[0020] Step S6: Add the uniformly mixed raw materials to a twin-screw extruder for melt blending and extrusion granulation to obtain thermoplastic polyester elastomer composite particles. The extrusion temperature is 180~220℃ and the screw speed is 220-250r / min.

[0021] Step S7: The prepared thermoplastic polyester elastomer composite particles are injection molded using an injection molding machine at an injection temperature of 180~220℃ to obtain a thermoplastic polyester elastomer composition modified by multidimensional fillers.

[0022] A third objective of this invention is to provide the application of a multidimensional filler-modified thermoplastic polyester elastomer composition in bearing dust cover seals. The thermoplastic polyester elastomer composition prepared by this invention exhibits high strength, elasticity, and temperature resistance. When used to prepare bearing dust cover seals, this composition can provide a long service life under conditions of frequent oscillation and high temperatures.

[0023] Compared with the prior art, the present invention has the following advantages: 1. This invention uses molybdenum disulfide-graphene oxide hybrid material, carbon fiber powder and inorganic nanoparticles for multidimensional synergistic modification. Through layered graphene and rod-shaped carbon fiber powder, a multidimensional skeleton is built, which plays a synergistic role in reinforcement and thermal conductivity in the composite material, thereby improving the strength and thermal conductivity of the composite material.

[0024] 2. By adding hybrid molybdenum disulfide and graphene oxide, the present invention achieves complementary tribological properties under different environmental conditions through the synergistic effect of molybdenum disulfide and graphene oxide, which greatly improves the friction reduction and wear resistance of the composite material and extends the service life of the composite material as a bearing dust cover.

[0025] 3. The addition of inorganic nanoparticles can enrich them in the micropores of graphene and carbon fiber powder skeleton, further improving the strength and toughness of the composition.

[0026] 4. This application modifies carbon fiber micropowder. Because carbon fiber micropowder has a smooth surface and poor compatibility with polymer materials, it is modified using a method of first acidification and oxidation followed by coupling agent modification. Acidification and oxidation with concentrated nitric acid gives the carbon fiber micropowder a certain amount of active functional groups on its surface. Based on this, a silane coupling agent is used for modification, resulting in better compatibility between the carbon fiber micropowder and the thermoplastic polyester elastomer.

[0027] 5. This application also modifies the inorganic nanoparticles with coupling agents, which improves the dispersibility of the inorganic nanoparticles. The inorganic nanoparticles are dispersed in the matrix material at the nanoscale, thereby improving the strength and toughness of the composite material.

[0028] This invention effectively improves the strength and thermal conductivity of thermoplastic polyester elastomers through multidimensional synergistic modification using molybdenum disulfide-graphene oxide hybrid materials, carbon fiber micropowder, and inorganic nanoparticles, thus broadening the application range of thermoplastic polyester elastomers in bearing dust cover seals. Detailed Implementation

[0029] The following provides a more detailed description of specific embodiments of the present invention. It should be understood that this illustrative description of the invention is not intended to limit the scope of protection of the invention.

[0030] Nano-alumina, purchased from Beijing Deco Island Gold Technology Co., Ltd., model number DK410-1; Graphene was purchased from Nanjing Pioneer Nanotechnology Co., Ltd. Carbon fiber powder was purchased from Yancheng Xiang Sheng Carbon Fiber Technology Co., Ltd. The thermoplastic polyester elastomer, model H55DMG, was purchased from Jiangyin Hechuang Elastomer New Material Technology Co., Ltd. Ammonium molybdate heptahydrate hydrate was purchased from Sinopharm Chemical Reagent Co., Ltd. Thioacetamide was purchased from Sinopharm Chemical Reagent Co., Ltd. Antioxidant 1010 was purchased from Shanghai Lingrui Chemical Co., Ltd. Nano silicon nitride, purchased from Beijing Deco Island Gold Technology Co., Ltd., model number DK-Si3N4-01.

[0031] Compare with Example 1 (Molybdenum disulfide instead of molybdenum disulfide-graphene oxide hybrid material) A thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers, comprising the following components by weight percentage: 2% molybdenum disulfide, 4% carbon fiber powder, 0.5% nano-alumina, 0.3% antioxidant 1010, and the remainder is thermoplastic polyester elastomer.

