Aging-resistant polyether ether ketone composite material and method for producing the same

Abstract

The application relates to the technical field of high polymer materials, in particular to an anti-aging polyether ether ketone composite material and a production method thereof; the anti-aging polyether ether ketone composite material is made of the following raw materials in parts by weight: 60-80 parts of polyether ether ketone, 20-40 parts of polyphenylene sulfide, 10-20 parts of carbon fiber, 5-8 parts of a compatilizer, 0.8-1.5 parts of a silane coupling agent, 0.3-0.6 parts of an antioxidant, 4-6 parts of an anti-aging additive, 6-10 parts of talcum powder, 3-5 parts of titanium nitride and 0.8-1.5 parts of polyethylene wax; wherein the melt index of the polyether ether ketone is 20-35 g / 10 min; the polyether ether ketone-based engineering plastic produced by the application not only has good mechanical properties, but more importantly, has excellent anti-aging performance, which can effectively prolong the service life and ensure the quality.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to an anti-aging polyether ether ketone composite material and its production method. Background Technology

[0002] Polyetheretherketone (PEEK) is a linear aromatic polymer compound with repeating units in its main chain. Its constituent units are oxy-p-phenylene-oxy-carbonyl-p-phenylene, and it is a semi-crystalline thermoplastic. PEEK possesses excellent mechanical properties, good self-lubricating properties, and resistance to chemical corrosion. It also exhibits flame retardancy, peel resistance, and abrasion resistance, making it suitable for high-end machinery, nuclear engineering, and aerospace technologies. Furthermore, it can be used as a high-temperature structural material and electrical insulation material, or combined with carbon fiber or carbon fiber composites to prepare reinforcing materials.

[0003] Due to its numerous advantages, polyetheretherketone (PEEK) is widely used in aerospace, automotive manufacturing, electronics, and medical devices. However, under prolonged exposure to environmental factors such as heat, oxygen, and ultraviolet radiation, PEEK and its composites still undergo a certain degree of aging, leading to a decline in their mechanical properties and thus limiting their service life in harsh outdoor environments or under prolonged high-temperature conditions. Therefore, this invention provides an anti-aging PEEK composite material and its production method to solve the aforementioned technical problems. Summary of the Invention

[0004] The polyether ether ketone-based engineering plastic produced by this invention not only has good mechanical properties, but more importantly, it also has excellent anti-aging properties, which can effectively extend its service life and ensure its quality.

[0005] To achieve the above objectives, the present invention provides the following technical solution: An anti-aging polyetheretherketone composite material is made from the following raw materials in parts by weight: 60-80 parts polyetheretherketone, 20-40 parts polyphenylene sulfide, 10-20 parts carbon fiber, 5-8 parts compatibilizer, 0.8-1.5 parts silane coupling agent, 0.3-0.6 parts antioxidant, 4-6 parts anti-aging additive, 6-10 parts talc, 3-5 parts titanium nitride, and 0.8-1.5 parts polyethylene wax; wherein the melt index of polyetheretherketone is 20-35 g / 10 min.

[0006] Furthermore, the preparation method of the anti-aging adjuvant includes the following steps: Step 1: Disperse functionalized spherical zinc oxide uniformly in N,N-dimethylformamide at a solid-liquid ratio of 1:10-20, and add 15-20% by mass of tert-butylacrylamide sulfonic acid and 0.8-1.5% by mass of sodium persulfate. After reacting at 80-85℃ for 3-4 hours, filter, wash and vacuum dry to obtain modified spherical zinc oxide. Step 2: Add 3-chloropropyltriethoxysilane to n-hexane at a dosage ratio of 0.02-0.03 mol / L, then add 10-20% of 1,3-benzenediol monobenzoate and 15-25% of sodium carbonate, respectively. Stir the reaction for 3-4 hours and filter out the supernatant. Disperse the modified spherical zinc oxide in the supernatant at a dosage ratio of 10-30 g / L, and add 2-3% of bismuth isooctanoate by mass of the modified spherical zinc oxide. Stir the reaction at 50-60℃ for 3-4 hours, then filter, wash with alcohol, and vacuum dry the product to obtain the final product.

