High-wear-resistance polyether-ether-ketone composite material and production process thereof
By preparing a composite of polyetheretherketone (PEEK), hyperbranched polyimide, and modified carbon nanotubes, the problem of insufficient comprehensive performance of PEEK resin was solved, and a PEEK composite material with high wear resistance and flame retardancy was achieved.
Patent Information
- Application Number
- CN202511751292.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-26
- Publication Date
- 2026-01-09
AI Technical Summary
Single polyetheretherketone resins are insufficient to meet the application requirements of different fields, while composite materials have the problem of insufficient comprehensive performance.
A high wear-resistant polyether ether ketone composite material was prepared by combining polyether ether ketone, hyperbranched polyimide and modified carbon nanotubes. The hyperbranched polyimide was prepared by reacting pyromellitic dianhydride with hyperbranched hydroxyl prepolymer, and the modified carbon nanotubes were prepared by reacting carboxylated carbon nanotubes with pyridine derivatives. Multifunctional groups were introduced to enhance interfacial adhesion.
It improves the wear resistance and flame retardancy of composite materials, while also enhancing interfacial bonding and thermal stability.
Abstract
Description
Technical Field
[0001] This invention relates to the field of composite material technology, specifically to a high wear-resistant polyether ether ketone composite material and its production process. Background Technology
[0002] Polyetheretherketone (PEEK) is a linear aromatic polymer compound. Its macromolecular backbone contains numerous aromatic rings and polar ketone groups, endowing the polymer with heat resistance and mechanical strength. Furthermore, the large number of ether bonds in the macromolecule contributes to its toughness; the more ether bonds, the better the toughness. PEEK possesses the following characteristics: high temperature resistance, excellent fatigue resistance comparable to alloy materials; chemical resistance, corrosion resistance similar to nickel steel, self-lubricating properties; fatigue resistance; radiation resistance; hydrolysis resistance; and easy processability. Due to its good high-temperature fluidity and high thermal decomposition temperature, it can be molded using extrusion, injection molding, compression molding, and blow molding.
[0003] Due to its excellent comprehensive properties, polyetheretherketone (PEEK) can replace traditional materials such as metals and ceramics in many specialized fields. Its high-temperature resistance, self-lubrication, wear resistance, and fatigue resistance make it one of the most popular high-performance engineering plastics today, primarily used in aerospace, automotive, electronics, and medical devices. However, single PEEK resins are insufficient to meet the requirements of different applications, while composite materials often suffer from inadequate overall performance. Therefore, this invention studies and prepares a high-wear-resistant PEEK composite material to address this problem. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide a high wear-resistant polyether ether ketone composite material and its production process.
[0005] The present invention proposes a technical solution to solve the above-mentioned technical problems: a high wear-resistant polyether ether ketone composite material, comprising the following raw material components in parts by weight: 50-70 parts of polyether ether ketone, 50-80 parts of hyperbranched polyimide, 1-3 parts of modified carbon nanotubes and 1-5 parts of lubricant; wherein the hyperbranched polyimide is prepared by reacting pyromellitic dianhydride, 4,4'-diaminodiphenyl ether with a hyperbranched hydroxyl prepolymer.
[0006] Preferably, the hyperbranched hydroxyl prepolymer is prepared by reacting polyhydroxypyridine with terminal hydroxyl hyperbranched poly(amine-ester); the polyhydroxypyridine is prepared by reacting p-hydroxyacetophenone and p-hydroxybenzaldehyde.
[0007] Preferably, the modified carbon nanotubes are prepared by reacting carboxylated carbon nanotubes with a pyridine derivative; the pyridine derivative is prepared by reacting trifluoromethylthiopyridine with 4-piperidinesulfonylaniline; and the trifluoromethylthiopyridine is prepared by reacting 2,6-dichloro-4-trifluoromethylpyridine with 4-(trifluoromethylthio)phenylboronic acid.
[0008] Preferably, the lubricant is one of stearamide, N,N'-ethylenebisstearamide, and oleamide.
[0009] Preferably, the preparation method of the high wear-resistant polyetheretherketone composite material includes the following specific steps: S1. A mixture of hydroxyl-terminated hyperbranched poly(amine-ester), N,N-dimethylformamide, potassium carbonate, and potassium iodide was prepared at a mass ratio of 7.5:50:1~3:0.1. The mixture was heated to 60~70℃ and stirred at 200~400 rpm for 50~70 min. A polyhydroxypyridine mixture, weighing 2.8~3.2 times the mass of the hydroxyl-terminated hyperbranched poly(amine-ester), was added dropwise at a rate of 1~3 ml / min. The mixture was heated to 100~110℃ and refluxed for 16~24 h. After cooling to room temperature, the mixture was precipitated with ice-cold diethyl ether, filtered, dissolved in N,N-dimethylformamide, precipitated again with ice-cold diethyl ether, and dried under vacuum to obtain the hyperbranched hydroxyl prepolymer. The mass ratio of polyhydroxypyridine to N,N-dimethylformamide in the polyhydroxypyridine mixture was 3~5:20. S2. Under a nitrogen atmosphere, 4,4'-diaminodiphenyl ether and N-methylpyrrolidone are mixed at a mass ratio of 3~5:50, stirred and dissolved, and placed in an ice bath