[0032] A method for preparing a thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers includes the following steps: Step S1: Add carbon fiber powder to a 65% nitric acid solution, stir and reflux at 100°C for 6 hours, then add distilled water to dilute the solution, and after filtration and multiple rinsing with distilled water, obtain acid-modified carbon fiber powder. The obtained acid-modified carbon fiber powder was dispersed in anhydrous ethanol and stirred for 30 minutes until it was evenly dispersed. Glacial acetic acid was added dropwise to adjust the pH of the solution to between 3 and 4. Under stirring conditions, KH560 silane coupling agent was added at a mass ratio of 3% of the carbon fiber powder and stirred for 60 minutes. Centrifuge, wash three times with anhydrous ethanol, wash three times with water, and then dry in a vacuum drying oven at 110℃ for 6 hours to obtain carbon fiber micro powder modified with silane coupling agent.

[0033] Step S2: Disperse nano-alumina in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid dropwise to adjust the pH of the solution to between 3 and 4. Add KH560 silane coupling agent slowly dropwise to the dispersion at a mass percentage of 3% of nano-alumina and stir for 60 minutes. Centrifuge, wash three times with anhydrous ethanol, then wash three times with water and centrifuge again. Finally, dry in a vacuum drying oven at 110°C for 6 hours.

[0034] Step S3: Dry the thermoplastic polyester elastomer in a vacuum drying oven at 80°C for 6 hours.

[0035] Step S4: Add molybdenum disulfide, modified carbon fiber powder, modified nano alumina, antioxidant 1010 and thermoplastic polyester elastomer to a high-speed mixer and mix evenly.

[0036] Step S5: Add the uniformly mixed raw materials to a twin-screw extruder for melt blending and extrusion granulation. The extrusion temperature is 200℃ and the screw speed is 230r / min.

[0037] Step S6: The prepared thermoplastic polyester elastomer composite particles are injection molded using an injection molding machine at an injection temperature of 210℃.

[0038] Comparative Example 2 (unmodified carbon fiber powder) A thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers, comprising the following components by weight percentage: 2% molybdenum disulfide-graphene oxide hybrid material, 4% carbon fiber powder, 0.5% nano-alumina, 0.3% antioxidant 1010, and the remainder thermoplastic polyester elastomer.

[0039] A method for preparing a thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers includes the following steps: Step S1: Add graphene to concentrated sulfuric acid with a mass concentration of 98% (the mass-volume ratio of graphene to concentrated sulfuric acid is 1:30 (g / mL)) to obtain a mixed solution. Place the mixed solution in an ice-water bath and stir continuously for 1 hour. Then, weigh out potassium permanganate and slowly add it to the above mixed solution (the mass ratio of graphene to potassium permanganate is 1:3). React at 35°C for 4 hours.

[0040] The above reaction solution was added to about 6 times the volume of deionized water. After stirring and mixing evenly under ice bath conditions, the mixture was heated to 80°C and stirred for 3 hours. Then, 30% hydrogen peroxide (the mass-volume ratio of graphene to hydrogen peroxide was 1:50 (g / mL)) was added and stirred to obtain a suspension.

[0041] The suspension was centrifuged at 1000 rad / min for 5 min, washed with 5% hydrochloric acid solution, and then washed three times with deionized water. The resulting precipitate was dispersed in deionized water to obtain a suspension of graphene oxide.

[0042] Add ammonium heptamolybdate hydrate and thioacetamide to the graphene oxide suspension (calculate the amount of ammonium heptamolybdate hydrate and thioacetamide based on the mass of molybdenum disulfide being 50% of the mass of graphene), stir until completely dissolved, and obtain a raw material mixture. Transfer the raw material mixture into a high-pressure reactor lined with polytetrafluoroethylene, react at 200°C for 24 hours, filter to obtain a black precipitate, wash three times with deionized water, and freeze-dry for later use.

