High-toughness wear-resistant engineering plastic product and processing preparation method thereof

Abstract

The invention relates to the technical field of polymer composite materials, in particular to a high-toughness wear-resistant engineering plastic product and a processing preparation method thereof. The high-toughness wear-resistant engineering plastic product is prepared from the following raw materials in parts by weight: 100 parts of polyphenylene sulfide resin, 15-30 parts of glass fibers, 3-8 parts of an additive, 1-5 parts of an additive, 2-5 parts of polytetrafluoroethylene powder and 0.3-1 part of an antioxidant, according to the invention, the combination of the resin and the fiber is enhanced through the additive, the toughness of the material is improved, the additive is combined with the catalyst precursor through a specific carrier and has a synergistic effect with polytetrafluoroethylene, the wear resistance and the mechanical strength are remarkably improved, and the product is prepared through the processes of raw material premixing, melt blending extrusion, injection molding and the like. The material has the advantages of high toughness, high wear resistance, stable size and the like, and is suitable for manufacturing engineering structural parts and wear-resistant parts with strict requirements on mechanical properties and durability.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, specifically to a high-toughness, wear-resistant engineering plastic product and its processing and preparation method. Background Technology

[0002] Engineering plastics have become an ideal alternative to metal materials in the fields of semiconductors, automobiles, electronics and electrical appliances and high-end equipment manufacturing due to their excellent mechanical properties, heat resistance and chemical stability. Among them, polyphenylene sulfide, as a semi-crystalline high-performance engineering plastic, is highly favored in harsh environments due to its outstanding high temperature resistance, corrosion resistance and inherent high strength.

[0003] In the prior art, polyphenylene sulfide (PPS) materials are inherently brittle and tough with insufficient wear resistance. To overcome these shortcomings, glass fiber is added for reinforcement and toughening, and polytetrafluoroethylene (PTFE) is introduced to improve wear resistance. However, the compatibility between glass fiber, PTFE and PPS matrix is ​​poor, and weak points are easily formed when they are blended. Based on this, the present invention provides a high-toughness wear-resistant engineering plastic product and its processing and preparation method. Summary of the Invention

[0004] The purpose of this invention is to provide a high-toughness, wear-resistant engineering plastic product and its processing and preparation method. The engineering plastic product prepared by this invention not only has excellent impact toughness but also excellent wear resistance, effectively improving the overall performance of polyphenylene sulfide engineering plastics under harsh working conditions.

[0005] To achieve the above objectives, the present invention provides the following technical solution: In one aspect, a high-toughness and wear-resistant engineering plastic product comprises the following raw materials in parts by weight: 100 parts polyphenylene sulfide resin, 15-30 parts glass fiber, 3-8 parts additives, 1-5 parts additives, 2-5 parts polytetrafluoroethylene powder, and 0.3-1 parts antioxidant. The raw materials for the additive include hydroquinone, 4,4'-difluorobenzophenone, anhydrous sodium carbonate, powder, and carboxyl-terminated liquid nitrile rubber. The raw materials for the additives include carrier materials and catalyst precursors.

[0006] Furthermore, the additive is prepared by the following method: S1: Hydroquinone, 4,4'-difluorobenzophenone and anhydrous sodium carbonate are mixed in a mass ratio of 1:(2.0-2.3):(1.1-1.3) to obtain a mixture. The mixture is then added to an N-methylpyrrolidone solution to obtain a first mixture, wherein the mass concentration of the N-methylpyrrolidone solution is 8%, and the mass of the N-methylpyrrolidone solution is 2.4-2.6 times that of the mixture. S2: Add powder to the first mixture, stir at 200-300 rpm, heat to 160-180℃, and continue the reaction for 1-1.5 h to obtain intermediate product A; S3: Mix intermediate product A with the second mixture and stir at 75-85℃ and 200-300 rpm for 1-1.5 hours to obtain the additive.

[0007] Furthermore, the powder is prepared by the following method: Step 1: Immerse zirconium oxide powder in sodium hydroxide solution at a solid-liquid ratio of 1g:(5-10)mL for 1.5-2.5h at 90-110℃, filter to obtain filter residue, wash the filter residue with deionized water until neutral, and then calcine at 300℃ for 0.5-1.5h. After calcination, disperse it in sodium dodecyl sulfate solution and sonicate it at 55-65℃ with a power of 400W for 20-30min to obtain intermediate product B. The mass concentration of sodium hydroxide solution is 5%, the mass concentration of sodium dodecyl sulfate solution is 0.3%, and the mass of sodium dodecyl sulfate solution is 5-10 times the mass of zirconium oxide powder. Step 2: Add the reaction solution to intermediate product B, stir at 200-300 rpm for 15-20 min at 30-40℃, then sonicate at 400W for 30 min. After sonication, stir and react at 45-50℃ for 0.5-1 h, filter to obtain filter residue, dry, pulverize, and pass through a 200-300 mesh sieve to obtain powder. The mass of the reaction solution is 5-10% of the mass of the zirconium oxide powder.