at 0~5℃. Pyromellitic dianhydride is added in 3~5 portions, with a total amount of 1.12~1.18 times the mass of 4,4'-diaminodiphenyl ether. After stirring and dissolving, the mixture is reacted for 30~50 min. Hyperbranched hydroxyl prepolymer, dehydrating agent acetic anhydride and catalyst pyridine are added. The mixture is heated to room temperature and reacted for 4~6 h. After standing for 12~24 h, it is coated onto the surface of a ceramic substrate and heat-treated at 220~240℃ for 10~20 min. After peeling, it is crushed to obtain hyperbranched polyimide. S3. Under a nitrogen atmosphere, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, palladium catalyst tris(dibenzylacetone)dipalladium, and anhydrous toluene were mixed in a mass ratio of 0.018~0.022:0.02:1 and stirred until homogeneous. Then, 0.26~0.28 times the mass of anhydrous toluene trifluoromethylthiopyridine and 0.25~0.26 times the mass of anhydrous toluene 4-piperidinesulfonylaniline were added. The mixture was heated to 100~110℃ and refluxed for 16~18h. After cooling to room temperature, the mixture was filtered through a diatomaceous earth pad, washed with ethyl acetate, concentrated under reduced pressure, and then purified and concentrated by silica gel column chromatography to obtain the pyridine derivative. S4. Carboxylated carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were mixed in a mass ratio of 10:1:0.001~0.002, heated to 70~72℃, refluxed for 24~26h, cooled to room temperature, filtered, washed 3~5 times with anhydrous tetrahydrofuran, and transferred to a solution of N,N-dimethylformamide containing 18~20% triethylamine (mass ratio of carboxylated carbon nanotubes to triethylamine of 50:2~3). Then, pyridine derivatives with a mass ratio of 3~4 times that of carboxylated carbon nanotubes were added, and the mixture was placed in an oil bath at 80~85℃ and reacted under a nitrogen atmosphere for 48~72h. After filtration, the mixture was washed 3~5 times with N,N-dimethylformamide, and then extracted with tetrahydrofuran and acetone by Soxhlet extraction for 18~24h in sequence. The mixture was then dried to obtain modified carbon nanotubes. S5. By weight, polyetheretherketone, hyperbranched polyimide, modified carbon nanotubes and lubricant are mixed in a high-speed mixer and mixed at 1000~3000 rpm for 8~12 min. The mixture is then transferred to a mold and preheated at 110~120℃ for 20~30 min. The mixture is then transferred to a vacuum sintering furnace and sintered at 370~380℃ for 25~35 min. The mixture is then cooled to room temperature to obtain a high wear-resistant polyetheretherketone composite material.
[0010] Preferably, in step S1 above, the preparation method of the hydroxyl-terminated hyperbranched poly(amine-ester) is as follows: under a nitrogen atmosphere, 1,1,1-trimethylolpropane, methyl N,N-dihydroxyethyl-3-aminopropionate and the catalyst p-toluenesulfonic acid are mixed in a mass ratio of 1.2~1.4:20:0.18~0.22, stirred evenly, and then N,N-dimethylformamide with a mass of 10~18 times that of 1,1,1-trimethylolpropane is added. The temperature is raised to 70~72℃ and reacted for 1~2 hours. The temperature is then raised to 110~120℃ and reacted for 6~8 hours. After cooling to room temperature, the product is precipitated with petroleum ether. After filtration, the product is dissolved in acetone and precipitated with petroleum ether. Finally, it is vacuum dried at 40~50℃ to obtain the hydroxyl-terminated hyperbranched poly(amine-ester).
[0011] Preferably, in step S1 above, the preparation method of polyhydroxypyridine is as follows: under a nitrogen atmosphere, p-hydroxyacetophenone, p-hydroxybenzaldehyde and glacial acetic acid are mixed in a mass ratio of 1:2~2.2:180~200, stirred and dissolved, and then ammonium acetate with a mass ratio of 5~8 times that of p-hydroxyacetophenone is added. The mixture is heated to 115~120℃ and refluxed for 6~8 hours. The mixture is filtered and washed 3~5 times with glacial acetic acid and deionized water in sequence. Then, it is recrystallized with ethyl acetate and petroleum ether in a volume ratio of 3:1 to obtain polyhydroxypyridine.
[0012] Preferably, in step S2 above, the mass ratio of 4,4'-diaminodiphenyl ether, hyperbranched hydroxyl prepolymer, dehydrating agent acetic anhydride, and catalyst pyridine is 2:0.2~0.4:0.1:0.02~0.03.
[0013] Preferably, in step S3 above, the preparation method of trifluoromethylthiopyridine is as follows: under a nitrogen atmosphere, 2,6-dichloro-4-trifluoromethylpyridine, 4-(trifluoromethylthio)phenylboronic acid, potassium phosphate, and 1,4-dioxane are mixed in a mass ratio of 1:1.2~1.4:3:30, stirred evenly, and then 0.002~0.01 times the mass of potassium phosphate catalyst tetra(triphenylphosphine)palladium is added. The temperature is raised to 90~92℃, and the reaction is carried out for 16~18h. The reaction is quenched with saturated ammonium chloride, then extracted with dichloromethane, washed 3~5 times with saturated brine, dried with anhydrous sodium sulfate, and purified by rotary evaporation under reduced pressure with petroleum ether and ethyl acetate in a volume ratio of 10~20:1 to obtain trifluoromethylthiopyridine.
[0014] Preferably, in step S4 above, the method for preparing carboxylated carbon nanotubes is as follows: multi-walled carbon nanotubes are mixed with mixed acid at a mass ratio of 1:30~50, ultrasonically dispersed evenly, placed in an oil bath at 60~70℃, reacted for 6~8 hours, the reaction is terminated with deionized water, filtered and washed with deionized water 5~8 times, and finally vacuum dried at 40~50℃ to obtain carboxylated carbon nanotubes; the volume ratio of concentrated sulfuric acid to concentrated nitric acid with a mass fraction of 68% in the mixed acid is 3~5:1.