[0043] Step S2: Disperse nano-alumina in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid dropwise to adjust the pH of the solution to between 3 and 4. Add KH560 silane coupling agent slowly dropwise to the dispersion at a mass percentage of 3% of nano-alumina and stir for 60 minutes. Centrifuge, wash three times with anhydrous ethanol, then wash three times with water and centrifuge again. Finally, dry in a vacuum drying oven at 110°C for 6 hours.

[0044] Step S3: Dry the thermoplastic polyester elastomer in a vacuum drying oven at 80°C for 6 hours.

[0045] Step S4: Add the molybdenum disulfide-graphene oxide hybrid material, carbon fiber powder, modified nano-alumina, antioxidant 1010 and thermoplastic polyester elastomer to a high-speed mixer and mix evenly.

[0046] Step S5: Add the uniformly mixed raw materials to a twin-screw extruder for melt blending and extrusion granulation. The extrusion temperature is 200℃ and the screw speed is 230r / min.

[0047] Step S6: The prepared thermoplastic polyester elastomer composite particles are injection molded using an injection molding machine at an injection temperature of 210℃.

[0048] Comparative Example 3 (without added inorganic nanoparticles) A thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers, comprising the following components by weight percentage: 2% molybdenum disulfide-graphene oxide hybrid material, 4% carbon fiber powder, 0.3% antioxidant 1010, and the remainder thermoplastic polyester elastomer.

[0049] A method for preparing a thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers includes the following steps: Step S1: Add graphene to concentrated sulfuric acid with a mass concentration of 98% (the mass-volume ratio of graphene to concentrated sulfuric acid is 1:30 (g / mL)) to obtain a mixed solution. Place the mixed solution in an ice-water bath and stir continuously for 1 hour. Then, weigh out potassium permanganate and slowly add it to the above mixed solution (the mass ratio of graphene to potassium permanganate is 1:3). React at 35°C for 4 hours.

[0050] The above reaction solution was added to about 6 times the volume of deionized water. After stirring and mixing evenly under ice bath conditions, the mixture was heated to 80°C and stirred for 3 hours. Then, 30% hydrogen peroxide (the mass-volume ratio of graphene to hydrogen peroxide was 1:50 (g / mL)) was added and stirred to obtain a suspension.

[0051] The suspension was centrifuged at 1000 rad / min for 5 min, washed with 5% hydrochloric acid solution, and then washed three times with deionized water. The resulting precipitate was dispersed in deionized water to obtain a suspension of graphene oxide.

[0052] Add ammonium heptamolybdate hydrate and thioacetamide to the graphene oxide suspension (calculate the amount of ammonium heptamolybdate hydrate and thioacetamide based on the mass of molybdenum disulfide being 50% of the mass of graphene), stir until completely dissolved, and obtain a raw material mixture. Transfer the raw material mixture into a high-pressure reactor lined with polytetrafluoroethylene, react at 200°C for 24 hours, filter to obtain a black precipitate, wash three times with deionized water, and freeze-dry for later use.

[0053] Step S2: Add carbon fiber powder to a 65% nitric acid solution and reflux at 100°C for 6 hours. Then dilute the solution with distilled water. After filtration and multiple rinsing with distilled water, acid-modified carbon fiber powder is obtained. Disperse the acid-modified carbon fiber powder in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid to adjust the pH of the solution to between 3 and 4. Under stirring, add KH560 silane coupling agent at a mass ratio of 3% of the carbon fiber powder and stir for 60 minutes. Centrifuge, wash with anhydrous ethanol three times, centrifuge three times with water, and then dry in a vacuum drying oven at 110°C for 6 hours to obtain carbon fiber powder modified with silane coupling agent.

[0054] Step S3: Dry the thermoplastic polyester elastomer in a vacuum drying oven at 80°C for 6 hours.

[0055] Step S4: Add the molybdenum disulfide-graphene oxide hybrid material, the modified carbon fiber powder, antioxidant 1010 and thermoplastic polyester elastomer to a high-speed mixer and mix evenly.

[0056] Step S5: Add the uniformly mixed raw materials to a twin-screw extruder for melt blending and extrusion granulation. The extrusion temperature is 200℃ and the screw speed is 230r / min.

[0057] Step S6: The prepared thermoplastic polyester elastomer composite particles are injection molded using an injection molding machine at an injection temperature of 210℃.

