An impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material and its preparation method

Abstract

This invention relates to the field of composite materials, specifically to an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene (UHMWPE) composite material and its preparation method. It addresses the problem that the impact resistance of existing UHMWPE materials needs improvement, and their relatively poor chemical corrosion resistance limits their application in demanding applications. This composite material uses UHMWPE as the main raw material, giving it excellent mechanical properties. Adding polyfluorocarbazole polymers and modified composite fillers significantly improves the impact resistance and corrosion resistance of the composite material, enhancing its impact resistance in practical applications. This ensures high reliability even in complex environments, thereby increasing the practical application value and service life of the composite material.

Description

Technical Field

[0001] This invention relates to the field of composite materials, specifically to an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material and its preparation method. Background Technology

[0002] Ultra-high molecular weight polyethylene (UHMWPE) possesses outstanding advantages due to its extremely high molecular weight, including a low coefficient of friction, excellent wear resistance, high mechanical strength, and excellent biocompatibility. It is widely used in mining machinery, textile machinery, medical implants, and chemical storage tank linings. However, the impact resistance of UHMWPE needs improvement. It is prone to creep deformation and cracking under load or stress conditions, and its chemical corrosion resistance is relatively poor; it is easily corroded or dissolved in strong alkaline or acidic environments, limiting its application in demanding applications.

[0003] Therefore, developing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material and its preparation method is of great practical significance. Summary of the Invention

[0004] In order to overcome the above-mentioned technical problems, the purpose of this invention is to provide an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material and its preparation method, which solves the problem that the impact resistance of existing ultra-high molecular weight polyethylene materials still needs to be improved, and their chemical corrosion resistance is relatively poor, which limits their application in high-requirement applications.

[0005] The objective of this invention can be achieved through the following technical solutions: In a first aspect, this application provides an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material, comprising the following components in parts by weight: The composition includes 90-95 parts of ultra-high molecular weight polyethylene, 5-17 parts of polyfluorocarbazole polymer, 0.5-4.5 parts of modified composite filler, 1-3 parts of lubricant, and 0.3-0.7 parts of antioxidant. The polyfluorocarbazole polymer is prepared by the following steps: Step a1: Add 2,7-dibromocarbazole, phenothiazine, triethylamine, and dichloromethane to a three-necked flask equipped with a stirrer, thermometer, constant pressure dropping funnel, and gas delivery tube. Purge with nitrogen for protection and stir the reaction at 0-5℃ and 200-300 r / min for 20-30 min. Then, while stirring, add methacryloyl chloride dropwise at a rate of 1-3 drops / s. After the addition is complete, raise the temperature to 25-30℃ and continue stirring for 20-30 h. After the reaction is complete, filter the reaction product under vacuum. Wash the filtrate 2-3 times with hydrochloric acid solution, sodium hydroxide solution, and saturated sodium chloride solution in sequence. Then dry with anhydrous sodium sulfate and filter under vacuum. Remove the solvent by rotary evaporation of the filtrate to obtain the alkenyl dibromocarbazole compound. Step a2: The alkenyl dibromocarbazole compound, 3,5-bis(trifluoromethyl)phenylboronic acid, tetra(triphenyl)phosphine-palladium, sodium carbonate, toluene, and deionized water were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the reaction was stirred at 25-30℃ and 200-300 r / min for 30-40 min. Then, the temperature was raised to 80-85℃ and the reaction was continued for 20-30 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filtrate was extracted with ethyl acetate 2-3 times. The extracts were combined and washed with distilled water and saturated sodium chloride solution 2-3 times in sequence. Then, the product was dried with anhydrous sodium sulfate and vacuum filtered. The solvent was removed by rotary evaporation of the filtrate to obtain the alkenyl polyfluorocarbazole compound. Step a3: Add the alkenyl polyfluorocarbazole compound, azobisisobutyronitrile, and ethanol to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir the reaction at 0-5℃ and 200-300 r / min for 30-40 min. Then raise the temperature to 80-85℃ and continue stirring for 10-15 h. After the reaction is complete, cool the reaction product to room temperature and add it to methanol. Then filter under vacuum and place the filter cake in a vacuum drying oven to dry at 40-50℃ for 6-10 h to obtain the polyfluorocarbazole polymer.

