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CN-122011731-A - High-wear-resistance anti-aging TPU composite material and preparation method thereof

CN122011731ACN 122011731 ACN122011731 ACN 122011731ACN-122011731-A

Abstract

The invention discloses a high wear-resistant anti-aging TPU composite material and a preparation method thereof, and relates to the technical field of TPU composite materials. The high wear-resistant anti-aging TPU composite material comprises, by weight, 90-100 parts of thermoplastic polyurethane elastomer, 5-12 parts of modified nano silicon dioxide, 8-15 parts of modified basalt fiber, 0.2-0.5 part of antioxidant 1010, 0.3-0.6 part of ultraviolet absorbent UV-531, 0.5-1.0 part of zinc stearate and 0.8-1.5 part of trimethylolpropane triacrylate. The high wear-resistant anti-aging TPU composite material has scientific raw material proportion, the compatibility of modified nano silicon dioxide and basalt fiber is enhanced by multi-step modification, the preparation process is standard, the quality is ensured by processes such as melt blending and secondary water cooling, the high wear-resistant anti-aging TPU composite material has excellent wear resistance and aging resistance, the mechanical property is good, and the application potential is large.

Inventors

  • SHI CHUANJIE

Assignees

  • 东莞市宇捷实业投资有限公司

Dates

Publication Date
20260512
Application Date
20260302

Claims (8)