[0058] Example 1 A thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers, comprising the following components by weight percentage: 2% molybdenum disulfide-graphene oxide hybrid material, 4% carbon fiber powder, 0.5% nano-alumina, 0.3% antioxidant 1010, and the remainder thermoplastic polyester elastomer.

[0059] A method for preparing a thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers includes the following steps: Step S1: Add graphene to concentrated sulfuric acid with a mass concentration of 98% (the mass-volume ratio of graphene to concentrated sulfuric acid is 1:30 (g / mL)) to obtain a mixed solution. Place the mixed solution in an ice-water bath and stir continuously for 1 hour. Then, weigh out potassium permanganate and slowly add it to the above mixed solution (the mass ratio of graphene to potassium permanganate is 1:3). React at 35°C for 4 hours.

[0060] The above reaction solution was added to about 6 times the volume of deionized water. After stirring and mixing evenly under ice bath conditions, the mixture was heated to 80°C and stirred for 3 hours. Then, 30% hydrogen peroxide (the mass-volume ratio of graphene to hydrogen peroxide was 1:50 (g / mL)) was added and stirred to obtain a suspension.

[0061] The suspension was centrifuged at 1000 rad / min for 5 min, washed with 5% hydrochloric acid solution, and then washed three times with deionized water. The resulting precipitate was dispersed in deionized water to obtain a suspension of graphene oxide.

[0062] Add ammonium heptamolybdate hydrate and thioacetamide to the graphene oxide suspension (calculate the amount of ammonium heptamolybdate hydrate and thioacetamide based on the mass of molybdenum disulfide being 50% of the mass of graphene), stir until completely dissolved, and obtain a raw material mixture. Transfer the raw material mixture into a high-pressure reactor lined with polytetrafluoroethylene, react at 200°C for 24 hours, filter to obtain a black precipitate, wash three times with deionized water, and freeze-dry for later use.

[0063] Step S2: Add carbon fiber powder to a 65% nitric acid solution and reflux at 100°C for 6 hours. Then dilute the solution with distilled water. After filtration and multiple rinsing with distilled water, acid-modified carbon fiber powder is obtained. Disperse the acid-modified carbon fiber powder in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid to adjust the pH of the solution to between 3 and 4. Under stirring, add KH560 silane coupling agent at a mass ratio of 3% of the carbon fiber powder and stir for 60 minutes. Centrifuge, wash with anhydrous ethanol three times, centrifuge three times with water, and then dry in a vacuum drying oven at 110°C for 6 hours to obtain carbon fiber powder modified with silane coupling agent.

[0064] Step S3: Disperse nano-alumina in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid dropwise to adjust the pH of the solution to between 3 and 4. Add KH560 silane coupling agent slowly dropwise to the dispersion at a mass percentage of 3% of nano-alumina and stir for 60 minutes. Centrifuge, wash three times with anhydrous ethanol, then wash three times with water and centrifuge again. Finally, dry in a vacuum drying oven at 110°C for 6 hours.

[0065] Step S4: Dry the thermoplastic polyester elastomer in a vacuum drying oven at 80°C for 6 hours.

[0066] Step S5: Add the molybdenum disulfide-graphene oxide hybrid material, modified carbon fiber powder, modified nano-alumina, antioxidant 1010 and thermoplastic polyester elastomer to a high-speed mixer and mix evenly.

[0067] Step S6: Add the uniformly mixed raw materials to a twin-screw extruder for melt blending and extrusion granulation. The extrusion temperature is 200℃ and the screw speed is 230r / min.

[0068] Step S7: The prepared thermoplastic polyester elastomer composite particles are injection molded using an injection molding machine at an injection temperature of 210℃.

[0069] Example 2 (Inorganic nanoparticles selected are nano-silicon nitride) A thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers, comprising the following components by weight percentage: 2% molybdenum disulfide-graphene oxide hybrid material, 4% carbon fiber powder, 0.5% nano silicon nitride, 0.3% antioxidant 1010, and the remainder thermoplastic polyester elastomer.