[0007] Furthermore, the preparation method of functionalized spherical zinc oxide is as follows: spherical zinc oxide is uniformly dispersed in an ethanol aqueous solution with a volume concentration of 85-90% at a dosage ratio of 30-60 g / L, and vinyltriethoxysilane at a mass of 20-30% of the spherical zinc oxide is added. After reacting at 60-70℃ for 2-3 hours, the product is filtered, washed, and dried sequentially to obtain functionalized spherical zinc oxide.

[0008] Furthermore, the method for preparing the spherical zinc oxide is as follows: zinc nitrate, sodium acetylcysteine, polyethyleneimine, and water are mixed in a mass ratio of 2-4:0.4-0.6:0.2-0.3:30-40, and the pH is adjusted to 12.3-12.8 with sodium hydroxide. The resulting mixture is subjected to hydrothermal reaction at 160-180℃ for 5-8 hours and then cooled to room temperature. The reaction product is then filtered, washed with water and ethanol 3-4 times each, dried, and calcined at high temperature to obtain the final product.

[0009] Furthermore, the drying temperature is 100-120℃, and the drying time is 12-15h; the high-temperature calcination temperature is set to 450-550℃, and the high-temperature calcination time is 2-3h.

[0010] Furthermore, the silane coupling agent is any one of γ-glycidyl etheroxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-mercaptopropyltriethoxysilane.

[0011] Furthermore, the carbon fiber has a length of 6-8 mm and a diameter of 10-12 μm; the talc powder has a particle size of 30-35 μm; and the titanium nitride has a particle size of 5-15 μm.

[0012] Furthermore, the antioxidant is any one of antioxidant 1010, antioxidant 1098, and antioxidant 168.

[0013] Furthermore, the compatibilizer is selected from any one of POE-g-GMA (polyolefin elastomer grafted with glycidyl methacrylate), SEBS-g-GMA (styrene-ethylene-butene-styrene block copolymer grafted with glycidyl methacrylate), and n-butyl acrylate-glycidyl methacrylate.

[0014] A method for producing an anti-aging polyetheretherketone composite material includes the following steps: Step 1: Accurately weigh each raw material, and dry polyether ether ketone and polyphenylene sulfide at 110-130℃ for 4-5 hours. Then, mix the dried polyether ether ketone and polyphenylene sulfide with the remaining raw materials except carbon fiber to obtain a mixture. The second step is to add carbon fiber to the mixture, mix it evenly, and then melt extrude and granulate it at 280-360℃ to obtain the anti-aging polyether ether ketone composite material.

[0015] Compared with the prior art, the beneficial effects of the present invention are: This invention uses zinc nitrate, sodium acetylcysteine, polyethyleneimine, and water as raw materials to prepare spherical zinc oxide with a porous and spherical morphology. Vinyltriethoxysilane is then used to modify the spherical zinc oxide to prepare vinylated spherical zinc oxide, i.e., functionalized spherical zinc oxide. The prepared spherical zinc oxide is uniformly dispersed in N,N-dimethylformamide and tert-butylacrylamide sulfonic acid is added. Under the action of sodium persulfate, tert-butylacrylamide sulfonic acid reacts chemically with the functionalized spherical zinc oxide. Ultimately, the tert-butylacrylamide sulfonic acid is chemically bonded and uniformly anchored on the surface of the spherical zinc oxide and the inner wall of its porous structure, thus obtaining modified spherical zinc oxide.