[0015] Compared with the prior art, the beneficial effects achieved by the present invention are: The high wear-resistant polyether ether ketone composite material prepared by the present invention is obtained by combining polyether ether ketone, hyperbranched polyimide and modified carbon nanotubes. Hyperbranched polyimide is prepared by reacting pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and hyperbranched hydroxyl prepolymer. The hyperbranched hydroxyl prepolymer is prepared by reacting polyhydroxypyridine with terminal hydroxyl hyperbranched poly(amine-ester). The polyhydroxypyridine is prepared by reacting p-hydroxyacetophenone and p-hydroxybenzaldehyde. The hyperbranched hydroxyl prepolymer acts as a crosslinking agent and enters the polyimide structure. It also introduces rigid triarylpyridine structural units, which enhances the interfacial bonding ability and improves the thermal stability. Modified carbon nanotubes are prepared by reacting carboxylated carbon nanotubes with pyridine derivatives. The pyridine derivatives are prepared by reacting trifluoromethylthiopyridine with 4-piperidinesulfonylaniline. Trifluoromethylthiopyridine is prepared by reacting 2,6-dichloro-4-trifluoromethylpyridine with 4-(trifluoromethylthio)phenylboronic acid. By introducing pyridine derivatives with pyridine, piperidine and sulfonyl groups onto the surface of carboxylated carbon nanotubes, the synergistic effect of multiple functional groups not only effectively prevents the aggregation of carbon nanotubes and enhances the interfacial adhesion with polyetheretherketone, but also improves the wear resistance and flame retardancy of the composite material. Detailed Implementation
[0016] The present invention will be specifically described below through embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those skilled in the art.
[0017] The multi-walled carbon nanotubes used in the embodiments and comparative examples of this invention have a diameter of 5-10 nm, a length of 1-2 μm, a purity of 99%, and a density of 0.15-0.35 g / cm³. 3 .
[0018] To more clearly illustrate the method provided by the present invention, the following examples will be used to describe in detail the various test methods for the high wear-resistant polyether ether ketone composite materials prepared in the examples and comparative examples: Flame retardancy: The high abrasion-resistant polyether ether ketone composite materials prepared in the examples and comparative examples were tested for limiting oxygen index in accordance with GB / T 2406.2.
[0019] Abrasion resistance: The abrasion resistance of the high abrasion-resistant polyether ether ketone composite materials prepared in the examples and comparative examples was tested according to GB / T 3960.
[0020] Thermal stability: The high wear-resistant polyether ether ketone composite materials prepared in the examples and comparative examples were tested using a melt index measuring instrument to measure the initial melt index at 380°C and the melt index after holding at 380°C for 5 hours, and the melt index change rate was calculated. Example
[0021] In this embodiment, the component mass fractions of the high wear-resistant polyether ether ketone composite material are as follows: 50 parts polyetheretherketone, 50 parts hyperbranched polyimide, 1 part modified carbon nanotubes, and 1 part lubricant.
[0022] The preparation process of the high wear-resistant polyether ether ketone composite material in this embodiment is as follows: S1. Under a nitrogen atmosphere, 1,1,1-trimethylolpropane, methyl N,N-dihydroxyethyl-3-aminopropionate, and the catalyst p-toluenesulfonic acid were mixed in a mass ratio of 1.2:20:0.18. After stirring until homogeneous, N,N-dimethylformamide (10 times the mass of 1,1,1-trimethylolpropane) was added. The mixture was heated to 70°C and reacted for 1 hour, then heated to 110°C and reacted for 6 hours. After cooling to room temperature, the mixture was precipitated with petroleum ether, filtered, dissolved in acetone, and precipitated again with petroleum ether. Finally, it was vacuum dried at 40°C to obtain a hydroxyl-terminated hyperbranched poly(amine-ester). Under a nitrogen atmosphere, p-hydroxyacetophenone, p-hydroxybenzaldehyde, and glacial acetic acid were mixed in a mass ratio of 1:2:180. After stirring and dissolving, ammonium acetate (5 times the mass of p-hydroxyacetophenone) was added. The mixture was heated to 115°C and refluxed for 6 hours. The mixture was filtered and washed three times successively with glacial acetic acid and deionized water, and then recrystallized with ethyl acetate and petroleum ether in a volume ratio of 3:1 to prepare polyhydroxypyridine. A mixture of terminal hydroxyl hyperbranched poly(amine-ester), N,N-dimethylformamide, potassium carbonate, and potassium iodide was prepared in a mass ratio of 7.5:50:1:0.1, heated to 60°C, and stirred at 200 rpm for 50 min. A polyhydroxypyridine mixture with a mass ratio of 2.8 times that of the terminal hydroxyl hyperbranched poly(amine-ester) was added dropwise at a rate of 1 ml / min. The mixture was heated to 100°C and refluxed for 16 h. After cooling to room temperature, the mixture was precipitated with glacial ether, filtered, dissolved in N,N-dimethylformamide, precipitated again with glacial ether, and dried under vacuum to obtain the hyperbranched hydroxyl prepolymer. The mass ratio of