  1. 1. The TPU composite material with high wear resistance and ageing resistance is characterized by comprising the following raw materials, by weight, 90-100 parts of thermoplastic polyurethane elastomer, 5-12 parts of modified nano silicon dioxide, 8-15 parts of modified basalt fiber, 0.2-0.5 part of antioxidant 1010, 0.3-0.6 part of ultraviolet absorbent UV-531, 0.5-1.0 part of zinc stearate and 0.8-1.5 part of trimethylolpropane triacrylate.
  2. 2. The TPU composite with high wear resistance and aging resistance according to claim 1, wherein the thermoplastic polyurethane elastomer has a Shore hardness of 85-95A, a number average molecular weight of 20000-30000 and an NCO/OH molar ratio of 1.05-1.15.
  3. 3. The high wear-resistant anti-aging TPU composite material of claim 1, wherein the modified nano silicon dioxide comprises the following specific preparation steps: a1, taking nano silicon dioxide, adding absolute ethyl alcohol, performing ultrasonic dispersion for 30min, adding dilute sulfuric acid solution with the concentration of 0.5mol/L, heating to 60-70 ℃, stirring and reacting for 2h, then adding a silane coupling agent KH550 into the system, continuing to perform heat preservation and reaction for 3h, performing centrifugal separation after the reaction is finished, washing for 3-4 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 80 ℃ for 6h to obtain first modified nano silicon dioxide; A2, adding toluene into the first modified nano silicon dioxide, carrying out ultrasonic dispersion for 20min, heating to 80-85 ℃, dropwise adding polyurethane prepolymer composed of isophorone diisocyanate and polyethylene glycol adipate into the system at the dropwise adding rate of 1-2ml/min, adding dibutyl tin dilaurate after the dropwise adding, carrying out heat preservation reaction for 4h, adding n-butanol, adding 0.01-0.02g dibutyl tin dilaurate, heating to 85 ℃ and continuing to react for 2h, carrying out centrifugal separation, washing toluene for 2 times, and carrying out vacuum drying at 60 ℃ for 8h to obtain second modified nano silicon dioxide; a3, taking the second modified nano silicon dioxide, adding N, N-dimethylformamide, performing ultrasonic dispersion for 15min, heating to 75-80 ℃, adding an antioxidant 1076 and adipic dihydrazide, performing heat preservation reaction for 5h, cooling to room temperature, performing centrifugal separation, washing with acetone for 3 times, and performing vacuum drying at 90 ℃ for 10h to obtain the modified nano silicon dioxide.
  4. 4. The high abrasion-resistant anti-aging TPU composite material according to claim 3, wherein the dosage ratio of nano silicon dioxide, absolute ethyl alcohol, dilute sulfuric acid solution and silane coupling agent KH550 in A1 is 100g:500-600ml:80-100ml:15-20ml; The first modified nano silicon dioxide, toluene, isophorone diisocyanate, polyethylene glycol adipate, dibutyl tin dilaurate and n-butyl alcohol are added in the A2 according to the dosage ratio of 100g:400-500ml:25-30ml:40-50g:0.31-0.52g:10-15ml, wherein the total dosage of dibutyl tin dilaurate is 0.31-0.52g, the first modified nano silicon dioxide, toluene, isophorone diisocyanate, polyethylene glycol adipate and n-butyl alcohol are added in the first polyurethane prepolymer grafting reaction, the second n-butyl alcohol end capping reaction is added in the second polyurethane prepolymer grafting reaction, the two ends of the polyethylene glycol adipate are hydroxyl groups, and the molecular weight is 1000; The dosage ratio of the second modified nano silicon dioxide to the N, N-dimethylformamide to the antioxidant 1076 to the adipic acid dihydrazide in the A3 is 100g:350-450ml:20-25g:10-15g.
  5. 5. The high wear-resistant anti-aging TPU composite material of claim 1, wherein the modified basalt fiber comprises the following specific preparation steps: B1, taking basalt fiber, placing the basalt fiber into a muffle furnace, heating to 450 ℃ at a speed of 5 ℃ per minute, preserving heat for 2 hours, removing surface organic impregnating compound to obtain degummed basalt fiber, taking degummed basalt fiber, adding sodium hydroxide solution with a concentration of 1mol/L, stirring at room temperature for reacting for 1.5 hours, then adding silane coupling agent KH560 into the system, heating to 50-60 ℃, stirring for reacting for 3 hours, washing to neutrality by deionized water after the reaction is finished, and drying at 100 ℃ for 4 hours to obtain first modified basalt fiber; B2, taking the first modified basalt fiber, placing the basalt fiber into a high-pressure reaction kettle, adding dimethylbenzene, heating to 120-130 ℃ in a nitrogen atmosphere, adding maleic anhydride and dibenzoyl peroxide, reacting for 6 hours in a heat-preserving way, cooling to room temperature, filtering, washing for 2 times with dimethylbenzene, and vacuum drying for 6 hours at 80 ℃ to obtain a second modified basalt fiber; And B3, taking the basalt fiber subjected to the second modification, adding butanone, performing ultrasonic dispersion for 20min, heating to 70-75 ℃, adding polycaprolactone diol and p-toluenesulfonic acid, performing heat preservation reaction for 4 hours, filtering, washing with butanone for 2 times, and performing vacuum drying at 100 ℃ for 8 hours to obtain the modified basalt fiber.
  6. 6. The high wear-resistant anti-aging TPU composite material according to claim 5, wherein the dosage ratio of degummed basalt fiber, sodium hydroxide solution and silane coupling agent KH560 in B1 is 100g:300-400ml:20-25ml; The dosage ratio of the first modified basalt fiber to the dimethylbenzene to the maleic anhydride to the dibenzoyl peroxide in the B2 is 100g:250-350ml:30-35g:1-1.5g; The dosage ratio of the second modified basalt fiber to the butanone to the polycaprolactone diol to the p-toluenesulfonic acid in the B3 is 100g:300-400ml:50-60g:0.5-0.8g.
  7. 7. A preparation method of a high wear-resistant anti-aging TPU composite material is characterized by comprising the following steps: S1, placing a thermoplastic polyurethane elastomer in a vacuum drying oven at 80 ℃ for drying for 4 hours, removing water, adding the dried thermoplastic polyurethane elastomer into a high-speed mixer, setting the rotating speed to be 800-1000r/min and the temperature to be 60-70 ℃, sequentially adding 0.5-1.0 part of zinc stearate, 0.2-0.5 part of antioxidant 1010 and 0.3-0.6 part of ultraviolet absorbent UV-531, mixing for 5 minutes, adding 5-12 parts of modified nano silicon dioxide, continuing mixing for 8 minutes, finally adding 8-15 parts of modified basalt fiber and 0.8-1.5 part of trimethylolpropane triacrylate, and mixing for 10 minutes to obtain a premix; S2, adding premix into a double-screw extruder, setting the temperatures of each section of the extruder, namely 160-170 ℃ in a first section, 175-185 ℃ in a second section, 185-195 ℃ in a third section and 185-190 ℃ in a machine head, wherein the screw speed is 200-250r/min, and the feeding rate is 20-30kg/h; S3, placing the composite material particles in a vacuum drying oven at 85 ℃ for drying for 3 hours, removing surface moisture, adopting an injection molding machine for injection molding, wherein the injection molding temperature is 180-195 ℃, the mold temperature is 40-50 ℃, the injection molding pressure is 80-100MPa, the holding pressure is 50-60MPa, and the holding time is 10-15S, so that the high wear-resistant anti-aging TPU composite material product is obtained.
  8. 8. The preparation method of the high wear-resistant anti-aging TPU composite material is characterized in that the water-cooling granulating process in the step S2 adopts a secondary cooling process, the first-stage cooling water temperature is 25-30 ℃, the material retention time is 3-5S, the second-stage cooling water temperature is 10-15 ℃, and the material retention time is 5-8S.

