Uvioresistant reinforced toughened pps material and process for its preparation

Abstract

This invention relates to the field of polymer materials technology, specifically to a UV-resistant reinforced and toughened PPS material and its preparation method. The invention involves mixing PPS, a toughening agent, a reinforcing agent, a silane coupling agent, an anti-aging composite material, an anti-aging material, and additives to obtain a mixture. This mixture is then melt-extruded, water-cooled, air-cooled, and pelletized to obtain a finished PPS material. The finished product prepared by this invention possesses excellent anti-aging properties and mechanical properties, thus having broad application prospects in the field of polymer materials technology.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a UV-resistant and toughened PPS material and its preparation method. Background Technology

[0002] Polyphenylene sulfide (PPS) is a high-performance thermoplastic with significant value in multiple dimensions. In strategic industries such as aerospace, new energy vehicles, and high-end electronics, PPS maintains excellent mechanical strength, dimensional stability, and chemical corrosion resistance at high temperatures. Its outstanding resistance to fuels, various solvents, and acids and alkalis makes it a preferred material for manufacturing engine peripheral components, fuel systems, precision electronic connectors, and packaging materials. Furthermore, PPS possesses excellent molding and processing properties, enabling the efficient manufacture of complex and precision parts through injection molding, extrusion, and other processes. This helps promote the replacement of steel with plastics in traditional metal components, achieving product lightweighting and integration, thereby reducing system energy consumption.

[0003] However, PPS materials themselves have relatively limited resistance to ultraviolet radiation. Under outdoor sunlight, high-energy ultraviolet rays can trigger photochemical reactions in the polymer molecular chains on the material's surface, primarily attacking the relatively weak CS bonds and benzene ring structures. This leads to surface chalking, discoloration, and decreased gloss, accompanied by increased brittleness and a significant decrease in mechanical properties such as tensile strength and impact strength. Furthermore, thermo-oxidative aging is also a major failure mechanism under long-term high-temperature and oxygen-rich environments. With increasingly stringent temperature resistance requirements in applications (such as the higher temperatures of automotive engine compartments) and the high-temperature molten state of PPS during processing, the material faces increasing oxidative pressure. Changes in molecular structure caused by thermo-oxidative aging affect the material's crystal morphology and dimensional stability, leading to deformation or failure of precision components.

[0004] To overcome the shortcomings of the prior art, the present invention provides a UV-resistant enhanced toughened PPS material and its preparation method. Summary of the Invention

[0005] The purpose of this invention is to provide a UV-resistant and toughened PPS material and its preparation method, so as to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A UV-resistant and toughened PPS material, by mass fraction, comprises 45-55% PPS, 3-5% toughening agent, 20-40% reinforcing agent, 0.1-0.3% silane coupling agent, 1.0-1.5% anti-aging composite material, 0.5-1.0% anti-aging material, with the balance being additives; The anti-aging composite material is obtained by uniformly mixing and dispersing modified anti-aging material and modified zinc oxide material; wherein the modified anti-aging material is obtained by grafting anti-ultraviolet material and antioxidant material after modification with coupling agent with nano zinc oxide as the core. The anti-aging material is based on nano-titanium dioxide, which is coated with silicon and modified with a coupling agent to obtain an aminated anti-UV material, and then grafted with an antioxidant material.

[0007] In a more optimized manner, PPS, model A610MG1, was provided by Dongguan Zhangmutou Yutao Plastics Co., Ltd.; the toughening agent was SEBS-g-MAH, provided by Ningbo Nengzhiguang New Material Technology Co., Ltd.; the reinforcing agent was glass fiber, 10μm in diameter, provided by Shandong Futai Fiber Co., Ltd.; and the silane coupling agent was KH560.

[0008] In a more optimized manner, the additives include a flame retardant and a lubricant in a mass ratio of 1:(0.5-0.7); the flame retardant is sodium hexametaphosphate; and the lubricant is PETS-AHS, provided by Shanghai Kaiyin Chemical Co., Ltd.