polyhydroxypyridine to N,N-dimethylformamide in the polyhydroxypyridine mixture was 3:20. S2. Under a nitrogen atmosphere, 4,4'-diaminodiphenyl ether and N-methylpyrrolidone were mixed at a mass ratio of 3:50, stirred and dissolved, and placed in an ice bath at 0°C. Pyromellitic dianhydride was added in three portions, with a total amount of 1.12 times the mass of 4,4'-diaminodiphenyl ether. After stirring and dissolving, the mixture was reacted for 30 min. Hyperbranched hydroxyl prepolymer, dehydrating agent acetic anhydride, and catalyst pyridine were added. The mass ratio of 4,4'-diaminodiphenyl ether, hyperbranched hydroxyl prepolymer, dehydrating agent acetic anhydride, and catalyst pyridine was 2:0.2:0.1:0.02. The mixture was heated to room temperature and reacted for another 4 h. After standing for 12 h, the mixture was coated onto the surface of a ceramic substrate and heat-treated at 220°C for 10 min. After peeling, the mixture was crushed to obtain hyperbranched polyimide. S3. Under a nitrogen atmosphere, 2,6-dichloro-4-trifluoromethylpyridine, 4-(trifluoromethylthio)phenylboronic acid, potassium phosphate, and 1,4-dioxane were mixed in a mass ratio of 1:1.2:3:30. After stirring until homogeneous, tetra(triphenylphosphine)palladium catalyst (0.002 times the mass of potassium phosphate) was added. The mixture was heated to 90°C and reacted for 16 h. The reaction was quenched with saturated ammonium chloride, extracted with dichloromethane, washed three times with saturated brine, dried over anhydrous sodium sulfate, and purified by rotary evaporation under reduced pressure with petroleum ether and ethyl acetate in a volume ratio of 10:1 to obtain trifluoromethylthiopyridine. Under a nitrogen atmosphere, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, palladium catalyst tris(dibenzylacetone)dipalladium, and anhydrous toluene were mixed at a mass ratio of 0.018:0.02:1 and stirred until homogeneous. Then, 0.26 times the mass of anhydrous toluene, trifluoromethylthiopyridine, and 0.25 times the mass of anhydrous toluene, 4-piperidinesulfonylaniline were added. The mixture was heated to 100°C and refluxed for 16 hours. After cooling to room temperature, the mixture was filtered through a diatomaceous earth pad, washed with ethyl acetate, concentrated under reduced pressure, and then purified and concentrated by silica gel column chromatography to obtain the pyridine derivative. S4. Multi-walled carbon nanotubes were mixed with a mixed acid at a mass ratio of 1:30, ultrasonically dispersed, and then placed in an oil bath at 60°C for 6 hours. The reaction was terminated with deionized water, filtered, and washed five times with deionized water. Finally, the mixture was vacuum dried at 40°C to obtain carboxylated carbon nanotubes. The volume ratio of concentrated sulfuric acid to 68% concentrated nitric acid in the mixed acid was 3:1. Carboxylated carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were mixed at a mass ratio of 10:1:0.001, heated to 70°C, and refluxed. After 24 hours, the mixture was cooled to room temperature, filtered, washed three times with anhydrous tetrahydrofuran, and transferred to a solution of N,N-dimethylformamide containing 18% triethylamine (mass ratio: 50:2). Then, pyridine derivatives with a mass ratio of 3 times that of carboxylated carbon nanotubes were added. The mixture was placed in an oil bath at 80°C and reacted under a nitrogen atmosphere for 48 hours. After filtration, the mixture was washed three times with N,N-dimethylformamide, and then extracted with tetrahydrofuran and acetone by Soxhlet extraction for 18 hours in sequence. After drying, modified carbon nanotubes were obtained. S5. By weight, polyetheretherketone, hyperbranched polyimide, modified carbon nanotubes and lubricant are mixed in a high-speed mixer and mixed at 1000 rpm for 8 min. The mixture is then transferred to a mold, preheated at 110℃ for 20 min, transferred to a vacuum sintering furnace, and sintered at 370℃ for 25 min. After cooling to room temperature, a high wear-resistant polyetheretherketone composite material is obtained. Example
[0023] In this embodiment, the component mass fractions of the high wear-resistant polyether ether ketone composite material are as follows: 60 parts polyetheretherketone, 65 parts hyperbranched polyimide, 2 parts modified carbon nanotubes, and 3 parts lubricant.
[0024] The preparation process of the high wear-resistant polyether ether ketone composite material in this embodiment is as follows: S1. Under a nitrogen atmosphere, 1,1,1-trimethylolpropane, methyl N,N-dihydroxyethyl-3-aminopropionate, and the catalyst p-toluenesulfonic acid were mixed in a mass ratio of 1.3:20:0.20. After stirring until homogeneous, N,N-dimethylformamide (14 times the mass of 1,1,1-trimethylolpropane) was added. The mixture was heated to 71°C and reacted for 1.5 h, then heated to 115°C and reacted for 7 h. After cooling to room temperature, the precipitate was obtained by precipitation with petroleum ether. After filtration, the precipitate was dissolved in acetone and precipitated again with petroleum ether. Finally, the precipitate was dried under vacuum at 45°C to obtain the hydroxyl-terminated hyperbranched poly(amine-ester). Under a nitrogen atmosphere, p-hydroxyacetophenone, p-hydroxybenzaldehyde, and glacial acetic acid were mixed in a mass ratio of 1:2.1:190. After stirring and dissolving, ammonium