[0006] In a preferred embodiment of the present invention, the ratio of 2,7-dibromocarbazole, phenothiazine, triethylamine, dichloromethane and methacryloyl chloride in step a1 is 10 mmol: 0.02-0.03 g: 6-7 mL: 40-50 mL: 10 mmol.

[0007] In a preferred embodiment of the present invention, the hydrochloric acid solution in step a1 has a mass fraction of 3-5%; the sodium hydroxide solution has a mass fraction of 8-10%.

[0008] In a preferred embodiment of the present invention, the ratio of the alkenyl dibromocarbazole compound, 3,5-bis(trifluoromethyl)phenylboronic acid, tetra(triphenyl)phosphine-palladium, sodium carbonate, toluene, and deionized water in step a2 is 10 mmol: 20 mmol: 0.13-0.17 g: 25-30 mmol: 40-50 mL: 10-15 mL.

[0009] In a preferred embodiment of the present invention, the ratio of the alkenyl polyfluorocarbazole compound, azobisisobutyronitrile, and ethanol in step a3 is 2g:0.02-0.03g:30-40mL.

[0010] In a preferred embodiment of the present invention, the modified composite filler is prepared by the following steps: Deionized water, ethanol, and silane coupling agent KH-560 were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred for 10-15 minutes at a temperature of 25-30℃ and a stirring rate of 200-300 r / min. The pH was then adjusted to 3-4 with glacial acetic acid, and the reaction was continued for 1-2 hours. Then, α-zirconium phosphate and glass fiber were added, and the mixture was heated to 80-85℃ and stirred for 6-10 hours. After the reaction was completed, the product was cooled to room temperature and then vacuum filtered. The filter cake was washed 2-3 times with distilled water and then placed in a vacuum drying oven and dried at a temperature of 60-70℃ for 3-5 hours to obtain the modified composite filler.

[0011] In a preferred embodiment of the present invention, the ratio of deionized water, ethanol, silane coupling agent KH-560, α-zirconium phosphate and glass fiber is 10-15mL: 90-100mL: 1-6g: 8-10g: 3-5g.

[0012] In a preferred embodiment of the present invention, the average particle size of the α-zirconium phosphate is 2 μm; the average diameter of the glass fiber is 15 μm and the average length is 70 μm.

[0013] Secondly, this application provides a method for preparing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material, comprising the following steps: Step 1: Weigh out 90-95 parts of ultra-high molecular weight polyethylene, 5-17 parts of polyfluorocarbazole polymer, 0.5-4.5 parts of modified composite filler, 1-3 parts of lubricant, and 0.3-0.7 parts of antioxidant according to the weight ratio, and set aside. Step 2: Mix ultra-high molecular weight polyethylene, polyfluorocarbazole polymer, modified composite filler, lubricant and antioxidant evenly, then place in a mixer and mix for 5-15 minutes at a temperature of 200-210℃ and a speed of 60-80 r / min. Then place in a flat platen hot press and hot press for 6-8 minutes at a temperature of 200-210℃ and a pressure of 18-20 MPa. Finally, hot press for 10-15 minutes at a temperature of 25-30℃ and a pressure of 18-20 MPa to obtain an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material.

[0014] In a preferred embodiment of the present invention, the ultra-high molecular weight polyethylene is UHMWPE, specifically Mitsui Chemicals XM220 from Japan.

[0015] In a preferred embodiment of the present invention, the lubricant is zinc stearate.

[0016] In a preferred embodiment of the present invention, the antioxidant is antioxidant 1010.

[0017] The beneficial effects of this invention are: This invention discloses an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene (UHMWPE) composite material and its preparation method. The method involves uniformly mixing UHMWPE, polyfluorocarbazole polymer, modified composite filler, lubricant, and antioxidant, followed by internal mixing and hot pressing to obtain the impact-resistant and corrosion-resistant UHMWPE composite material. This composite material uses UHMWPE as the main raw material, giving it excellent mechanical properties. The addition of polyfluorocarbazole polymer and modified composite filler significantly improves the impact resistance and corrosion resistance of the composite material, enhancing its impact resistance in practical applications. This ensures high reliability even in complex environments, thereby increasing the practical application value and service life of the composite material.