[0009] In a more optimized manner, the preparation process of the anti-aging composite material is as follows: Step S1: Add chloroacetic acid to an aqueous sodium hydroxide solution and stir at 25-30℃ for 0.5-1.0 h. After the reaction is complete, add benzotriazole and reflux at 110-120℃ for 3-5 h. After the reaction is complete, cool to 25-30℃, adjust pH to 3.0-3.5, cool to 0-2℃, and filter to obtain the UV-resistant material. Step S2: Add the UV-resistant material to the ethanol solution and stir until homogeneous to obtain the UV-resistant solution; add 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid to the ethanol solution and stir until homogeneous to obtain the antioxidant solution; add nano-zinc oxide to the ethanol aqueous solution and stir until homogeneous, then slowly add γ-aminopropyltriethoxysilane, adjust the pH of the solution to 3.0-3.5, and then add the UV-resistant solution and antioxidant solution dropwise in sequence. Reflux the reaction at 60-65℃ for 9-11 hours. After the reaction is complete, centrifuge, wash until pH is neutral, and dry to obtain the modified anti-aging material. Step S3: Mix nano zinc oxide, anhydrous ethanol, and ammonia, stir evenly, add phenyltriethoxysilane, ultrasonically disperse for 25-35 min, and then stir and react at 50-55℃ for 25-30 h. After the reaction is completed, wash with alcohol, dry, and grind to obtain modified zinc oxide material. Mix the modified anti-aging material and modified zinc oxide material, first mix at 10-15 rpm for 15 min, then mix at 20-25 rpm for 10 min to obtain anti-aging composite material.

[0010] In a more optimized manner, in step S1, the reaction mass ratio of sodium hydroxide, chloroacetic acid, and benzotriazole is (40-45):24:66.

[0011] In a more optimized manner, in step S2, the volume ratio of ethanol to deionized water in the ethanol aqueous solution is (3-4):1; the reaction mass ratio of nano zinc oxide, γ-aminopropyltriethoxysilane, anti-UV material, and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid is 2:(0.4-0.5):(0.8-1.0):(1.5-1.8).

[0012] In a more optimized manner, in step S3, the reaction mass ratio of nano zinc oxide and phenyltriethoxysilane is 1:(0.7-0.8); the mixing ratio of modified anti-aging material and modified zinc oxide material is (1.5-1.7):1.

[0013] In a more optimized manner, the preparation process of the anti-aging material is as follows: Step S1: Add tetraethyl orthosilicate to anhydrous ethanol and stir until homogeneous to obtain a tetraethyl orthosilicate solution; add γ-aminopropyltriethoxysilane to anhydrous ethanol and stir until homogeneous to obtain a modified solution; mix ethanol and deionized water, stir until homogeneous, add ammonia to adjust the pH of the solution to 9.5-10.0, then add nano-titanium dioxide, ultrasonically disperse for 15-25 min, then slowly add the tetraethyl orthosilicate solution dropwise, and after the dropwise addition is complete, slowly add the modified solution dropwise, and continue stirring the reaction for 7-9 h after the dropwise addition is complete. After the reaction is complete, wash, dry, and grind to obtain an aminated UV-resistant material. Step S2: Under nitrogen atmosphere, add the aminated UV-resistant material to deionized water, stir evenly, and then cool to 0-2℃. Then slowly add 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride solution and potassium carbonate aqueous solution, adjust the pH of the solution to 9-10, and after the addition is completed, raise the temperature to 25-30℃ and continue the reaction for 24-28 hours. After the reaction is completed, filter under negative pressure, wash and dry to obtain the anti-aging material.

[0014] In a more optimized manner, in step S1, the reaction mass ratio of nano-titanium dioxide, tetraethyl orthosilicate, and γ-aminopropyltriethoxysilane is 1:(0.23-0.25):(0.6-0.8).

[0015] In a more optimized manner, in step S2, the reaction mass ratio of the aminated UV-resistant material to 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride is 1:(0.80-0.95).

[0016] A method for preparing a UV-resistant reinforced and toughened PPS material includes the following steps: mixing PPS, toughening agent, reinforcing agent, silane coupling agent, anti-aging composite material, anti-aging material, and additives to obtain a mixture; subjecting the mixture to melt extrusion, water cooling, air cooling, and pelletizing to obtain the finished product; the melt extrusion temperature is 280-300℃.