[0016] Modified spherical zinc oxide was added to the upper layer solution generated after the reaction of 3-chloropropyltriethoxysilane, 1,3-benzene monobenzoate, and sodium carbonate. Finally, under the action of bismuth isooctanoate, 1,3-benzene monobenzoate was chemically grafted onto the surface of the modified spherical zinc oxide and into the porous interior of its structure, ultimately preparing an anti-aging additive. The resulting anti-aging additive has a spherical zinc oxide core and a double-layered coating structure on its surface, consisting of an inner coating of tert-butylacrylamide sulfonic acid and an outer coating of 1,3-benzene monobenzoate. This gives the final anti-aging additive a distinct core-shell structure. The synergistic effect of the spherical zinc oxide, tert-butylacrylamide sulfonic acid, and 1,3-benzene monobenzoate results in excellent anti-aging properties. When used in polyetheretherketone (PEEK) composites, it significantly improves their anti-aging performance, effectively extending their service life while ensuring their quality. Detailed Implementation

[0017] 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.

[0018] Plus wear resistance Example

[0019] An anti-aging polyetheretherketone composite material is made from the following raw materials in parts by weight: 60 parts polyetheretherketone, 20 parts polyphenylene sulfide, 10 parts carbon fiber, 5 parts POE-g-GMA compatibilizer, 0.8 parts γ-glycidyl etheroxypropyltrimethoxysilane, 0.3 parts antioxidant 1010, 4 parts anti-aging additive, 6 parts talc, 3 parts titanium nitride, and 0.8 parts polyethylene wax; wherein the melt index of polyetheretherketone is 20-35 g / 10 min; the length of carbon fiber is 6 mm and the diameter is 10 μm; the particle size of talc is 30 μm; and the particle size of titanium nitride is 5 μm.

[0020] The preparation method of anti-aging additives includes the following steps: Step 1: Disperse functionalized spherical zinc oxide uniformly in N,N-dimethylformamide at a solid-liquid ratio of 1:10, and add 15% by mass of tert-butylacrylamide sulfonic acid and 0.8% by mass of sodium persulfate of functionalized spherical zinc oxide. After reacting at 80℃ for 4 hours, filter, wash and vacuum dry to obtain modified spherical zinc oxide. Step 2: Add 3-chloropropyltriethoxysilane to n-hexane at a dosage ratio of 0.02 mol / L, then add 1,3-benzenediol monobenzoate (10% of 3-chloropropyltriethoxysilane) and sodium carbonate (15% of 3-chloropropyltriethoxysilane). Stir the reaction for 3 hours and filter out the supernatant. Disperse the modified spherical zinc oxide in the supernatant at a dosage ratio of 10 g / L, and add bismuth isooctanoate (2% of the modified spherical zinc oxide by mass). Stir the reaction at 50°C for 4 hours, then filter, wash with alcohol, and vacuum dry the product to obtain the final product.

[0021] The preparation method of functionalized spherical zinc oxide is as follows: spherical zinc oxide is uniformly dispersed in an 85% ethanol aqueous solution at a dosage ratio of 30 g / L, and vinyltriethoxysilane at a mass of 20% of the spherical zinc oxide is added. After reacting at 60℃ for 3 h, the product is filtered, washed and dried sequentially to obtain functionalized spherical zinc oxide.

[0022] The preparation method of spherical zinc oxide is as follows: zinc nitrate, sodium acetylcysteine, polyethyleneimine and water are mixed in a mass ratio of 2:0.4:0.2:30, and the pH is adjusted to 12.3 with sodium hydroxide. The resulting mixture is subjected to hydrothermal reaction at 160℃ for 8 hours and then cooled to room temperature. The reaction product is then filtered, washed three times each with water and ethanol, dried and calcined at high temperature to obtain the final product. The drying temperature is 100℃ and the drying time is 15 hours. The high-temperature calcination temperature is set at 450℃ and the high-temperature calcination time is 3 hours.

[0023] A method for producing an anti-aging polyetheretherketone composite material includes the following steps: Step 1: Accurately weigh each raw material, and dry polyether ether ketone and polyphenylene sulfide at 110°C for 5 hours. Then, mix the dried polyether ether ketone and polyphenylene sulfide with the remaining raw materials except carbon fiber to obtain a mixture. The second step is to add carbon fiber to the mixture, mix it evenly, and then melt extrude and granulate it at 360°C to obtain the anti-aging polyether ether ketone composite material.