[0018] In the preparation of impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composites, a polyfluorocarbazole polymer was first prepared. This was achieved through a reaction between 2,7-dibromocarbazole and methacryloyl chloride, where the NH bond on 2,7-dibromocarbazole reacts with the acyl chloride group of methacryloyl chloride, simultaneously introducing an alkenyl group to obtain an alkenyl dibromocarbazole compound. Then, through a reaction between the alkenyl dibromocarbazole compound and 3,5-bis(trifluoromethyl)phenylboronic acid, the bromine atom on the alkenyl dibromocarbazole compound reacts with the borate group on the 3,5-bis(trifluoromethyl)phenylboronic acid, introducing a large number of fluorine atoms to obtain an alkenyl polyfluorocarbazole compound. Finally, polymerization of the alkenyl group in the alkenyl polyfluorocarbazole compound yielded the polyfluorocarbazole polymer. This polyfluorocarbazole polymer contains numerous cyclic structures in its molecular structure, endowing it with excellent mechanical properties and thus improving the impact resistance of the composite material. Simultaneously, the fluorine atoms in its molecular structure possess extremely low surface energy and chemical inertness, enabling the formation of a corrosion-resistant barrier, resulting in excellent corrosion resistance of the composite material.

[0019] In the process of preparing impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite materials, a modified composite filler was also prepared. The composite filler was formed by compounding α-zirconium phosphate and glass fiber, and then modified using a silane coupling agent KH-560. The siloxane on the silane coupling agent KH-560 hydrolyzes to form silanol, which is grafted onto the surface of the composite filler. Simultaneously, epoxy groups are introduced, resulting in the modified composite filler. α-zirconium phosphate is a typical two-dimensional layered material that can form tortuous paths in the composite material, blocking the penetration of corrosive media. Glass fiber is dispersed in the composite material to form a fiber network, allowing the impact force to be effectively dispersed on the fiber network, avoiding excessive stress concentration in local areas and rapid cracking, significantly improving the impact resistance of the composite material. After modification, it can be uniformly dispersed in the composite material, allowing the reinforcement effect to be fully utilized. Furthermore, the introduced epoxy groups allow it to be chemically bonded to the composite material, significantly improving the overall performance of the composite material. Detailed Implementation

[0020] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0021] Example 1: This example describes a method for preparing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material, comprising the following steps: Step S1: 10 mmol of 2,7-dibromocarbazole, 0.02 g of phenothiazine, 6 mL of triethylamine, and 40 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, constant pressure dropping funnel, and gas delivery tube. Nitrogen gas was introduced for protection, and the reaction was stirred at 0 °C and a stirring rate of 200 r / min for 20 min. Then, 10 mmol of methacryloyl chloride was added dropwise while stirring, with the dropping rate controlled at 1 drop / s. After the addition was completed, the temperature was raised to 25 °C and the reaction was stirred for another 20 h. After the reaction was completed, the reaction product was vacuum filtered. The filtrate was washed twice with 3% hydrochloric acid solution, 8% sodium hydroxide solution, and saturated sodium chloride solution, respectively. Then, it was dried with anhydrous sodium sulfate, vacuum filtered, and the solvent was removed by rotary evaporation to obtain the alkenyl dibromocarbazole compound. Step S2: 10 mmol of alkenyl dibromocarbazole compound, 20 mmol of 3,5-bis(trifluoromethyl)phenylboronic acid, 0.13 g of tetra(triphenyl)phosphine-palladium, 25 mmol of sodium carbonate, 40 mL of toluene, and 10 mL of deionized water were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25 °C and 200 r / min for 30 min. Then, the temperature was raised to 80 °C and the mixture was stirred for 20 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filtrate was extracted twice with ethyl acetate. The extracts were combined and washed twice with distilled water and saturated sodium chloride solution, respectively. The mixture was then dried with anhydrous sodium sulfate and vacuum filtered. The solvent was removed by rotary evaporation of the filtrate to obtain the alkenyl polyfluorocarbazole compound. Step S3: Add 2g of alkenyl polyfluorocarbazole compound, 0.02g of azobisisobutyronitrile and 30mL of ethanol to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 0℃ and 200r / min for 30min. Then raise the temperature to 80℃ and continue stirring for 10h. After the reaction is completed, cool the reaction product to room temperature and add it to methanol. Then filter under vacuum and place the filter cake in a vacuum drying oven and dry at 40℃ for 6h to obtain polyfluorocarbazole polymer. Step S4: Add 10 mL of deionized water, 90 mL of ethanol, and 1 g of silane coupling agent KH-560 to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 25°C and 200 r / min for 10 min. Adjust the pH to 3 with glacial acetic acid, and continue stirring for 1 h. Then add 8 g of α-zirconium phosphate and 3 g of glass fiber, and heat to 80°C, continuing stirring for 6 h. After the reaction, cool the product to room temperature, then vacuum filter. Wash the filter cake twice with distilled water, and then place it in a vacuum drying oven at 60°C for 3 h to obtain the modified composite filler. The average particle size of the α-zirconium phosphate is 2 μm; the average diameter of the glass fiber is 15 μm, and the average length is 70 μm. Step S5: Weigh out 90 parts by weight of ultra-high molecular weight polyethylene, 5 parts by weight of polyfluorocarbazole polymer, 0.5 parts by weight of modified composite filler, 1 part by weight of lubricant, and 0.3 parts by weight of antioxidant, and set aside; the ultra-high molecular weight polyethylene is UHMWPE Mitsui Chemicals XM220; the lubricant is zinc stearate; the antioxidant is antioxidant 1010; Step S6: Mix ultra-high molecular weight polyethylene, polyfluorocarbazole polymer, modified composite filler, lubricant and antioxidant evenly, then place in a mixer and mix for 5 minutes at 200℃ and 60 r / min. Then place in a flat plate hot press and hot press for 6 minutes at 200℃ and 18 MPa. Finally, hot press for 10 minutes at 25℃ and 18 MPa to obtain an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material.