[0017] The beneficial effects of this invention are as follows: This invention is characterized by obtaining an anti-UV material through a substitution reaction by adding chloroacetic acid, sodium hydroxide, and benzotriazole. The benzotriazole structure can efficiently absorb ultraviolet light, and the introduction of carboxyl groups provides active sites for subsequent covalent bonding with aminated zinc oxide. Then, γ-aminopropyltriethoxysilane is used to modify nano-zinc oxide, resulting in a zinc oxide structure with active amino groups. Further, an anti-UV material with carboxyl groups and an antioxidant material, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, are added, and an amidation reaction occurs to obtain a modified anti-aging material. Nano-zinc oxide itself is a wide-bandgap semiconductor with strong absorption and reflection capabilities for ultraviolet light. Furthermore, this reaction firmly grafts two functional molecules onto the surface of ZnO nanoparticles via covalent bonds, fundamentally solving the problem of protective function failure caused by the easy migration and volatilization of small molecule additives, effectively improving the material's resistance to ultraviolet aging and antioxidant aging.

[0018] Furthermore, by modifying nano-zinc oxide with phenyltriethoxysilane, an anti-aging composite material with phenyl grafted onto its surface is obtained. The modified anti-aging material and the modified zinc oxide material are mixed and stirred in multiple stages to obtain the anti-aging composite material. The PPS matrix resin of this invention is a semi-crystalline aromatic polymer containing a large number of benzene ring structures in its molecular chain. Therefore, by grafting phenyl onto the surface of nano-zinc oxide, good compatibility between the anti-aging composite material and the PPS matrix can be ensured, achieving a uniform dispersion effect.

[0019] The key feature of this invention lies in the addition of nano-titanium dioxide, tetraethyl orthosilicate, and γ-aminopropyltriethoxysilane. Using nano-titanium dioxide as the core, it is coated with silicon and then modified with an amino coupling agent to obtain an aminated UV-resistant material. The phenolic antioxidant 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride is then mixed with the aminated UV-resistant material, undergoing a substitution reaction to obtain an anti-aging material. Titanium dioxide is a wide-bandgap semiconductor with extremely strong absorption and scattering capabilities for ultraviolet light. Furthermore, the SiO2 shell effectively blocks direct contact between TiO2 and the external environment, significantly inhibiting its photocatalytic activity and preventing the generation of reactive oxygen species under ultraviolet light, which would accelerate the oxidation of the polymer matrix. The introduction of amino groups as reaction sites for subsequent bonding of antioxidant functional molecules, and the covalent fixation of the phenolic antioxidant on the material surface, effectively enhances both the antioxidant performance and its stability within the material.

[0020] The present invention is characterized by mixing PPS, toughening agent, reinforcing agent, silane coupling agent, anti-aging composite material, anti-aging material, and additives, followed by melt extrusion, water cooling, air cooling, and pelletizing to obtain a finished PPS material. This finished product possesses excellent resistance to ultraviolet aging and oxidative aging, thus having broad application prospects in the field of polymer materials technology. Detailed Implementation

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] Raw material source: Nano zinc oxide, provided by Jinda Nanotechnology (Xiamen) Co., Ltd., model number JDGQP-004; nano titanium dioxide, provided by Dongguan Meidelong Plastics & Chemical Co., Ltd., grade number CR-828-170.