acetate (7 times the mass of p-hydroxyacetophenone) was added. The mixture was heated to 118°C and refluxed for 7 h. h, filtered and washed four times successively with glacial acetic acid and deionized water, then recrystallized with ethyl acetate and petroleum ether in a volume ratio of 3:1 to prepare polyhydroxypyridine; hydroxyl-terminated hyperbranched poly(amine-ester), N,N-dimethylformamide, potassium carbonate and potassium iodide were mixed in a mass ratio of 7.5:50:2:0.1, heated to 65℃, stirred at 300 rpm for 60 min, and polyhydroxypyridine mixture with a mass ratio of 3 times that of hydroxyl-terminated hyperbranched poly(amine-ester) was added dropwise at a rate of 2 ml / min, heated to 105℃, refluxed for 19 h, cooled to room temperature, precipitated with glacial ether, filtered, dissolved in N,N-dimethylformamide, precipitated with glacial ether, and dried under vacuum to obtain hyperbranched hydroxyl prepolymer; the mass ratio of polyhydroxypyridine to N,N-dimethylformamide in the polyhydroxypyridine mixture was 4:20; S2. Under a nitrogen atmosphere, 4,4'-diaminodiphenyl ether and N-methylpyrrolidone were mixed at a mass ratio of 4:50, stirred and dissolved, and placed in an ice bath at 3°C. Pyromellitic dianhydride, which was 1.15 times the mass of 4,4'-diaminodiphenyl ether, was added in four portions. After stirring and dissolving, the mixture was reacted for 40 min. Hyperbranched hydroxyl prepolymer, dehydrating agent acetic anhydride, and catalyst pyridine were added. The mass ratio of 4,4'-diaminodiphenyl ether, hyperbranched hydroxyl prepolymer, dehydrating agent acetic anhydride, and catalyst pyridine was 2:0.3:0.1:0.025. The mixture was heated to room temperature and reacted for another 5 h. After standing for 18 h, the mixture was coated onto the surface of a ceramic substrate and heat-treated at 230°C for 15 min. After peeling, the mixture was crushed to obtain hyperbranched polyimide. S3. Under a nitrogen atmosphere, 2,6-dichloro-4-trifluoromethylpyridine, 4-(trifluoromethylthio)phenylboronic acid, potassium phosphate, and 1,4-dioxane were mixed in a mass ratio of 1:1.3:3:30. After stirring until homogeneous, tetra(triphenylphosphine)palladium catalyst (0.008 times the mass of potassium phosphate) was added. The mixture was heated to 91°C and reacted for 17 h. The reaction was quenched with saturated ammonium chloride, extracted with dichloromethane, washed four times with saturated brine, dried over anhydrous sodium sulfate, and purified by rotary evaporation under reduced pressure with petroleum ether and ethyl acetate in a volume ratio of 15:1 to obtain trifluoromethylthiopyridine. Under a nitrogen atmosphere, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, palladium catalyst tris(dibenzylacetone)dipalladium, and anhydrous toluene were mixed in a mass ratio of 0.02:0.02:1 and stirred until homogeneous. Then, 0.27 times the mass of anhydrous toluene, trifluoromethylthiopyridine, and 0.255 times the mass of anhydrous toluene, 4-piperidinesulfonylaniline were added. The mixture was heated to 105°C and refluxed for 17 h. After cooling to room temperature, the mixture was filtered through a diatomaceous earth pad, washed with ethyl acetate, concentrated under reduced pressure, and then purified and concentrated by silica gel column chromatography to obtain the pyridine derivative. S4. Multi-walled carbon nanotubes were mixed with mixed acid at a mass ratio of 1:40, ultrasonically dispersed, and then placed in an oil bath at 65°C for 7 hours. The reaction was terminated with deionized water, filtered, and washed 7 times with deionized water. Finally, the mixture was vacuum dried at 45°C to obtain carboxylated carbon nanotubes. The volume ratio of concentrated sulfuric acid to concentrated nitric acid with a mass fraction of 68% in the mixed acid was 4:1. Carboxylated carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were mixed at a mass ratio of 10:1:0.0015, and the mixture was heated to 71°C and refluxed. After 25 hours, the mixture was cooled to room temperature, filtered, and washed four times with anhydrous tetrahydrofuran. The mixture was then transferred to a 19% (w / w) solution of N,N-dimethylformamide containing carboxylated carbon nanotubes at a mass ratio of 50:2.5 to triethylamine. Pyridine derivatives at 3.5 times the mass of carboxylated carbon nanotubes were added, and the mixture was placed in an oil bath at 83°C and reacted under a nitrogen atmosphere for 58 hours. After filtration, the mixture was washed four times with N,N-dimethylformamide, and then extracted with tetrahydrofuran and acetone in sequence for 22 hours. The mixture was then dried to obtain modified carbon nanotubes. S5. By weight, polyetheretherketone, hyperbranched polyimide, modified carbon nanotubes and lubricant are mixed in a high-speed mixer and mixed at 2000 rpm for 10 min. The mixture is then transferred to a mold, preheated at 115℃ for 25 min, transferred to a vacuum sintering furnace, and sintered at 375℃ for 30 min. After cooling to room temperature, a high wear-resistant polyetheretherketone composite material is obtained. Example
[0025] In this embodiment, the component mass fractions of the high wear-resistant polyether ether ketone composite material are as follows: 70 parts polyetheretherketone, 80 parts hyperbranched polyimide, 3 parts modified carbon nanotubes, and 5 parts lubricant.