[0008] Further, the reaction solution is prepared by the following method: cashew nut shell oil and formaldehyde solution are mixed at a mass ratio of 1:(1-2) to obtain a third mixture. Ammonia water is added to the third mixture, and the mixture is reacted at 55-65°C for 1.5-2.5 hours. After the reaction is completed, peracetic acid is added, and the mixture is reacted at 15-25°C for 1-2 hours to obtain intermediate product C. Intermediate product C is mixed with silane coupling agent KH560 at a mass ratio of (9-10):1. Glacial acetic acid is added, and the mixture is refluxed at 75-85°C for 3-4 hours to obtain reflux liquid. The reflux liquid is concentrated to 1 / 4-1 / 3 of the original volume to obtain the reaction solution. The mass concentration of formaldehyde solution is 37%, the mass concentration of ammonia water is 25-28%, the mass of ammonia water is 0.5% of the third mixture, the mass concentration of peracetic acid is 30%, the mass of peracetic acid is 60-70% of the mass of cashew nut shell oil, and the mass of glacial acetic acid is 15-25% of the mass of cashew nut shell oil.

[0009] Further, the additive is prepared by the following method: the carrier material and ethanol solution are mixed at a mass ratio of 1:(9-11) to obtain a fourth mixture, then a catalyst precursor is added, and the mixture is stirred at 60°C for 4-6 hours. After the reaction is completed, the mixture is vacuum dried at 80°C for 10-12 hours to obtain the additive. The mass of the catalyst precursor is 0.8-0.9% of the mass of the fourth mixture, and the volume concentration of the ethanol solution is 50%.

[0010] Further, the carrier material is prepared by the following method: 1,3,5-tricarboxybenzene and p-phenylenediamine are mixed in a molar ratio of 1:(1-2), N,N-dimethylformamide is added, and glacial acetic acid is added. The mixture is reacted at 120°C for 72 h. After the reaction is completed, the mixture is centrifuged and the precipitate is collected. The precipitate is washed sequentially with N,N-dimethylformamide and acetone. After washing, the mixture is vacuum activated at 150°C for 8 h to obtain the carrier material. The solid-liquid ratio of 1,3,5-tricarboxybenzene to N,N-dimethylformamide is 0.2 g:(12-18) mL, and the volume of glacial acetic acid is 5% of the volume of N,N-dimethylformamide.

[0011] Further, the catalyst precursor is prepared by the following method: zinc acetylacetonate is dispersed in a methanol solution, stirred at 35-45°C, 2-aminoacetylacetonate is added dropwise, and the mixture is refluxed at 60°C for 3-4 hours. After the reaction is completed, the crude product is obtained by rotary evaporation. The crude product is washed three times with n-hexane and dried under vacuum at 40°C for 5-6 hours to obtain the catalyst precursor.

[0012] Furthermore, in S3, the mass of the second mixture is 25-30% of the mass of the powder, and the second mixture is an acetone solution of terminal carboxyl liquid nitrile rubber with a mass concentration of 10-12%.

[0013] Furthermore, the mass ratio of zinc acetylacetonate, methanol solution, and 2-aminoacetylacetonate is 10:(95-105):(2.0-2.4), and the volume concentration of the methanol solution is 90%.

[0014] Secondly, the present invention also provides a method for processing and preparing high-toughness and wear-resistant engineering plastic products, comprising the following steps: Step 1: Add polyphenylene sulfide resin, additives, additives, polytetrafluoroethylene powder and antioxidant to a high-speed mixer and mix for 5-10 minutes to obtain a premix. Step 2: Add the premixed material and glass fiber together into a twin-screw extruder, and after melt blending, extrusion, cooling and granulation, obtain composite material granules; Step 3: The composite material granules are injection molded to obtain high-toughness and wear-resistant engineering plastic products.

[0015] Compared with the prior art, the beneficial effects of the present invention are: 1. In this invention, by introducing additives into the preparation of engineering plastics, the rigid segments in their molecular structure have good compatibility with the polyphenylene sulfide matrix, while the flexible segments in the carboxyl-terminated liquid nitrile rubber can effectively absorb and disperse impact energy, thereby improving the interfacial bonding between glass fiber and polyphenylene sulfide resin, transforming the traditional physical bonding into a synergistic chemical and physical bonding, achieving the effect of strengthening and toughening, so that the composite material obtains high strength while significantly improving toughness.