[0023] Example 1: Step S1: Chloroacetic acid was added to an aqueous sodium hydroxide solution and stirred at 30°C for 1.0 h. After the reaction was completed, benzotriazole was added, and the mixture was heated to 120°C and refluxed for 4 h. After the reaction was completed, the mixture was successively cooled to 30°C, the pH was adjusted to 3.5, the temperature was lowered to 2°C, and the mixture was filtered to obtain the UV-resistant material. The mass ratio of sodium hydroxide, chloroacetic acid, and benzotriazole was 43:24:66. Step S2: Add the UV-resistant material to the ethanol solution and stir until homogeneous to obtain the UV-resistant solution; add 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid to the ethanol solution and stir until homogeneous to obtain the antioxidant solution; add nano-zinc oxide to the ethanol aqueous solution and stir until homogeneous, then slowly add γ-aminopropyltriethoxysilane, adjust the pH of the solution to 3.5, and then add the UV-resistant solution and antioxidant solution dropwise in sequence. Reflux at 65℃ for 11 hours. After the reaction is complete, centrifuge, wash until pH is neutral, and dry to obtain the modified anti-aging material; the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 3.5:1; the reaction mass ratio of nano-zinc oxide, γ-aminopropyltriethoxysilane, UV-resistant material, and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid is 2:0.45:0.9:1.7; Step S3: Mix nano-zinc oxide, anhydrous ethanol, and ammonia, stir until homogeneous, add phenyltriethoxysilane, ultrasonically disperse for 35 min, then stir and react at 55℃ for 30 h. After the reaction, wash with alcohol, dry, and grind to obtain modified zinc oxide material. Mix modified anti-aging material and modified zinc oxide material, first at 15 rpm for 15 min, then at 25 rpm for 10 min to obtain anti-aging composite material. The mass ratio of nano-zinc oxide to phenyltriethoxysilane is 1:0.75; the mixing ratio of modified anti-aging material to modified zinc oxide material is 1.6:1. Step S4: Add tetraethyl orthosilicate to anhydrous ethanol and stir until homogeneous to obtain a tetraethyl orthosilicate solution; add γ-aminopropyltriethoxysilane to anhydrous ethanol and stir until homogeneous to obtain a modified solution; mix ethanol and deionized water, stir until homogeneous, add ammonia to adjust the pH of the solution to 10.0, then add nano-titanium dioxide, ultrasonically disperse for 25 min, then slowly add the tetraethyl orthosilicate solution dropwise. After the addition is complete, slowly add the modified solution dropwise. Continue stirring and reacting for 9 h after the addition is complete. After the reaction is complete, wash, dry, and grind to obtain an aminated UV-resistant material; the mass ratio of nano-titanium dioxide, tetraethyl orthosilicate, and γ-aminopropyltriethoxysilane is 1:0.24:0.7. Step S5: Under nitrogen atmosphere, the aminated UV-resistant material was added to deionized water, stirred evenly, and then cooled to 2°C. 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride solution and potassium carbonate aqueous solution were then slowly added dropwise to adjust the pH of the solution to 10. After the addition was complete, the temperature was raised to 30°C, and the reaction was continued for 28 hours. After the reaction was completed, the mixture was filtered under negative pressure, washed, and dried to obtain the anti-aging material. The mass ratio of the aminated UV-resistant material to 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride was 1:0.87. Step S6: Mix 50% PPS, 4% SEBS-g-MAH, 35% glass fiber, 0.2% KH560, 1.3% anti-aging composite material, 0.7% anti-aging material, and 8.8% additives by mass fraction to obtain a mixture; melt extrusion, water cooling, air cooling, and pelletizing to obtain the finished product; the melt extrusion temperature is 300℃; the additives include sodium hexametaphosphate and PETS-AHS in a mass ratio of 1:0.6.