[0022] Example 2: This example describes a method for preparing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material, comprising the following steps: Step S1: 10 mmol of 2,7-dibromocarbazole, 0.025 g of phenothiazine, 6.5 mL of triethylamine, and 45 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, constant pressure dropping funnel, and gas delivery tube. Nitrogen gas was introduced for protection, and the reaction was stirred at 3 °C and a stirring rate of 250 r / min for 25 min. Then, 10 mmol of methacryloyl chloride was added dropwise while stirring, with the dropping rate controlled at 2 drops / s. After the addition was completed, the temperature was raised to 28 °C and the reaction was stirred for another 25 h. After the reaction was completed, the reaction product was vacuum filtered. The filtrate was washed twice successively with 4% hydrochloric acid solution, 9% sodium hydroxide solution, and saturated sodium chloride solution. Then, it was dried with anhydrous sodium sulfate, vacuum filtered, and the solvent was removed by rotary evaporation to obtain the alkenyl dibromocarbazole compound. Step S2: 10 mmol of alkenyl dibromocarbazole compound, 20 mmol of 3,5-bis(trifluoromethyl)phenylboronic acid, 0.15 g of tetra(triphenyl)phosphine-palladium, 28 mmol of sodium carbonate, 45 mL of toluene, and 12 mL of deionized water were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 28 °C and 250 r / min for 35 min. Then, the temperature was raised to 82 °C and the mixture was stirred for another 25 h. After the reaction was completed, the product was cooled to room temperature and then vacuum filtered. The filtrate was extracted twice with ethyl acetate. The extracts were combined and washed twice with distilled water and saturated sodium chloride solution, respectively. The mixture was then dried with anhydrous sodium sulfate and vacuum filtered. The solvent was removed by rotary evaporation of the filtrate to obtain the alkenyl polyfluorocarbazole compound. Step S3: 2g of alkenyl polyfluorocarbazole compound, 0.025g of azobisisobutyronitrile and 35mL of ethanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 3℃ and 250r / min for 35min. Then the temperature was raised to 82℃ and the mixture was stirred for 12h. After the reaction was completed, the reaction product was cooled to room temperature and then added to methanol. The mixture was then vacuum filtered and the filter cake was placed in a vacuum drying oven and dried at 45℃ for 8h to obtain polyfluorocarbazole polymer. Step S4: Add 12 mL of deionized water, 95 mL of ethanol, and 3.5 g of silane coupling agent KH-560 to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Probe with nitrogen and stir for 12 min at 28°C and 250 r / min. Adjust the pH to 3.5 with glacial acetic acid and continue stirring for 1.5 h. Then add 9 g of α-zirconium phosphate and 4 g of glass fiber, and continue stirring for 8 h at 82°C. After the reaction, cool the product to room temperature, then vacuum filter. Wash the filter cake twice with distilled water and place it in a vacuum drying oven at 65°C for 4 h to obtain the modified composite filler. The average particle size of the α-zirconium phosphate is 2 μm; the average diameter of the glass fiber is 15 μm and the average length is 70 μm. Step S5: Weigh out 92 parts by weight of ultra-high molecular weight polyethylene, 11 parts by weight of polyfluorocarbazole polymer, 2.5 parts by weight of modified composite filler, 2 parts by weight of lubricant, and 0.5 parts by weight of antioxidant, and set aside; the ultra-high molecular weight polyethylene is UHMWPE Mitsui Chemicals XM220; the lubricant is zinc stearate; the antioxidant is antioxidant 1010; Step S6: Mix ultra-high molecular weight polyethylene, polyfluorocarbazole polymer, modified composite filler, lubricant and antioxidant evenly, then place in an internal mixer and mix for 10 minutes at 205℃ and 70 r / min. Then place in a flat plate hot press and hot press for 7 minutes at 205℃ and 19 MPa, then hot press for 12 minutes at 28℃ and 19 MPa to obtain impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material.