[0024] Example 2 The production method of the anti-aging polyether ether ketone composite material provided in this embodiment is basically the same as that in Example 1, except that the specific raw material ratios and the preparation methods of the anti-aging additives are different. The specific raw material ratios and the preparation methods of the anti-aging additives in this embodiment are as follows: An anti-aging polyether ether ketone composite material is made from the following raw materials in parts by weight: 70 parts polyether ether ketone, 30 parts polyphenylene sulfide, 15 parts carbon fiber, 6 parts SEBS-g-GMA compatibilizer, 1.2 parts γ-aminopropyltriethoxysilane, 0.5 parts antioxidant 1098, 5 parts anti-aging additive, 8 parts talc, 4 parts titanium nitride and 1 part polyethylene wax.

[0025] The preparation method of anti-aging additives includes the following steps: Step 1: Disperse functionalized spherical zinc oxide uniformly in N,N-dimethylformamide at a solid-liquid ratio of 1:15, and add 15% by mass of tert-butylacrylamide sulfonic acid and 1% by mass of sodium persulfate of functionalized spherical zinc oxide. After reacting at 80℃ for 4 hours, filter, wash and vacuum dry to obtain modified spherical zinc oxide. Step 2: Add 3-chloropropyltriethoxysilane to n-hexane at a dosage ratio of 0.03 mol / L, then add 1,3-benzenediol monobenzoate (15% of 3-chloropropyltriethoxysilane) and 20% sodium carbonate. Stir the reaction for 3 hours and filter out the supernatant. Disperse the modified spherical zinc oxide in the supernatant at a dosage ratio of 20 g / L, and add bismuth isooctanoate (2.5% of the modified spherical zinc oxide by mass). Stir the reaction at 55°C for 4 hours, then filter, wash with alcohol, and vacuum dry to obtain the final product.

[0026] The preparation method of functionalized spherical zinc oxide is as follows: spherical zinc oxide is uniformly dispersed in an ethanol aqueous solution with a volume concentration of 90% at a dosage ratio of 50 g / L, and vinyltriethoxysilane at a mass of 25% of the spherical zinc oxide is added. After reacting at 65°C for 3 h, the product is filtered, washed and dried sequentially to obtain functionalized spherical zinc oxide.

[0027] The preparation method of spherical zinc oxide is as follows: zinc nitrate, sodium acetylcysteine, polyethyleneimine and water are mixed in a mass ratio of 3:0.5:0.3:35, and the pH is adjusted to 12.5 with sodium hydroxide. The resulting mixture is subjected to hydrothermal reaction at 170℃ for 6 hours and then cooled to room temperature. The reaction product is then filtered, washed four times each with water and ethanol, dried and calcined at high temperature to obtain the final product. The drying temperature is 110℃ and the drying time is 15 hours. The high-temperature calcination temperature is set to 500℃ and the high-temperature calcination time is 3 hours.

[0028] Example 3 The production method of the anti-aging polyether ether ketone composite material provided in this embodiment is basically the same as that in Example 1, except that the specific raw material ratios and the preparation methods of the anti-aging additives are different. The specific raw material ratios and the preparation methods of the anti-aging additives in this embodiment are as follows: An anti-aging polyetheretherketone composite material is made from the following raw materials in parts by weight: 80 parts polyetheretherketone, 40 parts polyphenylene sulfide, 20 parts carbon fiber, 8 parts n-butyl acrylate-glycidyl acrylate, 1.5 parts γ-mercaptopropyltriethoxysilane, 0.6 parts antioxidant 168, 6 parts anti-aging additive, 10 parts talc, 5 parts titanium nitride and 1.5 parts polyethylene wax.