[0070] A method for preparing a thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers includes the following steps: Step S1: Add graphene to concentrated sulfuric acid with a mass concentration of 98% (the mass-volume ratio of graphene to concentrated sulfuric acid is 1:30 (g / mL)) to obtain a mixed solution. Place the mixed solution in an ice-water bath and stir continuously for 1 hour. Then, weigh out potassium permanganate and slowly add it to the above mixed solution (the mass ratio of graphene to potassium permanganate is 1:3). React at 35°C for 4 hours.

[0071] The above reaction solution was added to about 6 times the volume of deionized water. After stirring and mixing evenly under ice bath conditions, the mixture was heated to 80°C and stirred for 3 hours. Then, 30% hydrogen peroxide (the mass-volume ratio of graphene to hydrogen peroxide was 1:50 (g / mL)) was added and stirred to obtain a suspension.

[0072] The suspension was centrifuged at 1000 rad / min for 5 min, washed with 5% hydrochloric acid solution, and then washed three times with deionized water. The resulting precipitate was dispersed in deionized water to obtain a suspension of graphene oxide.

[0073] Add ammonium heptamolybdate hydrate and thioacetamide to the graphene oxide suspension (calculate the amount of ammonium heptamolybdate hydrate and thioacetamide based on the mass of molybdenum disulfide being 50% of the mass of graphene). After stirring until completely dissolved, transfer the mixed solution into a high-pressure reactor lined with polytetrafluoroethylene and react at 200°C for 24 hours. Filter to obtain a black precipitate, wash three times with deionized water, and freeze-dry for later use.

[0074] Step S2: Add carbon fiber powder to a 65% nitric acid solution and reflux at 100°C for 6 hours. Then dilute the solution with distilled water. After filtration and multiple rinsing with distilled water, acid-modified carbon fiber powder is obtained. Disperse the acid-modified carbon fiber powder in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid to adjust the pH of the solution to between 3 and 4. Under stirring, add KH560 silane coupling agent at a mass ratio of 3% of the carbon fiber powder and stir for 60 minutes. Centrifuge, wash three times with anhydrous ethanol and centrifuge, wash three times with water and centrifuge, and then dry in a vacuum drying oven at 110°C for 6 hours to obtain carbon fiber powder modified with silane coupling agent.

[0075] Step S3: Disperse nano-silicon nitride in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid dropwise to adjust the pH of the solution to between 3 and 4. Add KH560 silane coupling agent slowly dropwise to the dispersion at a ratio of 3% by mass of nano-silicon nitride and stir for 60 minutes. Centrifuge, wash three times with anhydrous ethanol, then wash three times with water and centrifuge again. Finally, dry in a vacuum drying oven at 110°C for 6 hours.

[0076] Step S4: Dry the thermoplastic polyester elastomer in a vacuum drying oven at 80°C for 6 hours.

[0077] Step S5: Add the molybdenum disulfide-graphene oxide hybrid material, modified carbon fiber powder, modified nano silicon nitride, antioxidant 1010 and thermoplastic polyester elastomer into a high-speed mixer and mix evenly.

[0078] Step S6: Add the uniformly mixed raw materials to a twin-screw extruder for melt blending and extrusion granulation. The extrusion temperature is 200℃ and the screw speed is 230r / min.

[0079] Step S7: The prepared thermoplastic polyester elastomer composite particles are injection molded using an injection molding machine at an injection temperature of 210℃.

[0080] Example 3 (Increasing the proportion of carbon fiber powder) A thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers, comprising the following components by weight percentage: 2% molybdenum disulfide-graphene oxide hybrid material, 5% carbon fiber powder, 0.5% nano-alumina, 0.3% antioxidant 1010, and the remainder thermoplastic polyester elastomer.

[0081] A method for preparing a thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers includes the following steps: Step S1: Add graphene to concentrated sulfuric acid with a mass concentration of 98% (the mass-volume ratio of graphene to concentrated sulfuric acid is 1:30 (g / mL)) to obtain a mixed solution. Place the mixed solution in an ice-water bath and stir continuously for 1 hour. Then, weigh out potassium permanganate and slowly add it to the above mixed solution (the mass ratio of graphene to potassium permanganate is 1:3). React at 35°C for 4 hours.