[0016] 2. In this invention, the rigid powder in the additive and polytetrafluoroethylene constitute a wear-resistant system. After surface modification, the rigid powder has a strong bond with the polyphenylene sulfide matrix, which can effectively support the load and resist plastic deformation. Meanwhile, polytetrafluoroethylene, as a solid lubricant, forms a transfer film during friction, which reduces the coefficient of friction. The two work synergistically to significantly improve the wear resistance and scratch resistance of the composite material.

[0017] 3. In this invention, by introducing a nanoporous carrier structure with additives, the carrier material has a regular porous structure. When these materials with porous structures are uniformly mixed into the plastic matrix, they play a role similar to a micro-skeleton, making the composite material harder and stronger, less prone to scratches and wear. When the composite material is about to crack due to impact, these dispersed hard particles can prevent the crack from expanding, making the material more impact-resistant and less prone to breakage, and making the resulting composite material more wear-resistant, more impact-resistant, and more durable. Attached Figure Description

[0018] Figure 1 The present invention provides a flowchart of a processing and preparation method for high-toughness and wear-resistant engineering plastic products. Detailed Implementation

[0019] 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.

[0020] It should be noted that the raw materials used in the following embodiments are all commercially available. Example 1

[0021] Preparation of the reaction solution: Cashew nut shell oil and formaldehyde solution were mixed at a mass ratio of 1:1 to obtain a third mixture. Ammonia water was added to the third mixture, and the mixture was reacted at 55°C for 1.5 h. After the reaction was completed, peracetic acid was added, and the mixture was reacted at 15°C for 1 h to obtain intermediate product C. Intermediate product C was mixed with silane coupling agent KH560 at a mass ratio of 9:1. Glacial acetic acid was added, and the mixture was refluxed at 75°C for 3 h to obtain reflux liquid. The reflux liquid was concentrated to 1 / 4 of the original volume to obtain the reaction solution. The mass concentration of formaldehyde solution was 37%, the mass concentration of ammonia water was 25%, the mass of ammonia water was 0.5% of the mass of the third mixture, the mass concentration of peracetic acid was 30%, the mass of peracetic acid was 60% of the mass of cashew nut shell oil, and the mass of glacial acetic acid was 15% of the mass of cashew nut shell oil.

[0022] Preparation of powder materials: Step 1: Immerse zirconium oxide powder in sodium hydroxide solution at a solid-liquid ratio of 1g:5mL for 1.5h at 90℃, filter to obtain filter residue, wash the filter residue with deionized water until neutral, and then calcine at 300℃ for 0.5h. After calcination, disperse it in sodium dodecyl sulfate solution and sonicate at 55℃ with a power of 400W for 20min to obtain intermediate product B. The mass concentration of sodium hydroxide solution is 5%, the mass concentration of sodium dodecyl sulfate solution is 0.3%, and the mass of sodium dodecyl sulfate solution is 5-10 times the mass of zirconium oxide powder. Step 2: Add the reaction solution to intermediate product B, stir at 200 rpm for 15 min at 30℃, then sonicate at 400W for 30 min, and after sonication, stir and react at 45℃ for 0.5 h. Filter to obtain filter residue, dry, pulverize, and pass through a 200-mesh sieve to obtain powder. The mass of the reaction solution is 5% of the mass of the zirconium oxide powder.

[0023] Preparation of additives: S1: Hydroquinone, 4,4'-difluorobenzophenone and anhydrous sodium carbonate are mixed in a mass ratio of 1:2:1.1 to obtain a mixture. The mixture is then added to an N-methylpyrrolidone solution to obtain a first mixture, wherein the mass concentration of the N-methylpyrrolidone solution is 8% and the mass of the N-methylpyrrolidone solution is 2.4 times that of the mixture. S2: Add powder to the first mixture, stir at 200 rpm, heat to 160°C, and continue to react for 1 hour to obtain intermediate product A; S3: Mix intermediate product A with the second mixture and stir at 200 rpm for 1 hour at 75°C to obtain the additive.

[0024] In S3, the mass of the second mixture is 25% of the mass of the powder material, and the second mixture is an acetone solution of terminal carboxyl liquid nitrile rubber with a mass concentration of 10%.

[0025] Preparation of catalyst precursor: Zinc acetylacetone was dispersed in methanol solution and stirred at 35°C. 2-Aminoacetylacetone was added dropwise and the mixture was refluxed at 60°C for 3 hours. After the reaction was completed, the crude product was obtained by rotary evaporation. The crude product was washed three times with n-hexane and dried under vacuum at 40°C for 5 hours to obtain the catalyst precursor.

[0026] The mass ratio of zinc acetylacetone, methanol solution, and 2-aminoacetylacetone is 10:95:2, and the volume concentration of the methanol solution is 90%.