[0029] The preparation method of anti-aging additives includes the following steps: Step 1: Disperse functionalized spherical zinc oxide uniformly in N,N-dimethylformamide at a solid-liquid ratio of 1:20, and add 20% by mass of tert-butylacrylamide sulfonic acid and 1.5% by mass of sodium persulfate of functionalized spherical zinc oxide. After reacting at 85°C for 3 hours, filter, wash and vacuum dry to obtain modified spherical zinc oxide. Step 2: Add 3-chloropropyltriethoxysilane to n-hexane at a dosage ratio of 0.03 mol / L, then add 1,3-benzenediol monobenzoate (20% of 3-chloropropyltriethoxysilane) and sodium carbonate (25% of 3-chloropropyltriethoxysilane). Stir the reaction for 4 hours and filter out the supernatant. Disperse the modified spherical zinc oxide in the supernatant at a dosage ratio of 30 g / L, and add bismuth isooctanoate (3% of the modified spherical zinc oxide by mass). Stir the reaction at 60°C for 3 hours, then filter, wash with alcohol, and vacuum dry to obtain the final product.

[0030] The preparation method of functionalized spherical zinc oxide is as follows: spherical zinc oxide is uniformly dispersed in an ethanol aqueous solution with a volume concentration of 90% at a dosage ratio of 60 g / L, and vinyltriethoxysilane with a mass of 30% of spherical zinc oxide is added. After reacting at 70℃ for 2 h, the product is filtered, washed and dried in sequence to obtain functionalized spherical zinc oxide.

[0031] The preparation method of spherical zinc oxide is as follows: zinc nitrate, sodium acetylcysteine, polyethyleneimine and water are mixed in a mass ratio of 4:0.6:0.3:40, and the pH is adjusted to 12.8 with sodium hydroxide. The resulting mixture is subjected to hydrothermal reaction at 180℃ for 5 hours and then cooled to room temperature. The reaction product is then filtered, washed four times each with water and ethanol, dried and calcined at high temperature to obtain the final product. The drying temperature is 120℃ and the drying time is 12 hours. The high-temperature calcination temperature is set at 550℃ and the high-temperature calcination time is 2 hours.

[0032] Comparative Example 1: The difference between this comparative example and Example 1 is that an equal amount of modified spherical zinc oxide is used instead of the anti-aging additive in this comparative example.

[0033] Comparative Example 2: The difference between this comparative example and Example 1 is that an equal amount of spherical zinc oxide is used instead of the anti-aging additive in this comparative example.

[0034] Performance Testing: The anti-aging polyetheretherketone composite material samples produced in Examples 1-3 and Comparative Examples 1-2 were prepared into test specimens with dimensions of 50×100×3mm (ISO 3167 standard dumbbell specimens), and tested according to GB / T 16422.3-2014 "Plastics - Laboratory Light Source Exposure Methods - Part 3: Fluorescent Ultraviolet Lamps". The specific test method was as follows: the test specimens were placed in an ultraviolet aging test chamber and continuously irradiated for 500 hours (UVA-340 lamp, irradiance 0.76 W / m², 60℃ illumination / 50℃ condensation cycle). Before and after the test, the notched impact strength of each test specimen was tested according to GB / T 1043.1-2008 "Determination of Impact Properties of Simply Supported Beams in Plastics", and the tensile strength of each test specimen was tested according to GB / T1040.2-2006.

[0035] Among them, the retention rate of notched impact strength of simply supported beam / % = Notched impact strength of simply supported beam after aging / Notched impact strength of simply supported beam after aging × 100%;

[0036] Tensile strength retention rate / % = Tensile strength after aging / Tensile strength before aging × 100%.

[0037] The test data and related calculation results obtained above are recorded in the table below:

[0038] By comparing and analyzing the relevant data in the table, it can be seen that the polyetheretherketone (PEEK)-based engineering plastic produced by this invention not only has good mechanical properties, but more importantly, it also has excellent anti-aging properties. This not only effectively extends its service life but also ensures its quality. Therefore, this invention provides an anti-aging PEEK composite material and its production method, which has a broader market prospect and is more suitable for widespread application.

[0039] 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.