[0023] Example 3: This example describes a method for preparing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material, comprising the following steps: Step S1: 10 mmol of 2,7-dibromocarbazole, 0.03 g of phenothiazine, 7 mL of triethylamine, and 50 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, constant pressure dropping funnel, and gas delivery tube. Nitrogen gas was introduced for protection, and the reaction was stirred at 5 °C and a stirring rate of 300 r / min for 30 min. Then, 10 mmol of methacryloyl chloride was added dropwise while stirring, with the dropping rate controlled at 3 drops / s. After the addition was completed, the temperature was raised to 30 °C and the reaction was stirred for another 30 h. After the reaction was completed, the reaction product was vacuum filtered. The filtrate was washed three times in succession with 5% hydrochloric acid solution, 10% sodium hydroxide solution, and saturated sodium chloride solution. Then, it was dried with anhydrous sodium sulfate, vacuum filtered, and the solvent was removed by rotary evaporation to obtain the alkenyl dibromocarbazole compound. Step S2: 10 mmol of alkenyl dibromocarbazole compound, 20 mmol of 3,5-bis(trifluoromethyl)phenylboronic acid, 0.17 g of tetra(triphenyl)phosphine-palladium, 30 mmol of sodium carbonate, 50 mL of toluene, and 15 mL of deionized water were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C and 300 r / min for 40 min. Then, the temperature was raised to 85 °C and the mixture was stirred for another 30 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filtrate was extracted three times with ethyl acetate. The extracts were combined and washed three times with distilled water and saturated sodium chloride solution, respectively. The mixture was then dried with anhydrous sodium sulfate and vacuum filtered. The solvent was removed by rotary evaporation of the filtrate to obtain the alkenyl polyfluorocarbazole compound. Step S3: Add 2g of alkenyl polyfluorocarbazole compound, 0.03g of azobisisobutyronitrile and 40mL of ethanol to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 5℃ and 300r / min for 40min. Then raise the temperature to 85℃ and continue stirring for 15h. After the reaction is completed, cool the reaction product to room temperature and add it to methanol. Then filter under vacuum and place the filter cake in a vacuum drying oven and dry at 50℃ for 10h to obtain polyfluorocarbazole polymer. Step S4: Add 15 mL of deionized water, 100 mL of ethanol, and 6 g of silane coupling agent KH-560 to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 30°C and 300 r / min for 15 min. Adjust the pH to 4 with glacial acetic acid and continue stirring for 2 h. Then add 10 g of α-zirconium phosphate and 5 g of glass fiber, and heat to 85°C, continuing stirring for 10 h. After the reaction, cool the product to room temperature, then vacuum filter. Wash the filter cake three times with distilled water and place it in a vacuum drying oven at 70°C for 5 h to obtain the modified composite filler. The average particle size of the α-zirconium phosphate is 2 μm; the average diameter of the glass fiber is 15 μm, and the average length is 70 μm. Step S5: Weigh out 95 parts by weight of ultra-high molecular weight polyethylene, 17 parts by weight of polyfluorocarbazole polymer, 4.5 parts by weight of modified composite filler, 3 parts by weight of lubricant, and 0.7 parts by weight of antioxidant, and set aside; the ultra-high molecular weight polyethylene is UHMWPE Mitsui Chemicals XM220; the lubricant is zinc stearate; the antioxidant is antioxidant 1010; Step S6: Mix ultra-high molecular weight polyethylene, polyfluorocarbazole polymer, modified composite filler, lubricant and antioxidant evenly, then place in a mixer and mix for 15 minutes at 210℃ and 80 r / min. Then place in a flat plate hot press and hot press for 8 minutes at 210℃ and 20 MPa, then hot press for 15 minutes at 30℃ and 20 MPa to obtain impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material.