Description

High-wear-resistance anti-aging TPU composite material and preparation method thereof Technical Field The invention relates to the technical field of TPU composite materials, in particular to a high wear-resistant anti-aging TPU composite material and a preparation method thereof. Background Thermoplastic polyurethane elastomers (TPU) are widely used in various fields such as automobile manufacturing, electronic appliances, medical devices, sports equipment, etc. as a polymer material having both high rubber elasticity and plastic processability, and by virtue of excellent mechanical strength, flexibility, oil resistance and environmental recyclability. However, in complex application scenes such as outdoor use, high-frequency friction, severe working conditions and the like, the conventional TPU material has obvious short plates, and the problems of insufficient wear resistance and weak ageing resistance are particularly remarkable, so that the application range and the service life are greatly limited. In the aspect of wear resistance, the traditional TPU material is easy to generate surface wear, cracks and even failure under the long-term friction effect, and particularly in high-frequency contact scenes such as automobile sealing strips, transmission parts, sole materials and the like, the performance attenuation caused by wear directly influences the use experience and safety of products. On the aspect of ageing resistance, the TPU material is exposed to environments such as sunlight irradiation, oxygen, temperature change and the like for a long time, oxidative degradation and molecular chain breakage are easy to occur, phenomena such as yellowing, hardening and embrittlement occur, elasticity is reduced, mechanical properties are degraded, and the appearance and the use reliability of the product are seriously affected. In the prior art, there are attempts to improve the performance of TPU by adding inorganic fillers, antioxidants, ultraviolet absorbers and the like, but a plurality of defects are common. For example, the unmodified inorganic filler has poor compatibility with the TPU matrix, is easy to agglomerate, is difficult to effectively improve the wear resistance, can possibly cause the mechanical property of the material to be reduced, has limited addition effect of a single anti-aging additive, cannot resist the dual effects of oxidation and ultraviolet aging at the same time, has complex partial modification process and higher cost, or has hidden environmental protection hazards, and is difficult to realize industrialized mass production. Along with the continuous improvement of material performance requirements of various industries, a TPU composite material which has excellent wear resistance and long-acting anti-aging capability and is stable and controllable in preparation process is needed in the market so as to meet the severe use requirements of the fields of outdoor products, automobile industry, high-end equipment and the like. Therefore, the high wear-resistant anti-aging TPU composite material with scientific formula, reasonable modification process and synergistic performance is developed, the performance defect of the traditional TPU material is overcome, and the high wear-resistant anti-aging TPU composite material has important practical significance and wide application prospect. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a high wear-resistant anti-aging TPU composite material and a preparation method thereof, and solves the problems of poor wear resistance, weak aging resistance, insufficient inorganic filler compatibility and single anti-aging auxiliary agent effect of the traditional TPU material. In order to achieve the above purpose, the invention is realized by the following technical scheme: The TPU composite material with high wear resistance and ageing resistance comprises the following raw materials, by weight, 90-100 parts of a thermoplastic polyurethane elastomer, 5-12 parts of modified nano silicon dioxide, 8-15 parts of modified basalt fiber, 0.2-0.5 part of antioxidant 1010, 0.3-0.6 part of ultraviolet absorbent UV-531, 0.5-1.0 part of zinc stearate and 0.8-1.5 part of trimethylolpropane triacrylate. Further, the Shore hardness of the thermoplastic polyurethane elastomer is 85-95A, so that the matrix is ensured to have enough bearing capacity to adapt to a wear-resistant scene, good processing fluidity is realized, the molding is convenient, the number average molecular weight is 20000-30000, the NCO/OH molar ratio is 1.05-1.15, the interface bonding stability with modified filler is ensured by precisely controlling the number average molecular weight and the NCO/OH molar ratio, and the mechanical property attenuation of the composite material due to the deviation of the matrix performance is avoided. Further, the specific preparation steps of the modified nano silicon dioxide are as follows: A1, taking nano silico