[0026] The preparation process of the high wear-resistant polyether ether ketone composite material in this embodiment is as follows: S1. Under a nitrogen atmosphere, 1,1,1-trimethylolpropane, methyl N,N-dihydroxyethyl-3-aminopropionate, and the catalyst p-toluenesulfonic acid were mixed in a mass ratio of 1.4:20:0.22. After stirring evenly, N,N-dimethylformamide (18 times the mass of 1,1,1-trimethylolpropane) was added. The mixture was heated to 72°C and reacted for 2 hours, then heated to 120°C and reacted for 8 hours. After cooling to room temperature, the precipitate was obtained with petroleum ether. After filtration, the precipitate was dissolved in acetone and precipitated again with petroleum ether. Finally, the precipitate was dried under vacuum at 50°C to obtain the hydroxyl-terminated hyperbranched poly(amine-ester). Under a nitrogen atmosphere, p-hydroxyacetophenone, p-hydroxybenzaldehyde, and glacial acetic acid were mixed in a mass ratio of 1: 2.2:200 were mixed and stirred until dissolved. Ammonium acetate (8 times the mass of p-hydroxyacetophenone) was added, and the mixture was heated to 120°C and refluxed for 8 hours. The mixture was filtered and washed five times successively with glacial acetic acid and deionized water. It was then recrystallized from ethyl acetate and petroleum ether in a volume ratio of 3:1 to obtain polyhydroxypyridine. Terminally hydroxyl hyperbranched poly(amine-ester), N,N-dimethylformamide, potassium carbonate, and potassium iodide were mixed in a mass ratio of 7.5:50:3:0.1 and heated to 70°C. The mixture was stirred at 400 rpm for 70 min, and then 3.2 times the mass of the terminal hydroxyl hyperbranched poly(amine-ester) polyhydroxypyridine mixture was added dropwise at a rate of 3 ml / min. The mixture was heated to 110 °C and refluxed for 24 h. After cooling to room temperature, the mixture was precipitated with ice-cold diethyl ether, filtered, dissolved in N,N-dimethylformamide, precipitated again with ice-cold diethyl ether, and dried under vacuum to obtain the hyperbranched hydroxyl prepolymer. The mass ratio of polyhydroxypyridine to N,N-dimethylformamide in the polyhydroxypyridine mixture was 5:20. S2. Under a nitrogen atmosphere, 4,4'-diaminodiphenyl ether and N-methylpyrrolidone were mixed at a mass ratio of 5:50, stirred and dissolved, and placed in an ice bath at 5°C. Pyromellitic dianhydride, which was 1.18 times the mass of 4,4'-diaminodiphenyl ether, was added in 5 portions. After stirring and dissolving, the mixture was reacted for 50 min. Hyperbranched hydroxyl prepolymer, dehydrating agent acetic anhydride, and catalyst pyridine were added. The mass ratio of 4,4'-diaminodiphenyl ether, hyperbranched hydroxyl prepolymer, dehydrating agent acetic anhydride, and catalyst pyridine was 2:0.4:0.1:0.02~0.03. The mixture was heated to room temperature and reacted for 6 h. After standing for 24 h, it was coated onto the surface of a ceramic substrate and heat-treated at 240°C for 20 min. After peeling, it was crushed to obtain hyperbranched polyimide. S3. Under a nitrogen atmosphere, 2,6-dichloro-4-trifluoromethylpyridine, 4-(trifluoromethylthio)phenylboronic acid, potassium phosphate, and 1,4-dioxane were mixed in a mass ratio of 1:1.4:3:30. After stirring until homogeneous, tetra(triphenylphosphine)palladium catalyst (0.01 times the mass of potassium phosphate) was added. The mixture was heated to 92°C and reacted for 18 hours. The reaction was quenched with saturated ammonium chloride, extracted with dichloromethane, washed five times with saturated brine, dried over anhydrous sodium sulfate, and purified by rotary evaporation under reduced pressure with petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain trifluoromethylthiopyridine. Under a nitrogen atmosphere, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, palladium catalyst tris(dibenzylacetone)dipalladium, and anhydrous toluene were mixed at a mass ratio of 0.022:0.02:1 and stirred until homogeneous. Then, 0.28 times the mass of anhydrous toluene in trifluoromethylthiopyridine and 0.26 times the mass of anhydrous toluene in 4-piperidinesulfonylaniline were added. The mixture was heated to 110°C and refluxed for 18 hours. After cooling to room temperature, the mixture was filtered through a diatomaceous earth pad, washed with ethyl acetate, concentrated under reduced pressure, and then purified and concentrated by silica gel column chromatography to obtain the pyridine derivative. S4. Multi-walled carbon nanotubes were mixed with a mixed acid at a mass ratio of 1:50, ultrasonically dispersed, and then placed in an oil bath at 70°C for 8 hours. The reaction was terminated with deionized water, filtered, and washed 8 times with deionized water. Finally, the mixture was vacuum dried at 50°C to obtain carboxylated carbon nanotubes. The volume ratio of concentrated sulfuric acid to concentrated nitric acid (68% by mass) in the mixed acid was 5:1. Carboxylated carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were mixed at a mass ratio of 10:1:0.002, heated to 72°C, and refluxed. After 26 hours, the mixture was cooled to room temperature, filtered, washed five times with anhydrous tetrahydrofuran, and transferred to a 20% (w / w) solution of N,N-dimethylformamide containing carboxylated carbon nanotubes at a mass ratio of 50:3. Then, pyridine derivatives at a mass ratio of 4 times that of carboxylated carbon nanotubes were added. The mixture was placed in an oil bath at 85°C and reacted under a nitrogen atmosphere for 72 hours. After filtration, the mixture was washed five times with N,N-dimethylformamide, and then extracted with tetrahydrofuran and acetone in sequence for 24 hours. After drying, modified carbon nanotubes were obtained. S5. By weight, polyetheretherketone, hyperbranched polyimide, modified carbon nanotubes and lubricant are mixed in a high-speed mixer and mixed at 3000 rpm for 12 min. The mixture is then transferred to a mold, preheated at 120℃ for 30 min, transferred to a vacuum sintering furnace, and sintered at 380℃ for 35 min. The mixture is then cooled to room temperature to obtain a high wear-resistant polyetheretherketone composite material.
[0027] Comparative Example 1 The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between this high wear-resistant polyether ether ketone composite material and Example 2 is that the hyperbranched polyimide is prepared by reacting pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and polyhydroxypyridine.
[0028] Comparative Example 2 The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between this high wear-resistant polyether ether ketone composite material and Example 2 is that the hyperbranched polyimide is prepared by reacting pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and terminal hydroxyl hyperbranched poly(amine-ester).
[0029] Comparative Example 3 The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between this high wear-resistant polyether ether ketone composite material and Example 2 is that it is prepared by combining polyether ether ketone, polyimide and modified carbon nanotubes. The polyimide is prepared by reacting pyromellitic dianhydride and 4,4'-diaminodiphenyl ether.
[0030] Comparative Example 4 The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between this high wear-resistant polyether ether ketone composite material and Example 2 is that the modified carbon nanotubes are prepared by reacting carboxylated carbon nanotubes with 4-piperidine sulfonyl aniline.
[0031] Comparative Example 5 The preparation method of Comparative Example 5 is the same as that of Example 2. The difference between this high wear-resistant polyether ether ketone composite material and Example 2 is that the modified carbon nanotubes are only carboxylated carbon nanotubes.