[0082] The above reaction solution was added to about 6 times the volume of deionized water. After stirring and mixing evenly under ice bath conditions, the mixture was heated to 80°C and stirred for 3 hours. Then, 30% hydrogen peroxide (the mass-volume ratio of graphene to hydrogen peroxide was 1:50 (g / mL)) was added and stirred to obtain a suspension.

[0083] The suspension was centrifuged at 1000 rad / min for 5 min, washed with 5% hydrochloric acid solution, and then washed three times with deionized water. The resulting precipitate was dispersed in deionized water to obtain a suspension of graphene oxide.

[0084] Add ammonium heptamolybdate hydrate and thioacetamide to the graphene oxide suspension (calculate the amount of ammonium heptamolybdate hydrate and thioacetamide based on the mass of molybdenum disulfide being 50% of the mass of graphene), stir until completely dissolved, and obtain a raw material mixture. Transfer the raw material mixture into a high-pressure reactor lined with polytetrafluoroethylene, react at 200°C for 24 hours, filter to obtain a black precipitate, wash three times with deionized water, and freeze-dry for later use.

[0085] Step S2: Add carbon fiber powder to a 65% nitric acid solution and reflux at 100°C for 6 hours. Then dilute the solution with distilled water. After filtration and multiple rinsing with distilled water, acid-modified carbon fiber powder is obtained. Disperse the acid-modified carbon fiber powder in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid to adjust the pH of the solution to between 3 and 4. Under stirring, add KH560 silane coupling agent at a mass ratio of 3% of the carbon fiber powder and stir for 60 minutes. Centrifuge, wash with anhydrous ethanol three times, centrifuge three times with water, and then dry in a vacuum drying oven at 110°C for 6 hours to obtain carbon fiber powder modified with silane coupling agent.

[0086] Step S3: Disperse nano-alumina in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid dropwise to adjust the pH of the solution to between 3 and 4. Add KH560 silane coupling agent slowly dropwise to the dispersion at a mass percentage of 3% of nano-alumina and stir for 60 minutes. Centrifuge, wash three times with anhydrous ethanol, then wash three times with water and centrifuge again. Finally, dry in a vacuum drying oven at 110°C for 6 hours.

[0087] Step S4: Dry the thermoplastic polyester elastomer in a vacuum drying oven at 80°C for 6 hours.

[0088] Step S5: Add the molybdenum disulfide-graphene oxide hybrid material, modified carbon fiber powder, modified nano-alumina, antioxidant 1010 and thermoplastic polyester elastomer to a high-speed mixer and mix evenly.

[0089] Step S6: Add the uniformly mixed raw materials to a twin-screw extruder for melt blending and extrusion granulation. The extrusion temperature is 200℃ and the screw speed is 230r / min.

[0090] Step S7: The prepared thermoplastic polyester elastomer composite particles are injection molded using an injection molding machine at an injection temperature of 210℃.

[0091] Example 4 (Increasing the proportion of molybdenum disulfide-graphene oxide hybrid material) A thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers, comprising the following components by weight percentage: Molybdenum disulfide-graphene oxide hybrid material 3%, carbon fiber powder 4%, nano alumina 0.5%, antioxidant 1010 0.3%, thermoplastic polyester elastomer balance.

[0092] A method for preparing a thermoplastic polyester elastomer composition synergistically modified with multidimensional fillers includes the following steps: Step S1: Add graphene to concentrated sulfuric acid with a mass concentration of 98% (the mass-volume ratio of graphene to concentrated sulfuric acid is 1:30 (g / mL)) to obtain a mixed solution. Place the mixed solution in an ice-water bath and stir continuously for 1 hour. Then, weigh out potassium permanganate and slowly add it to the above mixed solution (the mass ratio of graphene to potassium permanganate is 1:3). React at 35°C for 4 hours.

[0093] The above reaction solution was added to about 6 times the volume of deionized water. After stirring and mixing evenly under ice bath conditions, the mixture was heated to 80°C and stirred for 3 hours. Then, 30% hydrogen peroxide (the mass-volume ratio of graphene to hydrogen peroxide was 1:50 (g / mL)) was added and stirred to obtain a suspension.