[0024] Example 2: Step S1: Chloroacetic acid was added to an aqueous sodium hydroxide solution and stirred at 27°C for 0.7 h. After the reaction was completed, benzotriazole was added, and the mixture was heated to 115°C and refluxed for 4 h. After the reaction was completed, the mixture was cooled to 27°C, the pH was adjusted to 3.2, the temperature was lowered to 1°C, and the mixture was filtered to obtain the UV-resistant material. The mass ratio of sodium hydroxide, chloroacetic acid, and benzotriazole was 43:24:66. Step S2: Add the UV-resistant material to the ethanol solution and stir until homogeneous to obtain the UV-resistant solution; add 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid to the ethanol solution and stir until homogeneous to obtain the antioxidant solution; add nano-zinc oxide to the ethanol aqueous solution and stir until homogeneous, then slowly add γ-aminopropyltriethoxysilane, adjust the pH of the solution to 3.2, and then add the UV-resistant solution and antioxidant solution dropwise in sequence. Reflux at 63℃ for 10 hours. After the reaction is complete, centrifuge, wash until pH is neutral, and dry to obtain the modified anti-aging material; the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 3.5:1; the mass ratio of nano-zinc oxide, γ-aminopropyltriethoxysilane, UV-resistant material, and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid is 2:0.45:0.9:1.7. Step S3: Mix nano-zinc oxide, anhydrous ethanol, and ammonia water, stir evenly, add phenyltriethoxysilane, ultrasonically disperse for 30 min, and then stir and react at 53℃ for 27 h. After the reaction, wash with alcohol, dry, and grind to obtain modified zinc oxide material. Mix modified anti-aging material and modified zinc oxide material, first mix at 13 rpm for 15 min, then mix at 23 rpm for 10 min to obtain anti-aging composite material. The reaction mass ratio of nano-zinc oxide to phenyltriethoxysilane is 1:0.75; the mixing ratio of modified anti-aging material to modified zinc oxide material is 1.6:1. Step S4: Add tetraethyl orthosilicate to anhydrous ethanol and stir until homogeneous to obtain a tetraethyl orthosilicate solution; add γ-aminopropyltriethoxysilane to anhydrous ethanol and stir until homogeneous to obtain a modified solution; mix ethanol and deionized water, stir until homogeneous, add ammonia to adjust the pH of the solution to 9.7, then add nano-titanium dioxide, ultrasonically disperse for 20 min, then slowly add the tetraethyl orthosilicate solution dropwise. After the addition is complete, slowly add the modified solution dropwise. Continue stirring and reacting for 8 h after the addition is complete. After the reaction is complete, wash, dry, and grind to obtain an aminated UV-resistant material; the mass ratio of nano-titanium dioxide, tetraethyl orthosilicate, and γ-aminopropyltriethoxysilane is 1:0.24:0.7. Step S5: Under nitrogen atmosphere, the aminated UV-resistant material was added to deionized water, stirred evenly, and then cooled to 1°C. 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride solution and potassium carbonate aqueous solution were then slowly added dropwise to adjust the pH of the solution to 9.5. After the addition was complete, the temperature was raised to 27°C, and the reaction was continued for 26 hours. After the reaction was completed, the mixture was filtered under negative pressure, washed, and dried to obtain the anti-aging material. The mass ratio of the aminated UV-resistant material to 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride was 1:0.87. Step S6: Mix 50% PPS, 4% SEBS-g-MAH, 35% glass fiber, 0.2% KH560, 1.3% anti-aging composite material, 0.7% anti-aging material, and 8.8% additives by mass fraction to obtain a mixture; melt extrusion, water cooling, air cooling, and pelletizing to obtain the finished product; the melt extrusion temperature is 290℃; the additives include sodium hexametaphosphate and PETS-AHS in a mass ratio of 1:0.6.