[0027] Preparation of the carrier material: 1,3,5-tricarboxybenzene and p-phenylenediamine were mixed in a molar ratio of 1:1, N,N-dimethylformamide was added, and glacial acetic acid was added. The mixture was reacted at 120°C for 72 h. After the reaction was completed, the mixture was centrifuged and the precipitate was collected. The precipitate was washed sequentially with N,N-dimethylformamide and acetone. After washing, the mixture was activated under vacuum at 150°C for 8 h to obtain the carrier material. The solid-liquid ratio of 1,3,5-tricarboxybenzene to N,N-dimethylformamide was 0.2 g: 12 mL, and the volume of glacial acetic acid was 5% of the volume of N,N-dimethylformamide.

[0028] Preparation of additive: The carrier material and ethanol solution are mixed at a mass ratio of 1:9 to obtain a fourth mixture. The catalyst precursor is then added and the mixture is stirred at 60°C for 4 hours. After the reaction is completed, the mixture is vacuum dried at 80°C for 10 hours to obtain the additive. The mass of the catalyst precursor is 0.8% of the mass of the fourth mixture, and the volume concentration of the ethanol solution is 50%.

[0029] Raw material preparation: 100 parts polyphenylene sulfide resin, 15 parts glass fiber, 3 parts additives, 1 part additive, 2 parts polytetrafluoroethylene powder, 0.3 parts antioxidant.

[0030] A method for processing and preparing high-toughness, wear-resistant engineering plastic products includes the following steps: Step 1: Add polyphenylene sulfide resin, additives, additives, polytetrafluoroethylene powder and antioxidant to a high-speed mixer and mix for 5 minutes to obtain a premix. Step 2: Add the premixed material and glass fiber together into a twin-screw extruder, and after melt blending, extrusion, cooling and granulation, obtain composite material granules; Step 3: The composite material granules are injection molded to obtain high-toughness and wear-resistant engineering plastic products. Example 2

[0031] Preparation of the reaction solution: Cashew nut shell oil and formaldehyde solution were mixed at a mass ratio of 1:1.5 to obtain a third mixture. Ammonia water was added to the third mixture, and the mixture was reacted at 60℃ for 2 hours. After the reaction was completed, peracetic acid was added, and the mixture was reacted at 20℃ for 1.5 hours to obtain intermediate product C. Intermediate product C was mixed with silane coupling agent KH560 at a mass ratio of 9.5:1. Glacial acetic acid was added, and the mixture was refluxed at 80℃ for 3.5 hours to obtain reflux liquid. The reflux liquid was concentrated to 1 / 3 of the original volume to obtain the reaction solution. The mass concentration of formaldehyde solution was 37%, the mass concentration of ammonia water was 26%, the mass of ammonia water was 0.5% of the mass of the third mixture, the mass concentration of peracetic acid was 30%, the mass of peracetic acid was 65% of the mass of cashew nut shell oil, and the mass of glacial acetic acid was 20% of the mass of cashew nut shell oil.

[0032] Preparation of powder materials: Step 1: Immerse zirconium oxide powder in sodium hydroxide solution at a solid-liquid ratio of 1g:7mL for 2 hours at 100℃, filter to obtain filter residue, wash the filter residue with deionized water until neutral, and then calcine at 300℃ for 1 hour. After calcination, disperse it in sodium dodecyl sulfate solution and sonicate at 60℃ with a power of 400W for 25 minutes to obtain intermediate product B. The mass concentration of sodium hydroxide solution is 5%, the mass concentration of sodium dodecyl sulfate solution is 0.3%, and the mass of sodium dodecyl sulfate solution is 7 times the mass of zirconium oxide powder. Step 2: Add the reaction solution to intermediate product B, stir at 250 rpm for 17 min at 35℃, then sonicate at 400 W for 30 min. After sonication, stir and react at 47℃ for 1 h, filter to obtain filter residue, dry, pulverize, and pass through a 300 mesh sieve to obtain powder. The mass of the reaction solution is 7% of the mass of the zirconium oxide powder.

[0033] Preparation of additives: S1: Hydroquinone, 4,4'-difluorobenzophenone and anhydrous sodium carbonate are mixed in a mass ratio of 1:2.1:1.2 to obtain a mixture. The mixture is then added to an N-methylpyrrolidone solution to obtain a first mixture, wherein the mass concentration of the N-methylpyrrolidone solution is 8% and the mass of the N-methylpyrrolidone solution is 2.5 times that of the mixture. S2: Add powder to the first mixture, stir at 250 rpm, heat to 170°C, and continue the reaction for 1.5 h to obtain intermediate product A; S3: Mix intermediate product A with the second mixture and stir at 250 rpm for 1.5 h at 80 °C to obtain the additive.

[0034] In S3, the mass of the second mixture is 27% of the mass of the powder material, and the second mixture is an acetone solution of terminal carboxyl liquid nitrile rubber with a mass concentration of 11%.