[0040] 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. An anti-aging polyetheretherketone composite material, characterized in that, It is made from the following raw materials in parts by weight: 60-80 parts polyetheretherketone, 20-40 parts polyphenylene sulfide, 10-20 parts carbon fiber, 5-8 parts compatibilizer, 0.8-1.5 parts silane coupling agent, 0.3-0.6 parts antioxidant, 4-6 parts anti-aging additive, 6-10 parts talc, 3-5 parts titanium nitride and 0.8-1.5 parts polyethylene wax; The preparation method of the anti-aging additive includes the following steps: Step 1: Disperse functionalized spherical zinc oxide uniformly in N,N-dimethylformamide at a solid-liquid ratio of 1:10-20, and add 15-20% by mass of tert-butylacrylamide sulfonic acid and 0.8-1.5% by mass of sodium persulfate. After reacting at 80-85℃ for 3-4 hours, filter, wash and vacuum dry to obtain modified spherical zinc oxide. Step 2: Add 3-chloropropyltriethoxysilane to n-hexane at a dosage ratio of 0.02-0.03 mol / L, then add 10-20% of 1,3-benzenediol monobenzoate and 15-25% of sodium carbonate, respectively. Stir the reaction for 3-4 hours and filter out the supernatant. Disperse the modified spherical zinc oxide in the supernatant at a dosage ratio of 10-30 g / L, and add 2-3% of the modified spherical zinc oxide by mass of bismuth isooctanoate. Stir the reaction at 50-60℃ for 3-4 hours, then filter, wash with alcohol, and vacuum dry the product to obtain the final product. The preparation method of the functionalized spherical zinc oxide is as follows: spherical zinc oxide is uniformly dispersed in an ethanol aqueous solution with a volume concentration of 85-90% at a dosage ratio of 30-60 g / L, and vinyltriethoxysilane at a mass of 20-30% of the spherical zinc oxide is added. After reacting at 60-70℃ for 2-3 hours, the product is filtered, washed and dried sequentially to obtain the functionalized spherical zinc oxide. The method for preparing the spherical zinc oxide is as follows: zinc nitrate, sodium acetylcysteine, polyethyleneimine and water are mixed in a mass ratio of 2-4:0.4-0.6:0.2-0.3:30-40, and the pH is adjusted to 12.3-12.8 with sodium hydroxide. The resulting mixture is subjected to hydrothermal reaction at 160-180℃ for 5-8 hours and then cooled to room temperature. The reaction product is then filtered, washed with water and ethanol 3-4 times each, dried and calcined at high temperature to obtain the final product.

2. The anti-aging polyetheretherketone composite material according to claim 1, characterized in that, The high-temperature calcination temperature is set to 450-550℃, and the high-temperature calcination time is 2-3 hours.

3. The anti-aging polyetheretherketone composite material according to claim 1, characterized in that: The silane coupling agent is any one of γ-glycidyl etheroxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-mercaptopropyltriethoxysilane.

4. The anti-aging polyetheretherketone composite material according to claim 1, characterized in that: The carbon fiber has a length of 6-8 mm and a diameter of 10-12 μm; the talc powder has a particle size of 30-35 μm; and the titanium nitride has a particle size of 5-15 μm.

5. The anti-aging polyetheretherketone composite material according to claim 1, characterized in that: The antioxidant is any one of antioxidant 1010, antioxidant 1098, and antioxidant 168.

6. The anti-aging polyetheretherketone composite material according to claim 1, characterized in that: The compatibilizer is selected from any one of POE-g-GMA, SEBS-g-GMA, and n-butyl acrylate-glycidyl acrylate.

7. A method for producing an anti-aging polyetheretherketone composite material according to any one of claims 1-6, characterized in that, Includes the following steps: Step 1: Accurately weigh each raw material, and dry polyether ether ketone and polyphenylene sulfide at 110-130℃ for 4-5 hours. Then, mix the dried polyether ether ketone and polyphenylene sulfide with the remaining raw materials except carbon fiber to obtain a mixture. The second step is to add carbon fiber to the mixture, mix it evenly, and then melt extrude and granulate it at 280-360℃ to obtain the anti-aging polyether ether ketone composite material.

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