[0032] Comparative Example 6 The preparation method of Comparative Example 6 is the same as that of Example 2. The difference between this high wear-resistant polyether ether ketone composite material and Example 2 is that it is only prepared by combining polyether ether ketone and hyperbranched polyimide.
[0033] Example of effect Table 1 below shows the performance test results of the high wear-resistant polyetheretherketone composite materials prepared in the examples and comparative examples; Table 1 Limiting Oxygen Index (LOI) Wear amount (mg) Melt flow index change rate (%) Example 1 41.9% 1.3 6.04 Example 2 42.1% 0.8 5.89 Example 3 41.7% 1.2 5.99 Comparative Example 1 40.8% 1.5 8.79 Comparative Example 2 40.5% 1.7 9.46 Comparative Example 3 40.4% 1.9 9.97 Comparative Example 4 38.2% 7.4 6.46 Comparative Example 5 37.4% 8.6 6.78 Comparative Example 6 37.0% 10.5 6.94 As can be seen from the performance data comparison in Table 1, the high wear-resistant polyether ether ketone composite material prepared by the present invention is not only lightweight, but also has excellent thermal stability, wear resistance and flame retardancy. A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 reveals that the polyhydroxypyridine obtained by reacting p-hydroxyacetophenone and p-hydroxybenzaldehyde, and the hyperbranched hydroxyl prepolymer obtained by reacting terminal hydroxyl hyperbranched poly(amine-ester), participate in the preparation of polyimide. The resulting hyperbranched polyimide acts as a crosslinking agent in the polyimide structure, and also introduces rigid triarylpyridine structural units, which enhances the interfacial bonding ability and improves thermal stability.
[0034] Comparison of experimental data from Examples 1, 2, 3 and Comparative Examples 4 and 5 reveals that introducing pyridine derivatives with pyridine, piperidine and sulfonyl groups onto the surface of carboxylated carbon nanotubes, with the synergistic effect of multiple functional groups, not only effectively prevents the aggregation of carbon nanotubes and enhances the interfacial adhesion with polyether ether ketone, but also improves the wear resistance and flame retardancy of the composite material.
[0035] Obviously, the above embodiments are merely examples to clearly illustrate the embodiments of the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all embodiments here. However, these obvious variations or modifications derived from the spirit of the present invention are still within the protection scope of the present invention.
Claims
1. A high-wear-resistant polyetheretherketone composite material, characterized in that, The raw material components include the following parts by weight: 50-70 parts of polyether ether ketone, 50-80 parts of hyperbranched polyimide, 1-3 parts of modified carbon nanotubes, and 1-5 parts of lubricant; wherein the hyperbranched polyimide is prepared by reacting pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and hyperbranched hydroxyl prepolymer.
2. The high wear-resistant polyetheretherketone composite material according to claim 1, characterized in that, The hyperbranched hydroxyl prepolymer is prepared by reacting polyhydroxypyridine with terminal hydroxyl hyperbranched poly(amine-ester); the polyhydroxypyridine is prepared by reacting p-hydroxyacetophenone and p-hydroxybenzaldehyde.
3. The high wear-resistant polyetheretherketone composite material according to claim 1, characterized in that, The modified carbon nanotubes are prepared by reacting carboxylated carbon nanotubes with pyridine derivatives; the pyridine derivatives are prepared by reacting trifluoromethylthiopyridine with 4-piperidinesulfonylaniline; the trifluoromethylthiopyridine is prepared by reacting 2,6-dichloro-4-trifluoromethylpyridine with 4-(trifluoromethylthio)phenylboronic acid.
4. The high wear-resistant polyetheretherketone composite material according to claim 1, characterized in that, The lubricant is one of stearamide, N,N'-ethylene bis-stearamide, and oleamide.
5. The preparation process of a high wear-resistant polyetheretherketone composite material according to claim 1, characterized in that, The specific steps include the following: S1. A mixture of hydroxyl-terminated hyperbranched poly(amine-ester), N,N-dimethylformamide, potassium carbonate, and potassium iodide was prepared at a mass ratio of 7.5:50:1~3:0.