[0035] Preparation of catalyst precursor: Zinc acetylacetone was dispersed in methanol solution and stirred at 40°C. 2-aminoacetylacetone was added dropwise and the mixture was refluxed at 60°C for 3.5 h. After the reaction was completed, the crude product was obtained by rotary evaporation. The crude product was washed three times with n-hexane and dried under vacuum at 40°C for 5.5 h to obtain the catalyst precursor.

[0036] The mass ratio of zinc acetylacetone, methanol solution, and 2-aminoacetylacetone is 10:100:2.2, and the volume concentration of the methanol solution is 90%.

[0037] Preparation of the carrier material: 1,3,5-tricarboxybenzene and p-phenylenediamine were mixed in a molar ratio of 1:1.5, N,N-dimethylformamide was added, and glacial acetic acid was added. The mixture was reacted at 120°C for 72 h. After the reaction was completed, the mixture was centrifuged and the precipitate was collected. The precipitate was washed sequentially with N,N-dimethylformamide and acetone. After washing, the mixture was activated under vacuum at 150°C for 8 h to obtain the carrier material. The solid-liquid ratio of 1,3,5-tricarboxybenzene to N,N-dimethylformamide was 0.2 g: 16 mL, and the volume of glacial acetic acid was 5% of the volume of N,N-dimethylformamide.

[0038] Preparation of additive: The carrier material and ethanol solution are mixed at a mass ratio of 1:10 to obtain a fourth mixture. The catalyst precursor is then added and the mixture is stirred at 60°C for 5 hours. After the reaction is completed, the mixture is vacuum dried at 80°C for 11 hours to obtain the additive. The mass of the catalyst precursor is 0.85% of the mass of the fourth mixture, and the volume concentration of the ethanol solution is 50%.

[0039] Raw material preparation: 100 parts polyphenylene sulfide resin, 20 parts glass fiber, 6 parts additives, 3 parts additives, 4 parts polytetrafluoroethylene powder, and 0.7 parts antioxidant.

[0040] A method for processing and preparing high-toughness, wear-resistant engineering plastic products includes the following steps: Step 1: Add polyphenylene sulfide resin, additives, additives, polytetrafluoroethylene powder and antioxidant to a high-speed mixer and mix for 7 minutes to obtain a premix. Step 2: Add the premixed material and glass fiber together into a twin-screw extruder, and after melt blending, extrusion, cooling and granulation, obtain composite material granules; Step 3: The composite material granules are injection molded to obtain high-toughness and wear-resistant engineering plastic products. Example 3

[0041] Preparation of the reaction solution: Cashew nut shell oil and formaldehyde solution were mixed at a mass ratio of 1:2 to obtain a third mixture. Ammonia water was added to the third mixture, and the mixture was reacted at 65°C for 2.5 h. After the reaction was completed, peracetic acid was added, and the mixture was reacted at 25°C for 2 h to obtain intermediate product C. Intermediate product C was mixed with silane coupling agent KH560 at a mass ratio of 10:1. Glacial acetic acid was added, and the mixture was refluxed at 85°C for 4 h to obtain reflux liquid. The reflux liquid was concentrated to 1 / 3 of the original volume to obtain the reaction solution. The mass concentration of formaldehyde solution was 37%, the mass concentration of ammonia water was 28%, the mass of ammonia water was 0.5% of the mass of the third mixture, the mass concentration of peracetic acid was 30%, the mass of peracetic acid was 70% of the mass of cashew nut shell oil, and the mass of glacial acetic acid was 25% of the mass of cashew nut shell oil.

[0042] Preparation of powder materials: Step 1: Immerse zirconium oxide powder in sodium hydroxide solution at a solid-liquid ratio of 1g:10mL for 2.5h at 110℃, filter to obtain filter residue, wash the filter residue with deionized water until neutral, and then calcine at 300℃ for 1.5h. After calcination, disperse it in sodium dodecyl sulfate solution and sonicate at 65℃ with a power of 400W for 30min to obtain intermediate product B. The mass concentration of sodium hydroxide solution is 5%, the mass concentration of sodium dodecyl sulfate solution is 0.3%, and the mass of sodium dodecyl sulfate solution is 10 times the mass of zirconium oxide powder. Step 2: Add the reaction solution to intermediate product B, stir at 300 rpm for 20 min at 40℃, then sonicate at 400 W for 30 min, after sonication, stir and react at 50℃ for 1 h, filter to obtain filter residue, dry, pulverize, and pass through a 300 mesh sieve to obtain powder material, wherein the mass of the reaction solution is 10% of the mass of the zirconium oxide powder.

[0043] Preparation of additives: S1: Hydroquinone, 4,4'-difluorobenzophenone and anhydrous sodium carbonate are mixed in a mass ratio of 1:2.3:1.3 to obtain a mixture. The mixture is then added to an N-methylpyrrolidone solution to obtain a first mixture, wherein the mass concentration of the N-methylpyrrolidone solution is 8% and the mass of the N-methylpyrrolidone solution is 2.6 times that of the mixture. S2: Add powder to the first mixture, stir at 300 rpm, heat to 180°C, and continue the reaction for 1.5 h to obtain intermediate product A; S3: Mix intermediate product A with the second mixture and stir at 300 rpm for 1.5 h at 85 °C to obtain the additive.

