A polyphenylene sulfide composite material and a method for producing the same

Abstract

The application provides a kind of polyphenyl sulfide composite material and its preparation method, belong to high polymer material technical field, the polyphenyl sulfide composite material includes the following weight parts raw materials:130-150 parts polyphenyl sulfide, 40-50 parts functionalized glass fiber, 10-20 parts reinforcing auxiliary agent, 3-6 parts compatilizer, 1-3 parts nucleating agent, 1-2 parts lubricant, 1-2 parts antioxidant. Among them, the reinforcing auxiliary agent is vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and / or methyl methacrylate-butadiene-styrene terpolymer;The functionalized glass fiber is obtained by reaction of amino grafted polyphenyl sulfide and silane modified glass fiber.The polyphenyl sulfide composite material prepared by the application not only has good mechanical properties and high temperature resistance, but also has excellent toughness and wear resistance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to a kind of polyphenylene sulfide composite material and its preparation method. BACKGROUND

[0002] Polyphenylene sulfide (PPS for short) is a semi-crystalline thermoplastic special engineering plastic. With its unique molecular structure and performance advantages, it has become an important raw material in the field of high-performance materials. The main chain of polyphenylene sulfide is composed of benzene rings and sulfur atoms connected alternately, which endows the material with excellent high-temperature resistance, chemical stability and flame retardance, and the long-term use temperature can reach more than 200℃. In addition, polyphenylene sulfide has high mechanical strength and good dimensional stability, and shows strong chemical corrosion resistance in acids, bases and organic solvents, making it widely used in high-end fields such as electronics, automobile manufacturing, aerospace, etc. For example, in the automotive field, polyphenylene sulfide is used to manufacture high-temperature resistant sensor housings; in the electronics field, its flame retardant properties are suitable for precision connectors; and in the environmental protection field, its corrosion resistance supports the long-term operation of chemical filtration equipment. With the growing global demand for lightweight and extreme environment-resistant materials, the market size of polyphenylene sulfide continues to expand.

[0003] Currently, the methods for industrial production of polyphenylene sulfide include melt polycondensation and solution polycondensation. Melt polycondensation directly reacts monomers to form polymers at high temperature, although the process is simple, but the reaction conditions are harsh and the by-products are difficult to remove, resulting in wide molecular weight distribution and uneven mechanical properties. Solution polycondensation uses polar solvents as medium, although it can improve molecular weight control, but the solvent recovery cost is high and the residual solvent can contaminate the product, limiting the economic efficiency of large-scale production. In the modification of composite materials, traditional methods often use glass fiber or carbon fiber reinforcement, which can improve mechanical properties, but the interface bonding force between fiber and matrix is insufficient, and delamination may occur during long-term use; while adding inorganic fillers can reduce cost, but it significantly damages the toughness of the material. In addition, the existing process has limited ability to control the crystallinity of polyphenylene sulfide, which makes the product prone to size shrinkage or warping at high temperatures, and it is difficult to meet the tolerance requirements of precision parts. These problems seriously restrict the further application of polyphenylene sulfide materials in high-end equipment manufacturing.

[0004] In recent years, many studies have reported attempts to optimize the performance of polyphenylene sulfide materials through various approaches: for example, introducing nanofillers such as carbon nanotubes, graphene, etc. to improve the thermal conductivity and strength of the composite material, but the agglomeration of nanoparticles leads to uneven performance improvement; using plasma treatment or silane coupling agent to improve the interface bonding between the fiber and the matrix, but the process is complex and increases the production cost; developing new catalyst systems such as ionic liquids to reduce the polycondensation temperature, but such catalysts have the problems of difficult recovery and possible environmental risks. Therefore, it is urgent to develop a new kind of high-performance polyphenylene sulfide composite material and its preparation method, which not only has good high-temperature resistance and mechanical properties, but also significantly improves the toughness and impact strength, thereby expanding the application range of polyphenylene sulfide composite materials. SUMMARY

[0005] The purpose of the present application is to provide a preparation method of a polyphenylene sulfide composite material, which further improves the toughness and wear resistance of the material while maintaining good mechanical properties and high-temperature resistance of the material by adding specific functionalized glass fibers and reinforcing aids to the polyphenylene sulfide resin.

[0006] In order to achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0007] The present application provides a polyphenylene sulfide composite material, which comprises the following raw material components by weight:

[0008] 130-150 parts of polyphenylene sulfide, 40-50 parts of functionalized glass fiber, 10-20 parts of reinforcing aid, 3-6 parts of compatibilizer, 1-3 parts of nucleating agent, 1-2 parts of lubricant, and 1-2 parts of antioxidant.