[0025] Example 3: Step S1: Chloroacetic acid was added to an aqueous sodium hydroxide solution and stirred at 25°C for 0.5 h. After the reaction was completed, benzotriazole was added, and the mixture was heated to 110°C and refluxed for 4 h. After the reaction was completed, the mixture was successively cooled to 25°C, the pH was adjusted to 3.0, the temperature was lowered to 0°C, and the mixture was filtered to obtain the UV-resistant material. The mass ratio of sodium hydroxide, chloroacetic acid, and benzotriazole was 43:24:66. Step S2: Add the UV-resistant material to the ethanol solution and stir until homogeneous to obtain the UV-resistant solution; add 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid to the ethanol solution and stir until homogeneous to obtain the antioxidant solution; add nano-zinc oxide to the ethanol aqueous solution and stir until homogeneous, then slowly add γ-aminopropyltriethoxysilane, adjust the pH of the solution to 3.0, and then add the UV-resistant solution and antioxidant solution dropwise in sequence. Reflux at 60℃ for 9 hours. After the reaction is complete, centrifuge, wash until pH is neutral, and dry to obtain the modified anti-aging material; the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 3.5:1; the mass ratio of nano-zinc oxide, γ-aminopropyltriethoxysilane, UV-resistant material, and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid is 2:0.45:0.9:1.7. Step S3: Mix nano-zinc oxide, anhydrous ethanol, and ammonia, stir until homogeneous, add phenyltriethoxysilane, ultrasonically disperse for 25 min, then stir and react at 50℃ for 25 h. After the reaction, wash with alcohol, dry, and grind to obtain modified zinc oxide material. Mix modified anti-aging material and modified zinc oxide material, first at 10 rpm for 15 min, then at 20 rpm for 10 min to obtain anti-aging composite material. The mass ratio of nano-zinc oxide to phenyltriethoxysilane is 1:0.75; the mixing ratio of modified anti-aging material to modified zinc oxide material is 1.6:1. Step S4: Add tetraethyl orthosilicate to anhydrous ethanol and stir until homogeneous to obtain a tetraethyl orthosilicate solution; add γ-aminopropyltriethoxysilane to anhydrous ethanol and stir until homogeneous to obtain a modified solution; mix ethanol and deionized water, stir until homogeneous, add ammonia to adjust the pH of the solution to 9.5, then add nano-titanium dioxide, ultrasonically disperse for 15 min, then slowly add the tetraethyl orthosilicate solution dropwise. After the addition is complete, slowly add the modified solution dropwise. Continue stirring and reacting for 7 h after the addition is complete. After the reaction is complete, wash, dry, and grind to obtain an aminated UV-resistant material; the mass ratio of nano-titanium dioxide, tetraethyl orthosilicate, and γ-aminopropyltriethoxysilane is 1:0.24:0.7. Step S5: Under nitrogen atmosphere, the aminated UV-resistant material was added to deionized water, stirred evenly, and then cooled to 0°C. 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride solution and potassium carbonate aqueous solution were then slowly added dropwise to adjust the pH of the solution to 9. After the addition was complete, the temperature was raised to 25°C, and the reaction was continued for 24 hours. After the reaction was completed, the mixture was filtered under negative pressure, washed, and dried to obtain the anti-aging material. The mass ratio of the aminated UV-resistant material to 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride was 1:0.87. Step S6: Mix 50% PPS, 4% SEBS-g-MAH, 35% glass fiber, 0.2% KH560, 1.3% anti-aging composite material, 0.7% anti-aging material, and 8.8% additives by mass fraction to obtain a mixture; melt extrusion, water cooling, air cooling, and pelletizing to obtain the finished product; the melt extrusion temperature is 280℃; the additives include sodium hexametaphosphate and PETS-AHS in a mass ratio of 1:0.6.

[0026] Comparative Example 1: The anti-aging composite material was removed, and the rest was the same as in Example 1. The specific steps are as follows: Step S1: Tetraethyl orthosilicate was added to anhydrous ethanol and stirred evenly to obtain a tetraethyl orthosilicate solution; γ-aminopropyltriethoxysilane was added to anhydrous ethanol and stirred evenly to obtain a modified solution; ethanol and deionized water were mixed and stirred evenly, and ammonia was added to adjust the pH of the solution to 10.0. Then nano-titanium dioxide was added, and ultrasonic dispersion was carried out for 25 min. Then tetraethyl orthosilicate solution was slowly added dropwise. After the addition was completed, the modified solution was slowly added dropwise. After the addition was completed, the reaction was stirred for 9 h. After the reaction was completed, the mixture was washed, dried, and ground to obtain an aminated anti-UV material; the reaction mass ratio of nano-titanium dioxide, tetraethyl orthosilicate, and γ-aminopropyltriethoxysilane was 1:0.24:0.7. Step S2: Under nitrogen atmosphere, the aminated UV-resistant material was added to deionized water, stirred evenly, and then cooled to 2°C. 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride solution and potassium carbonate aqueous solution were then slowly added dropwise to adjust the pH of the solution to 10. After the addition was complete, the temperature was raised to 30°C, and the reaction was continued for 28 hours. After the reaction was completed, the mixture was filtered under negative pressure, washed, and dried to obtain the anti-aging material. The mass ratio of the aminated UV-resistant material to 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride was 1:0.87. Step S3: Mix 51.3% PPS, 4% SEBS-g-MAH, 35% glass fiber, 0.2% KH560, 0.7% anti-aging material, and 8.8% additives by mass fraction to obtain a mixture; melt extrusion, water cooling, air cooling, and pelletizing to obtain the finished product; the melt extrusion temperature is 300℃; the additives include sodium hexametaphosphate and PETS-AHS in a mass ratio of 1:0.6.