[0044] In S3, the mass of the second mixture is 30% of the mass of the powder material, and the second mixture is an acetone solution of terminal carboxyl liquid nitrile rubber with a mass concentration of 12%.

[0045] Preparation of catalyst precursor: Zinc acetylacetone was dispersed in methanol solution and stirred at 45°C. 2-Aminoacetylacetone was added dropwise and the mixture was refluxed at 60°C for 4 hours. After the reaction was completed, the crude product was obtained by rotary evaporation. The crude product was washed three times with n-hexane and dried under vacuum at 40°C for 6 hours to obtain the catalyst precursor.

[0046] The mass ratio of zinc acetylacetone, methanol solution, and 2-aminoacetylacetone is 10:105:2.4, and the volume concentration of the methanol solution is 90%.

[0047] Preparation of the carrier material: 1,3,5-tricarboxybenzene and p-phenylenediamine were mixed in a molar ratio of 1:2, N,N-dimethylformamide was added, and glacial acetic acid was added. The mixture was reacted at 120°C for 72 h. After the reaction was completed, the mixture was centrifuged and the precipitate was collected. The precipitate was washed sequentially with N,N-dimethylformamide and acetone. After washing, the mixture was activated under vacuum at 150°C for 8 h to obtain the carrier material. The solid-liquid ratio of 1,3,5-tricarboxybenzene to N,N-dimethylformamide was 0.2 g: 18 mL, and the volume of glacial acetic acid was 5% of the volume of N,N-dimethylformamide.

[0048] Preparation of additive: The carrier material and ethanol solution were mixed at a mass ratio of 1:11 to obtain a fourth mixture. The catalyst precursor was then added and the mixture was stirred at 60°C for 6 hours. After the reaction was completed, the mixture was vacuum dried at 80°C for 12 hours to obtain the additive. The mass of the catalyst precursor was 0.9% of the mass of the fourth mixture, and the volume concentration of the ethanol solution was 50%.

[0049] Raw material preparation: 100 parts polyphenylene sulfide resin, 30 parts glass fiber, 8 parts additives, 5 parts additives, 5 parts polytetrafluoroethylene powder, and 1 part antioxidant.

[0050] A method for processing and preparing high-toughness, wear-resistant engineering plastic products includes the following steps: Step 1: Add polyphenylene sulfide resin, additives, additives, polytetrafluoroethylene powder and antioxidant to a high-speed mixer and mix for 10 minutes to obtain a premix. Step 2: Add the premixed material and glass fiber together into a twin-screw extruder, and after melt blending, extrusion, cooling and granulation, obtain composite material granules; Step 3: The composite material granules are injection molded to obtain high-toughness and wear-resistant engineering plastic products.

[0051] Comparative Example 1: The difference between this comparative example and Example 1 is that this comparative example does not contain any additives.

[0052] Comparative Example 2 differs from Example 1 in that it does not contain any additives.

[0053] Comparative Example 3 differs from Example 1 in that zirconium oxide powder is used instead of powder material in this comparative example.

[0054] Comparative Example 4 differs from Example 1 in that it uses a carrier material without catalyst loading instead of additives.

[0055] Performance testing: Performance tests were conducted on the high-toughness, wear-resistant engineering plastic products treated in Examples 1-3 and Comparative Examples 1-4. The test data are recorded in the table below: Table 1 Testing items Notched impact strength of cantilever beam (kJ / m²) Wear and tear (mg) Heat distortion temperature (°C) Example 1 12.5 8.1 258 Example 2 13.7 7.5 260 Example 3 13.5 7.8 259 Comparative Example 1 6.8 15.6 242 Comparative Example 2 9.2 12.3 247 Comparative Example 3 8.1 14.1 244 Comparative Example 4 10.5 11.7 248 In the performance testing, the notched impact strength test of the cantilever beam is in accordance with GB / T 1843-2008, the wear test is in accordance with GB / T 3960-2016, and the heat distortion temperature test is in accordance with GB / T 1634.2-2019.