[0094] The suspension was centrifuged at 1000 rad / min for 5 min, washed with 5% hydrochloric acid solution, and then washed three times with deionized water. The resulting precipitate was dispersed in deionized water to obtain a suspension of graphene oxide.

[0095] Add ammonium heptamolybdate hydrate and thioacetamide to the graphene oxide suspension (calculate the amount of ammonium heptamolybdate hydrate and thioacetamide based on the mass of molybdenum disulfide being 50% of the mass of graphene), stir until completely dissolved, and obtain a raw material mixture solution. Transfer the raw material mixture solution into a high-pressure reactor lined with polytetrafluoroethylene, react at 200°C for 24 hours, filter to obtain a black precipitate, wash three times with deionized water, and freeze-dry for later use.

[0096] Step S2: Add carbon fiber powder to a 65% nitric acid solution and reflux at 100°C for 6 hours. Then dilute the solution with distilled water. After filtration and multiple rinsing with distilled water, acid-modified carbon fiber powder is obtained. Disperse the acid-modified carbon fiber powder in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid to adjust the pH of the solution to between 3 and 4. Under stirring, add KH560 silane coupling agent at a mass ratio of 3% of the carbon fiber powder and stir for 60 minutes. Centrifuge, wash three times with anhydrous ethanol and centrifuge, wash three times with water and centrifuge, and then dry in a vacuum drying oven at 110°C for 6 hours to obtain carbon fiber powder modified with silane coupling agent.

[0097] Step S3: Disperse nano-alumina in anhydrous ethanol and stir for 30 minutes until uniformly dispersed. Add glacial acetic acid dropwise to adjust the pH of the solution to between 3 and 4. Add KH560 silane coupling agent slowly dropwise to the dispersion at a mass percentage of 3% of nano-alumina and stir for 60 minutes. Centrifuge, wash three times with anhydrous ethanol, then wash three times with water and centrifuge again. Finally, dry in a vacuum drying oven at 110°C for 6 hours.

[0098] Step S4: Dry the thermoplastic polyester elastomer in a vacuum drying oven at 80°C for 6 hours.

[0099] Step S5: Add the molybdenum disulfide-graphene oxide hybrid material, modified carbon fiber powder, modified nano-alumina, antioxidant 1010 and thermoplastic polyester elastomer to a high-speed mixer and mix evenly.

[0100] Step S6: Add the uniformly mixed raw materials to a twin-screw extruder for melt blending and extrusion granulation. The extrusion temperature is 200℃ and the screw speed is 230r / min.

[0101] Step S7: The prepared thermoplastic polyester elastomer composite particles are injection molded using an injection molding machine at an injection temperature of 210℃.

[0102] The performance test method for thermoplastic polyester elastomer compositions is as follows: Tensile strength: Test method: GB / T 1040.2 / 1A-2006, see the test method for tensile strength of type 1A specimen; Elongation at break: Test method: GB / T 1040.2 / 1A-2006, see the test method for elongation at break of plastics; Wear amount: Test method: GB / T 9867-2008, see the test method for relative volumetric wear amount.

[0103] The thermoplastic polyester elastomer compositions prepared in Comparative Examples 1, 2, and 3, as well as Examples 1, 2, 3, and 4, were tested for tensile strength, elongation at break, and wear. The results are as follows: Table 1. Performance test results of the thermoplastic polyester elastomer compositions in the comparative examples and embodiments.