1. The mixture was heated to 60~70℃ and stirred at 200~400 rpm for 50~70 min. A polyhydroxypyridine mixture, weighing 2.8~3.2 times the mass of the hydroxyl-terminated hyperbranched poly(amine-ester), was added dropwise at a rate of 1~3 ml / min. The mixture was heated to 100~110℃ and refluxed for 16~24 h. After cooling to room temperature, the mixture was precipitated with ice-cold diethyl ether, filtered, dissolved in N,N-dimethylformamide, precipitated again with ice-cold diethyl ether, and dried under vacuum to obtain the hyperbranched hydroxyl prepolymer. The mass ratio of polyhydroxypyridine to N,N-dimethylformamide in the polyhydroxypyridine mixture was 3~5:
20. S2. Under a nitrogen atmosphere, 4,4'-diaminodiphenyl ether and N-methylpyrrolidone are mixed at a mass ratio of 3~5:50, stirred and dissolved, and placed in an ice bath at 0~5℃. Pyromellitic dianhydride is added in 3~5 portions, with a total amount of 1.12~1.18 times the mass of 4,4'-diaminodiphenyl ether. After stirring and dissolving, the mixture is reacted for 30~50 min. Hyperbranched hydroxyl prepolymer, dehydrating agent acetic anhydride and catalyst pyridine are added. The mixture is heated to room temperature and reacted for 4~6 h. After standing for 12~24 h, it is coated onto the surface of a ceramic substrate and heat-treated at 220~240℃ for 10~20 min. After peeling, it is crushed to obtain hyperbranched polyimide. S3. Under a nitrogen atmosphere, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, palladium catalyst tris(dibenzylacetone)dipalladium, and anhydrous toluene were mixed in a mass ratio of 0.018~0.022:0.02:1 and stirred until homogeneous. Then, 0.26~0.28 times the mass of anhydrous toluene trifluoromethylthiopyridine and 0.25~0.26 times the mass of anhydrous toluene 4-piperidinesulfonylaniline were added. The mixture was heated to 100~110℃ and refluxed for 16~18h. After cooling to room temperature, the mixture was filtered through a diatomaceous earth pad, washed with ethyl acetate, concentrated under reduced pressure, and then purified and concentrated by silica gel column chromatography to obtain the pyridine derivative. S4. Carboxylated carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were mixed in a mass ratio of 10:1:0.001~0.002, heated to 70~72℃, refluxed for 24~26h, cooled to room temperature, filtered, washed 3~5 times with anhydrous tetrahydrofuran, and transferred to a solution of N,N-dimethylformamide containing 18~20% triethylamine (mass ratio of carboxylated carbon nanotubes to triethylamine of 50:2~3). Then, pyridine derivatives with a mass ratio of 3~4 times that of carboxylated carbon nanotubes were added, and the mixture was placed in an oil bath at 80~85℃ and reacted under a nitrogen atmosphere for 48~72h. After filtration, the mixture was washed 3~5 times with N,N-dimethylformamide, and then extracted with tetrahydrofuran and acetone by Soxhlet extraction for 18~24h in sequence. The mixture was then dried to obtain modified carbon nanotubes. S5. By weight, polyetheretherketone, hyperbranched polyimide, modified carbon nanotubes and lubricant are mixed in a high-speed mixer and mixed at 1000~3000 rpm for 8~12 min. The mixture is then transferred to a mold and preheated at 110~120℃ for 20~30 min. The mixture is then transferred to a vacuum sintering furnace and sintered at 370~380℃ for 25~35 min. The mixture is then cooled to room temperature to obtain a high wear-resistant polyetheretherketone composite material.
6. The preparation process of a high wear-resistant polyetheretherketone composite material according to claim 5, characterized in that, In step S1 above, the preparation method of the hydroxyl-terminated hyperbranched poly(amine-ester) is as follows: Under a nitrogen atmosphere, 1,1,1-trimethylolpropane, methyl N,N-dihydroxyethyl-3-aminopropionate and the catalyst p-toluenesulfonic acid are mixed in a mass ratio of 1.2~1.4:20:0.18~0.22 and stirred evenly. Then, 10~18 times the mass of 1,1,1-trimethylolpropane and N,N-dimethylformamide are added. The temperature is raised to 70~72℃ and reacted for 1~2 hours. The temperature is then raised to 110~120℃ and reacted for 6~8 hours. After cooling to room temperature, the product is precipitated with petroleum ether. After filtration, the product is dissolved in acetone and precipitated with petroleum ether. Finally, the product is dried under vacuum at 40~50℃ to obtain the hydroxyl-terminated hyperbranched poly(amine-ester).
7. The preparation process of a high wear-resistant polyetheretherketone composite material according to claim 5, characterized in that, In step S1 above, the preparation method of polyhydroxypyridine is as follows: under a nitrogen atmosphere, p-hydroxyacetophenone, p-hydroxybenzaldehyde and glacial acetic acid are mixed in a mass ratio of 1:2~2.2:180~200, stirred and dissolved, and then ammonium acetate with a mass ratio of 5~8 times that of p-hydroxyacetophenone is added. The mixture is heated to 115~120℃ and refluxed for 6~8 hours. The mixture is filtered and washed 3~5 times with glacial acetic acid and deionized water in sequence. Then, it is recrystallized with ethyl acetate and petroleum ether in a volume ratio of 3:1 to obtain polyhydroxypyridine.
8. The preparation process of a high wear-resistant polyetheretherketone composite material according to claim 5, characterized in that, In step S2 above, the mass ratio of 4,4'-diaminodiphenyl ether, hyperbranched hydroxyl prepolymer, dehydrating agent acetic anhydride, and catalyst pyridine is 2:0.2~0.4:0.1:0.02~0.
03.
9. The preparation process of a high wear-resistant polyetheretherketone composite material according to claim 5, characterized in that, In step S3 above, the preparation method of trifluoromethylthiopyridine is as follows: Under a nitrogen atmosphere, 2,6-dichloro-4-trifluoromethylpyridine, 4-(trifluoromethylthio)phenylboronic acid, potassium phosphate, and 1,4-dioxane are mixed in a mass ratio of 1:1.2~1.4:3:30, stirred evenly, and then 0.002~0.01 times the mass of potassium phosphate catalyst tetra(triphenylphosphine)palladium is added. The temperature is raised to 90~92℃, and the reaction is carried out for 16~18h. The reaction is quenched with saturated ammonium chloride, then extracted with dichloromethane, washed 3~5 times with saturated brine, dried with anhydrous sodium sulfate, and purified by rotary evaporation under reduced pressure with petroleum ether and ethyl acetate in a volume ratio of 10~20:1 to obtain trifluoromethylthiopyridine.
10. The preparation process of a high wear-resistant polyetheretherketone composite material according to claim 5, characterized in that, In step S4 above, the method for preparing carboxylated carbon nanotubes is as follows: multi-walled carbon nanotubes are mixed with mixed acid at a mass ratio of 1:30~50, ultrasonically dispersed evenly, placed in an oil bath at 60~70℃, reacted for 6~8 hours, the reaction was terminated with deionized water, filtered and washed with deionized water 5~8 times, and finally vacuum dried at 40~50℃ to obtain carboxylated carbon nanotubes; the volume ratio of concentrated sulfuric acid to concentrated nitric acid with a mass fraction of 68% in the mixed acid is 3~5:1.