[0027] Comparative Example 2: The anti-aging composite material and anti-aging material were removed, and the rest was the same as in Example 1. The specific steps are as follows: 52% PPS, 4% SEBS-g-MAH, 35% glass fiber, 0.2% KH560 and 8.8% additives were mixed by mass fraction to obtain a mixture; the mixture was melt extruded, water-cooled, air-cooled and pelletized to obtain the finished product; the melt extrusion temperature was 300℃; the additives included sodium hexametaphosphate and PETS-AHS in a mass ratio of 1:0.6.

[0028] Testing and experimentation:

[0029] Damp heat aging test: Referring to GB / T 1040.2-2022 standard, the PPS product prepared by this invention was injection molded to obtain type 1A dumbbell-shaped specimens. The specimens were immersed in deionized water and subjected to a damp heat aging test at 80℃ for 1000 hours. Then, the tensile properties of the specimens were tested using a universal testing machine at a tensile speed of 10 mm / min.

[0030] UV Aging Test: Referring to GB / T 1040.2-2022 standard, the PPS product prepared according to this invention was injection molded to obtain type 1A dumbbell-shaped samples. The samples were placed in an accelerated aging test chamber and irradiated with UV lamps for 1000 hours. Tensile properties were then tested using a universal testing machine at a tensile speed of 10 mm / min. The results are shown in the table below:

[0031] Conclusion: In Examples 1-3, the dosage remained unchanged, with only some reaction parameters modified. Experimental data showed no significant fluctuations in the performance of the samples.

[0032] Comparative Example 1: The anti-aging composite material was removed, and the rest was the same as in Example 1. The experimental data showed that, compared with Example 1, the tensile strength decreased to 129.1 MPa after the damp heat aging test and to 148.9 MPa after the ultraviolet aging test. The reason for this is that the zinc oxide contained in the anti-aging composite material has strong absorption and reflection capabilities for ultraviolet light. At the same time, the material also contains a variety of antioxidant materials and ultraviolet absorbing materials, so it has excellent anti-aging properties. Therefore, after removing it, both the antioxidant aging resistance and the ultraviolet aging resistance are reduced.

[0033] Comparative Example 2: The anti-aging composite material and the anti-aging material were removed, and the rest was the same as in Example 1. The experimental data showed that, compared with Example 1, the tensile strength decreased to 120.4 MPa after the damp heat aging test and decreased to 137.7 MPa after the ultraviolet aging test. The reason for this is that, based on Comparative Example 1, Comparative Example 2 further removed the anti-aging material. The titanium dioxide material contained in the anti-aging material has good ultraviolet absorption capacity, and the antioxidant groups on the surface of the material also have good antioxidant properties. Therefore, after removing the anti-aging material, the antioxidant aging resistance and the ultraviolet aging resistance were further reduced.

[0034] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process method article or apparatus.

[0035] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A UV-resistant, reinforced, and toughened PPS material, characterized in that: By mass fraction, it contains 45-55% PPS, 3-5% toughening agent, 20-40% reinforcing agent, 0.1-0.3% silane coupling agent, 1.0-1.5% anti-aging composite material, 0.5-1.0% anti-aging material, and the balance is additives; The anti-aging composite material is obtained by uniformly mixing and dispersing modified anti-aging material and modified zinc oxide material; The modified anti-aging material is based on nano zinc oxide, which is modified with a coupling agent and then grafted with UV-resistant and antioxidant materials. The anti-aging material is obtained by using nano-titanium dioxide as the core, which is coated with silicon and modified with a coupling agent to obtain an aminated anti-UV material, and then grafted with an antioxidant material.