Claims

1. A thermoplastic polyester elastomer composition synergistically modified with a multidimensional filler, characterized by, Includes the following components by mass percentage: The composition includes 1-3% molybdenum disulfide-graphene oxide hybrid material, 3-5% carbon fiber powder, 0.1-1% inorganic nanoparticles, 0.1-0.5% antioxidant, and the balance being thermoplastic polyester elastomer; wherein the inorganic nanoparticles are one or more of nano-silica, nano-alumina, and nano-silicon nitride; wherein the carbon fiber powder is carbon fiber powder that has undergone acidification and oxidation followed by modification with a silane coupling agent; and wherein the inorganic nanoparticles are inorganic nanoparticles modified with a silane coupling agent. The preparation method of the molybdenum disulfide-graphene oxide hybrid material is as follows: (1) Add graphene to concentrated sulfuric acid with a mass concentration of 98% to obtain a mixed solution. Place the mixed solution in an ice-water bath and stir continuously for 1 hour. Then weigh potassium permanganate and slowly add it to the above mixed solution. React at 35°C for 4 hours to obtain a reaction solution. (2) Add the above reaction solution to deionized water, stir and mix evenly under ice bath conditions, heat to 80°C and stir for 3 hours, then add 30% hydrogen peroxide and stir to obtain a suspension. (3) After centrifuging the suspension at 1000 rad / min for 5 min, wash it with 5% hydrochloric acid solution and then wash it three times with deionized water. Disperse the precipitate in deionized water to obtain a suspension of graphene oxide. (4) Add ammonium heptamolybdate hydrate and thioacetamide to the suspension of graphene oxide, stir until completely dissolved to obtain a raw material mixture, transfer the raw material mixture into a high-pressure reactor lined with polytetrafluoroethylene, react at 200°C for 24 hours, filter to obtain a black precipitate, wash three times with deionized water and freeze dry for later use.

2. The multi-dimensional filler synergistically modified thermoplastic polyester elastomer composition according to claim 1, characterized by, The antioxidant is antioxidant 1010.

3. The method for producing a multi-dimensional filler synergistically modified thermoplastic polyester elastomer composition according to any one of claims 1 to 2, characterized by, include: Dry the thermoplastic polyester elastomer; The molybdenum disulfide-graphene oxide hybrid material, carbon fiber powder, inorganic nanoparticles, antioxidants and thermoplastic polyester elastomers are added to a high-speed mixer and mixed evenly. The uniformly mixed raw materials are added to a twin-screw extruder for melt blending and extrusion granulation to obtain thermoplastic polyester elastomer composite particles; The prepared thermoplastic polyester elastomer composite particles were injection molded using an injection molding machine to form a thermoplastic polyester elastomer composition.

4. The method for producing a multi-dimensional filler synergistically modified thermoplastic polyester elastomer composition according to claim 3, characterized by, The carbon fiber powder is a modified carbon fiber powder, and the operation method is as follows: Carbon fiber powder was added to a 65% nitric acid solution and acidified by stirring and reflux at 100°C. Then, distilled water was added to dilute the solution. After filtration and multiple rinsing with distilled water, acidified modified carbon fiber powder was obtained. The obtained acid-modified carbon fiber powder was dispersed in anhydrous ethanol and stirred until it was evenly dispersed. Glacial acetic acid was added dropwise to adjust the pH of the solution to between 3 and 4. Under stirring conditions, KH560 silane coupling agent was added at a mass ratio of 3% of carbon fiber powder, and stirred for 60 minutes. The carbon fiber powder was washed and centrifuged three times with anhydrous ethanol, then washed and centrifuged three times with water; and dried in a vacuum drying oven to obtain carbon fiber micropowder modified with silane coupling agent.

5. The method for preparing the thermoplastic polyester elastomer composition with multidimensional filler synergistic modification according to claim 3, characterized in that, The inorganic nanoparticles are modified inorganic nanoparticles, and the operation method is as follows: Inorganic nanoparticles were dispersed in anhydrous ethanol and stirred until uniformly dispersed. Glacial acetic acid was added dropwise to adjust the pH of the solution to between 3 and 4. KH560 silane coupling agent was slowly added dropwise to the dispersion at a mass percentage of 3% of inorganic nanoparticles under stirring conditions. The mixture was then washed with anhydrous ethanol and centrifuged three times, followed by washing with water and centrifuging three times. Finally, the mixture was dried in a vacuum drying oven.

6. The application of thermoplastic polyester elastomer compositions synergistically modified with multidimensional fillers in bearing dust cover seals, characterized in that... The thermoplastic polyester elastomer composition is the thermoplastic polyester elastomer composition according to any one of claims 1-2, or the thermoplastic polyester elastomer composition obtained by the preparation method according to any one of claims 3-5.

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