[0056] According to the performance test data, the cantilever beam notched impact strength of the high-toughness wear-resistant engineering plastic products prepared in Examples 1-3 was significantly higher than that of Comparative Examples 1-4. This indicates that the additive constructed a strong interface layer between the polyphenylene sulfide matrix and the glass fiber. Among them, the polyether ether ketone oligomer generated in situ from hydroquinone and difluorobenzophenone, as a rigid segment, has good compatibility with the polyphenylene sulfide matrix, while the carboxyl-terminated liquid nitrile rubber, as a flexible segment, absorbs and dissipates a large amount of energy. This interface structure, which combines rigidity and flexibility, elevates the traditional physical bonding to a synergistic combination of chemical and physical processes, improves stress transfer efficiency, and prevents crack initiation and propagation. In contrast, Comparative Example 1, due to the complete absence of this additive, had the weakest interface bonding and the worst impact performance. Comparative Example 3 used zirconia that was not sufficiently surface-modified, which had weak interfacial bonding with the matrix and was prone to becoming a stress concentration point, thus limiting the improvement of toughness. This invention, through ingenious interface design, solves the technical problems of poor compatibility between rigid fillers and plastic matrices and the decrease in modulus caused by traditional toughening methods.

[0057] The wear resistance test results of Examples 1-3 are far superior to all comparative examples, indicating that the multiple wear resistance mechanisms in this invention play a key role. The rigid powder material in the additive, after effective surface treatment and polymer coating, is firmly bonded to the matrix and acts as the main load-bearing skeleton during friction, effectively resisting plastic deformation. At the same time, the polytetrafluoroethylene powder, as a solid lubricant, can form a transfer film on the surface of the friction pair, reducing the coefficient of friction. Furthermore, the additive can act as a rigid nanomaterial to reinforce and toughen the matrix itself. Comparative examples 2 and 4 have higher wear rates due to the lack of such toughening material, while comparative examples 1 and 3 have poor wear resistance due to the lack of complete rigid support and lubrication effect. This invention significantly improves the durability and reliability of the product under harsh working conditions by constructing an integrated wear-resistant defense line through hard load-bearing and solid lubrication.

[0058] The test data of heat distortion temperature show that all embodiments, while achieving excellent toughness and wear resistance, still maintain the inherent high heat resistance of polyphenylene sulfide resin. The polyether ether ketone oligomer in the additive is itself a high-performance heat-resistant polymer. Its introduction not only does not reduce the thermal stability of the material, but also enhances the rigid network of the material at high temperatures through interaction with the polyphenylene sulfide matrix. However, due to the interfacial bonding problem, Comparative Examples 1 and 3 have to some extent damaged the integrity and structural integrity of the material, resulting in a slight loss of its thermal performance.

[0059] By comparing and analyzing the relevant data in the table, it can be seen that the high-toughness and wear-resistant engineering plastic products prepared by this invention not only possess excellent impact toughness and wear resistance, but also maintain the inherent heat resistance properties of the matrix material. This indicates that the high-performance engineering plastic formulation and preparation process based on polyphenylene sulfide provided by this invention has a broader market prospect and is more suitable for application in harsh working conditions such as automotive parts and mechanical transmission components.

[0060] 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.

[0061] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high-toughness, wear-resistant engineering plastic product, characterized in that, The raw materials include the following parts by weight: 100 parts polyphenylene sulfide resin, 15-30 parts glass fiber, 3-8 parts additives, 1-5 parts additives, 2-5 parts polytetrafluoroethylene powder, and 0.3-1 parts antioxidant. The raw materials for the additive include hydroquinone, 4,4'-difluorobenzophenone, anhydrous sodium carbonate, powder, and carboxyl-terminated liquid nitrile rubber. The raw materials for the additives include carrier materials and catalyst precursors.

2. The high-toughness, wear-resistant engineering plastic product according to claim 1, characterized in that, The additive is prepared by the following method: S1: Hydroquinone, 4,4'-difluorobenzophenone and anhydrous sodium carbonate are mixed in a mass ratio of 1:(2.0-2.3):(1.1-1.3) to obtain a mixture. The mixture is then added to an N-methylpyrrolidone solution to obtain a first mixture, wherein the mass concentration of the N-methylpyrrolidone solution is 8%, and the mass of the N-methylpyrrolidone solution is 2.4-2.6 times that of the mixture. S2: Add powder to the first mixture, stir at 200-300 rpm, heat to 160-180℃, and continue the reaction for 1-1.5 h to obtain intermediate product A; S3: Mix intermediate product A with the second mixture and stir at 75-85℃ and 200-300 rpm for 1-1.5 hours to obtain the additive.

3. The high-toughness, wear-resistant engineering plastic product according to claim 2, characterized in that, The powder is prepared by the following method: Step 1: Immerse zirconium oxide powder in sodium hydroxide solution at a solid-liquid ratio of 1g:(5-10)mL for 1.5-2.5h at 90-110℃, filter to obtain filter residue, wash the filter residue with deionized water until neutral, and then calcine at 300℃ for 0.5-1.5h. After calcination, disperse it in sodium dodecyl sulfate solution and sonicate it at 55-65℃ with a power of 400W for 20-30min to obtain intermediate product B. The mass concentration of sodium hydroxide solution is 5%, the mass concentration of sodium dodecyl sulfate solution is 0.3%, and the mass of sodium dodecyl sulfate solution is 5-10 times the mass of zirconium oxide powder. Step 2: Add the reaction solution to intermediate product B, stir at 200-300 rpm for 15-20 min at 30-40℃, then sonicate at 400W for 30 min. After sonication, stir and react at 45-50℃ for 0.5-1 h, filter to obtain filter residue, dry, pulverize, and pass through a 200-300 mesh sieve to obtain powder. The mass of the reaction solution is 5-10% of the mass of the zirconium oxide powder.