[0024] Comparative Example 1: This comparative example illustrates a method for preparing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material, comprising the following steps: Step S1: Weigh out 95 parts by weight of ultra-high molecular weight polyethylene, 3 parts by weight of lubricant and 0.7 parts by weight of antioxidant, and set aside; the ultra-high molecular weight polyethylene is UHMWPE Mitsui Chemicals XM220 from Japan; the lubricant is zinc stearate; the antioxidant is antioxidant 1010; Step S2: Mix ultra-high molecular weight polyethylene, lubricant and antioxidant evenly, then place in a mixer and mix for 15 minutes at 210℃ and 80 r / min. Then place in a flatbed hot press and hot press for 8 minutes at 210℃ and 20 MPa. Finally, hot press for 15 minutes at 30℃ and 20 MPa to obtain an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material.

[0025] Comparative Example 2: This comparative example illustrates a method for preparing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material, comprising the following steps: Step S1: 10 mmol of 2,7-dibromocarbazole, 0.03 g of phenothiazine, 7 mL of triethylamine, and 50 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, constant pressure dropping funnel, and gas delivery tube. Nitrogen gas was introduced for protection, and the reaction was stirred at 5 °C and a stirring rate of 300 r / min for 30 min. Then, 10 mmol of methacryloyl chloride was added dropwise while stirring, with the dropping rate controlled at 3 drops / s. After the addition was completed, the temperature was raised to 30 °C and the reaction was stirred for another 30 h. After the reaction was completed, the reaction product was vacuum filtered. The filtrate was washed three times in succession with 5% hydrochloric acid solution, 10% sodium hydroxide solution, and saturated sodium chloride solution. Then, it was dried with anhydrous sodium sulfate, vacuum filtered, and the solvent was removed by rotary evaporation to obtain the alkenyl dibromocarbazole compound. Step S2: 10 mmol of alkenyl dibromocarbazole compound, 20 mmol of 3,5-bis(trifluoromethyl)phenylboronic acid, 0.17 g of tetra(triphenyl)phosphine-palladium, 30 mmol of sodium carbonate, 50 mL of toluene, and 15 mL of deionized water were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C and 300 r / min for 40 min. Then, the temperature was raised to 85 °C and the mixture was stirred for another 30 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filtrate was extracted three times with ethyl acetate. The extracts were combined and washed three times with distilled water and saturated sodium chloride solution, respectively. The mixture was then dried with anhydrous sodium sulfate and vacuum filtered. The solvent was removed by rotary evaporation of the filtrate to obtain the alkenyl polyfluorocarbazole compound. Step S3: Add 2g of alkenyl polyfluorocarbazole compound, 0.03g of azobisisobutyronitrile and 40mL of ethanol to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 5℃ and 300r / min for 40min. Then raise the temperature to 85℃ and continue stirring for 15h. After the reaction is completed, cool the reaction product to room temperature and add it to methanol. Then filter under vacuum and place the filter cake in a vacuum drying oven and dry at 50℃ for 10h to obtain polyfluorocarbazole polymer. Step S4: Weigh out 95 parts by weight of ultra-high molecular weight polyethylene, 17 parts by weight of polyfluorocarbazole polymer, 3 parts by weight of lubricant and 0.7 parts by weight of antioxidant, and set aside; the ultra-high molecular weight polyethylene is UHMWPE Mitsui Chemicals XM220; the lubricant is zinc stearate; the antioxidant is antioxidant 1010. Step S5: Mix ultra-high molecular weight polyethylene, polyfluorocarbazole polymer, lubricant and antioxidant evenly, then place in a mixer and mix for 15 minutes at 210℃ and 80 r / min. Then place in a flatbed hot press and hot press for 8 minutes at 210℃ and 20 MPa, then hot press for 15 minutes at 30℃ and 20 MPa to obtain an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material.