2. The UV-resistant and toughened PPS material according to claim 1, characterized in that: The preparation process of the anti-aging composite material is as follows: Step S1: Mix chloroacetic acid and sodium hydroxide aqueous solution, stir and react at 25-30℃ for 0.5-1.0h, then add benzotriazole, heat to 110-120℃ and reflux for 3-5h. After the reaction is completed, cool, adjust pH, cool down and filter to obtain UV-resistant material. Step S2: Add the UV-resistant material to the ethanol solution to obtain the UV-resistant solution; 3,5-Di-tert-butyl-4-hydroxyphenylpropionic acid was added to an ethanol solution to obtain an antioxidant solution; nano zinc oxide was added to an ethanol aqueous solution, followed by the addition of γ-aminopropyltriethoxysilane, and the pH of the solution was adjusted to 3.0-3.

5. Then, an anti-UV solution and an antioxidant solution were added dropwise, and the mixture was refluxed at 60-65℃ for 9-11 hours. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the modified anti-aging material. Step S3: Mix nano zinc oxide, anhydrous ethanol, and ammonia, then add phenyltriethoxysilane. After ultrasonic dispersion, stir and react at 50-55℃ for 25-30 hours. After the reaction, wash with alcohol, dry, and grind to obtain modified zinc oxide material. Mix the modified anti-aging material and modified zinc oxide material. First, mix at 10-15 rpm for 15 minutes, then mix at 20-25 rpm for 10 minutes to obtain anti-aging composite material.

3. The UV-resistant and toughened PPS material according to claim 2, characterized in that: In step S1, the mass ratio of sodium hydroxide, chloroacetic acid, and benzotriazole is (40-45):24:

66.

4. The UV-resistant and toughened PPS material according to claim 2, characterized in that: In step S2, the volume ratio of ethanol to deionized water in the ethanol-water solution is (3-4):1; the reaction mass ratio of nano zinc oxide, γ-aminopropyltriethoxysilane, anti-UV material, and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid is 2:(0.4-0.5):(0.8-1.0):(1.5-1.8).

5. The UV-resistant and toughened PPS material according to claim 2, characterized in that: In step S3, the reaction mass ratio of nano zinc oxide and phenyltriethoxysilane is 1:(0.7-0.8); the mixing ratio of modified anti-aging material and modified zinc oxide material is (1.5-1.7):

1.

6. The UV-resistant and toughened PPS material according to claim 1, characterized in that: The preparation process of the anti-aging material is as follows: Step S1: Tetraethyl orthosilicate is added to anhydrous ethanol to obtain a tetraethyl orthosilicate solution; γ-aminopropyltriethoxysilane is added to anhydrous ethanol to obtain a modified solution; ethanol and deionized water are mixed, and ammonia is added to adjust the pH of the solution to 9.5-10.0, then nano-titanium dioxide is added, ultrasonically dispersed, and then the tetraethyl orthosilicate solution is added dropwise. After the addition is complete, the modified solution is added dropwise. After the addition is complete, the reaction is stirred for 7-9 hours. After the reaction is complete, the material is washed, dried, and ground to obtain an aminated UV-resistant material. Step S2: Under nitrogen atmosphere, add the aminated UV-resistant material to deionized water, stir evenly, and then cool to 0-2℃. Then add 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride solution and potassium carbonate aqueous solution dropwise to adjust the pH of the solution to 9-10. After the addition is completed, raise the temperature to 25-30℃ and continue the reaction for 24-28 hours. After the reaction is completed, filter under negative pressure, wash and dry to obtain the anti-aging material.

7. The UV-resistant reinforced and toughened PPS material according to claim 6, characterized in that: In step S1, the reaction mass ratio of nano-titanium dioxide, tetraethyl orthosilicate, and γ-aminopropyltriethoxysilane is 1:(0.23-0.25):(0.6-0.8).

8. The UV-resistant reinforced and toughened PPS material according to claim 6, characterized in that: In step S2, the reaction mass ratio of the aminated UV-resistant material to 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride is 1:(0.80-0.95).

9. A method for preparing a UV-resistant and toughened PPS material according to any one of claims 1-8, characterized in that: Includes the following steps: PPS, toughening agent, reinforcing agent, silane coupling agent, anti-aging composite material, anti-aging material, and additives are mixed to obtain a mixture; the mixture is then melt-extruded, water-cooled, air-cooled, and pelletized to obtain the finished product; the melt extrusion temperature is 280-300℃.

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