4. The high-toughness, wear-resistant engineering plastic product according to claim 3, characterized in that, The reaction solution is prepared by the following method: cashew nut shell oil and formaldehyde solution are mixed at a mass ratio of 1:(1-2) to obtain a third mixture. Ammonia water is added to the third mixture, and the mixture is reacted at 55-65°C for 1.5-2.5 hours. After the reaction is completed, peracetic acid is added, and the mixture is reacted at 15-25°C for 1-2 hours to obtain intermediate product C. Intermediate product C is mixed with silane coupling agent KH560 at a mass ratio of (9-10):

1. Glacial acetic acid is added, and the mixture is refluxed at 75-85°C for 3-4 hours to obtain reflux liquid. The reflux liquid is concentrated to 1 / 4-1 / 3 of the original volume to obtain the reaction solution. The mass concentration of formaldehyde solution is 37%, the mass concentration of ammonia water is 25-28%, the mass of ammonia water is 0.5% of the mass of the third mixture, the mass concentration of peracetic acid is 30%, the mass of peracetic acid is 60-70% of the mass of cashew nut shell oil, and the mass of glacial acetic acid is 15-25% of the mass of cashew nut shell oil.

5. The high-toughness, wear-resistant engineering plastic product according to claim 1, characterized in that, The additive is prepared by the following method: the carrier material and ethanol solution are mixed at a mass ratio of 1:(9-11) to obtain a fourth mixture, then a catalyst precursor is added, and the mixture is stirred at 60°C for 4-6 hours. After the reaction is completed, the mixture is vacuum dried at 80°C for 10-12 hours to obtain the additive. The mass of the catalyst precursor is 0.8-0.9% of the mass of the fourth mixture, and the volume concentration of the ethanol solution is 50%.

6. The high-toughness, wear-resistant engineering plastic product according to claim 5, characterized in that, The carrier material is prepared by the following method: 1,3,5-tricarboxymethylbenzene and p-phenylenediamine are mixed in a molar ratio of 1:(1-2), N,N-dimethylformamide is added, and glacial acetic acid is added. The mixture is reacted at 120°C for 72 h. After the reaction is completed, the mixture is centrifuged and the precipitate is collected. The precipitate is washed sequentially with N,N-dimethylformamide and acetone. After washing, the mixture is activated under vacuum at 150°C for 8 h to obtain the carrier material. The solid-liquid ratio of 1,3,5-tricarboxymethylbenzene to N,N-dimethylformamide is 0.2 g:(12-18) mL, and the volume of glacial acetic acid is 5% of the volume of N,N-dimethylformamide.

7. The high-toughness, wear-resistant engineering plastic product according to claim 4, characterized in that, The catalyst precursor was prepared by the following method: zinc acetylacetone was dispersed in a methanol solution and stirred at 35-45°C. 2-aminoacetylacetone was added dropwise and the mixture was refluxed at 60°C for 3-4 hours. After the reaction was completed, the crude product was obtained by rotary evaporation. The crude product was washed three times with n-hexane and dried under vacuum at 40°C for 5-6 hours to obtain the catalyst precursor.

8. The high-toughness, wear-resistant engineering plastic product according to claim 2, characterized in that, The mass of the second mixture in S3 is 25-30% of the mass of the powder material, and the second mixture is an acetone solution of terminal carboxyl liquid nitrile rubber with a mass concentration of 10-12%.

9. The high-toughness, wear-resistant engineering plastic product according to claim 7, characterized in that, The mass ratio of zinc acetylacetone, methanol solution, and 2-aminoacetylacetone is 10:(95-105):(2.0-2.4), and the volume concentration of the methanol solution is 90%.

10. The processing and preparation method of the high-toughness wear-resistant engineering plastic product according to claims 1-9, characterized in that, Includes the following steps: Step 1: Add polyphenylene sulfide resin, additives, additives, polytetrafluoroethylene powder and antioxidant to a high-speed mixer and mix for 5-10 minutes to obtain a premix. Step 2: Add the premixed material and glass fiber together into a twin-screw extruder, and after melt blending, extrusion, cooling and granulation, obtain composite material granules; Step 3: The composite material granules are injection molded to obtain high-toughness and wear-resistant engineering plastic products.

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