[0026] Comparative Example 3: This comparative example illustrates a method for preparing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material, comprising the following steps: Step S1: Add 15 mL of deionized water, 100 mL of ethanol, and 6 g of silane coupling agent KH-560 to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 30°C and 300 r / min for 15 min. Adjust the pH to 4 with glacial acetic acid and continue stirring for 2 h. Then add 10 g of α-zirconium phosphate and 5 g of glass fiber, and heat to 85°C, continuing stirring for 10 h. After the reaction, cool the product to room temperature, then vacuum filter. Wash the filter cake three times with distilled water and place it in a vacuum drying oven at 70°C for 5 h to obtain the modified composite filler. The average particle size of the α-zirconium phosphate is 2 μm; the average diameter of the glass fiber is 15 μm, and the average length is 70 μm. Step S2: Weigh out 95 parts by weight of ultra-high molecular weight polyethylene, 4.5 parts by weight of modified composite filler, 3 parts by weight of lubricant, and 0.7 parts by weight of antioxidant, and set aside; the ultra-high molecular weight polyethylene is UHMWPE Mitsui Chemicals XM220 from Japan; the lubricant is zinc stearate; and the antioxidant is antioxidant 1010. Step S3: Mix ultra-high molecular weight polyethylene, modified composite filler, lubricant and antioxidant evenly, then place in a mixer and mix for 15 minutes at 210℃ and 80 r / min. Then place in a flat plate hot press and hot press for 8 minutes at 210℃ and 20 MPa. Finally, hot press for 15 minutes at 30℃ and 20 MPa to obtain an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material.

[0027] Comparative Example 4: This comparative example illustrates a method for preparing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material, comprising the following steps: Step S1: Weigh out 95 parts by weight of ultra-high molecular weight polyethylene (UHMWPE), 17 parts by weight of 3,5-bis(trifluoromethyl)phenylboronic acid, 4.5 parts by weight of composite filler, 3 parts by weight of lubricant, and 0.7 parts by weight of antioxidant, and set aside. The UHMWPE is Mitsui Chemicals XM220 (UHMWPE); the lubricant is zinc stearate; the antioxidant is antioxidant 1010; and the composite filler is a mixture of α-zirconium phosphate and glass fiber in a mass ratio of 10:5. Step S2: Mix ultra-high molecular weight polyethylene, 3,5-bis(trifluoromethyl)phenylboronic acid, composite filler, lubricant and antioxidant evenly, then place in a mixer and mix for 15 minutes at 210℃ and 80 r / min. Then place in a flatbed hot press and hot press for 8 minutes at 210℃ and 20 MPa, then hot press for 15 minutes at 30℃ and 20 MPa to obtain an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material.

[0028] The impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composites of Examples 1-3 and Comparative Examples 1-4 were tested for impact strength according to GB / T 1043.1-2008; wherein, the acid resistance test was conducted by immersing the samples in a 10% hydrochloric acid solution for 14 days; and the alkali resistance test was conducted by immersing the samples in a 10% sodium hydroxide solution for 14 days.

[0029] The test results are shown in the table below:

[0030] Referring to the data in the table above, and based on the comparison between Examples 1-3 and Comparative Examples 1-4, it can be seen that the addition of polyfluorocarbazole polymer and modified composite filler can significantly improve the impact strength and impact strength after acid and alkali corrosion of ultra-high molecular weight polyethylene composite material, indicating that the ultra-high molecular weight polyethylene composite material of this application has excellent impact resistance and corrosion resistance.

[0031] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0032] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. An impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material, characterized in that, Includes the following components by weight: The composition includes 90-95 parts of ultra-high molecular weight polyethylene, 5-17 parts of polyfluorocarbazole polymer, 0.5-4.5 parts of modified composite filler, 1-3 parts of lubricant, and 0.3-0.7 parts of antioxidant. The polyfluorocarbazole polymer is prepared by the following steps: Step a1: 2,7-Dibromocarbazole, phenothiazine, triethylamine and dichloromethane were stirred and reacted. Then, methacryloyl chloride was added dropwise and the reaction was continued with stirring. After the reaction was completed, the reaction product was filtered under vacuum. The filtrate was washed successively with hydrochloric acid solution, sodium hydroxide solution and saturated sodium chloride solution. After drying and vacuum filtration, the filtrate was evaporated by rotary evaporation to obtain alkenyl dibromocarbazole compound. Step a2: The alkenyl dibromocarbazole compound, 3,5-bis(trifluoromethyl)phenylboronic acid, tetra(triphenyl)phosphine palladium, sodium carbonate, toluene, and deionized water were stirred and reacted. After the reaction was completed, the reaction product was cooled and then vacuum filtered. The filtrate was extracted and washed successively with distilled water and saturated sodium chloride solution. After drying and vacuum filtering, the filtrate was rotary evaporated to obtain the alkenyl polyfluorocarbazole compound. Step a3: The alkenyl polyfluorocarbazole compound, azobisisobutyronitrile and ethanol were stirred and reacted. After the reaction was completed, the reaction product was cooled and then added to methanol. After vacuum filtration, the filter cake was dried to obtain the polyfluorocarbazole polymer.

2. The impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material according to claim 1, characterized in that, The ratio of 2,7-dibromocarbazole, phenothiazine, triethylamine, dichloromethane, and methacryloyl chloride used in step a1 is 10 mmol: 0.02-0.03 g: 6-7 mL: 40-50 mL: 10 mmol.

3. The impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material according to claim 1, characterized in that, The hydrochloric acid solution in step a1 has a mass fraction of 3-5%; the sodium hydroxide solution has a mass fraction of 8-10%.

4. The impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material according to claim 1, characterized in that, The ratio of the alkenyl dibromocarbazole compound, 3,5-bis(trifluoromethyl)phenylboronic acid, tetra(triphenyl)phosphine-palladium, sodium carbonate, toluene, and deionized water in step a2 is 10 mmol: 20 mmol: 0.13-0.17 g: 25-30 mmol: 40-50 mL: 10-15 mL.

5. The impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material according to claim 1, characterized in that, The ratio of the alkenyl polyfluorocarbazole compound, azobisisobutyronitrile, and ethanol used in step a3 is 2g:0.02-0.03g:30-40mL.

6. The impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material according to claim 1, characterized in that, The modified composite filler is prepared by the following steps: Deionized water, ethanol, and silane coupling agent KH-560 were stirred and reacted. The pH was then adjusted with glacial acetic acid, followed by the addition of α-zirconium phosphate and glass fiber, and the reaction was continued with stirring. After the reaction was completed, the reaction product was cooled, then vacuum filtered, and the filter cake was washed with distilled water and dried to obtain the modified composite filler.

7. The impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material according to claim 6, characterized in that, The ratio of deionized water, ethanol, silane coupling agent KH-560, α-zirconium phosphate, and glass fiber is 10-15mL: 90-100mL: 1-6g: 8-10g: 3-5g.

8. The impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material according to claim 6, characterized in that, The average particle size of the α-zirconium phosphate is 2 μm; the average diameter of the glass fiber is 15 μm and the average length is 70 μm.

9. A method for preparing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material as described in any one of claims 1-8, characterized in that, Includes the following steps: Step 1: Weigh out 90-95 parts of ultra-high molecular weight polyethylene, 5-17 parts of polyfluorocarbazole polymer, 0.5-4.5 parts of modified composite filler, 1-3 parts of lubricant, and 0.3-0.7 parts of antioxidant according to the weight ratio, and set aside. Step 2: Mix ultra-high molecular weight polyethylene, polyfluorocarbazole polymer, modified composite filler, lubricant and antioxidant evenly, then place in a mixer and mix for 5-15 minutes at a temperature of 200-210℃ and a speed of 60-80 r / min. Then place in a flat platen hot press and hot press for 6-8 minutes at a temperature of 200-210℃ and a pressure of 18-20 MPa. Finally, hot press for 10-15 minutes at a temperature of 25-30℃ and a pressure of 18-20 MPa to obtain an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material.

10. The method for preparing an impact-resistant and corrosion-resistant ultra-high molecular weight polyethylene composite material according to claim 9, characterized in that, The ultra-high molecular weight polyethylene is UHMWPE, specifically Mitsui Chemicals XM220 from Japan; the lubricant is zinc stearate; and the antioxidant is antioxidant 1010.

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