[0009] Preferably, the preparation method of the functionalized glass fiber comprises the following steps:

[0010] Titanium tetraisopropylate is mixed with an ethanol aqueous solution, nitric acid is added dropwise under stirring conditions, and stirring is performed to obtain a precursor solution; glass fiber is mixed with hydrochloric acid, heated and stirred, filtered, and dried to obtain pretreated glass fiber; the pretreated glass fiber is mixed with anhydrous ethanol, then the precursor solution is added, heated and stirred, allowed to stand, filtered, washed with water, and dried to obtain nano-TiO2 modified glass fiber; the nano-TiO2 modified glass fiber and (3-glycidoxypropyl) methyl diethoxysilane are added to an ethanol aqueous solution, heated and stirred, filtered, and dried to obtain silane-modified glass fiber;

[0011] Mixing concentrated nitric acid and concentrated sulfuric acid, then adding polyphenylene sulfide, heating reaction, precipitation, filtration, drying, to obtain nitro grafted polyphenylene sulfide; mixing sodium borohydride, copper chloride and N-methyl pyrrolidone, then adding nitro grafted polyphenylene sulfide, heating reaction, precipitation, filtration, drying, to obtain amino grafted polyphenylene sulfide; mixing amino grafted polyphenylene sulfide and N-methyl pyrrolidone, then adding silane modified glass fiber, heating reaction, reduced pressure distillation, drying, to obtain functionalized glass fiber.

[0012] The present application significantly improves the toughness and wear resistance of the material by using the functionalized and modified glass fiber in the raw material formula of the polyphenylene sulfide composite material, while ensuring that the composite material has good mechanical strength and high temperature resistance.

[0013] In the preparation process, the surface of the glass fiber is first etched by hydrochloric acid to form a micro-nano scale rough structure, and then nano TiO2 particles are loaded by sol-gel method, which has high hardness and forms physical interlocking with the polyphenylene sulfide matrix, enhancing the load transfer efficiency; at the same time, the epoxy group of 3-epoxypropoxypropylmethyldiethoxysilane reacts with the amino group of the subsequent amino grafted polyphenylene sulfide to form a covalent bond bridging network between the fiber and the matrix, significantly improving the interfacial bonding force, effectively inhibiting crack propagation and promoting energy dissipation; the loaded nano TiO2 not only acts as a rigid reinforcing phase to resist the furrow effect in the wear process, but also forms a hydrogen bond with the silane structure to synergistically strengthen the interface, and the amino grafted polyphenylene sulfide molecular chain and the matrix polyphenylene sulfide form a continuous phase through chain entanglement and co-crystallization effect, further blurring the interface phase region; in the dynamic friction process, the chemically bonded interface reduces the generation of abrasive particles caused by fiber-matrix debonding, and the high thermal conductivity of nano TiO2 accelerates the diffusion of friction heat, avoiding the adhesion wear caused by local heating. In addition, the multi-scale rough structure on the surface of the functionalized glass fiber increases the real contact area, making the stress distribution more uniform and delaying the occurrence of fatigue wear. The present application synergistically acts through the above interface chemical bonding, nano reinforcing phase and topological structure, so that the composite material absorbs energy through multiple mechanisms such as fiber pull-out, crack deflection and interface plastic deformation when subjected to impact, and inhibits material loss through hard protective layer and stable interface during wear process, thereby realizing the simultaneous improvement of toughness and wear resistance.

[0014] Preferably, the weight ratio of titanium tetraisopropylate, ethanol aqueous solution and nitric acid is 7-15:40-60:5-10; the weight ratio of the pretreated glass fiber and the precursor solution is 7-15:20-40; the weight ratio of the nano TiO2 modified glass fiber and (3-epoxypropoxypropyl) methyl diethoxysilane is 10-20:0.5-1.

[0015] Preferably, the weight ratio of the concentrated nitric acid, concentrated sulfuric acid, and polyphenylene sulfide is 40-50:1-10:2-8; the weight ratio of the sodium borohydride, copper chloride, and nitro-grafted polyphenylene sulfide is 1-3:0.3-0.8:2-5; and the weight ratio of the amino-grafted polyphenylene sulfide and silane-modified glass fiber is 1-3:4-6.

[0016] Further, the method for preparing the functionalized glass fiber comprises the following steps:

[0017] 7-15 parts by weight of titanium isopropylate is mixed with 40-60 parts by weight of 80-90 wt% aqueous ethanol solution, 5-10 parts by weight of 10-15 wt% nitric acid is added dropwise under stirring at 22-27℃ and 200-400 rpm, the dropping time is 10-20 min, after the dropping is completed, the stirring is continued for 20-30 min, to obtain a precursor solution; 7-15 parts by weight of glass fiber is mixed with 40-60 parts by weight of 1-2 wt% hydrochloric acid, stirring is carried out at 60-70℃ and 200-400 rpm for 3-5 h, filtration is carried out, drying is carried out, to obtain pretreated glass fiber; 7-15 parts by weight of pretreated glass fiber is mixed with 50-70 parts by weight of anhydrous ethanol, then 20-40 parts by weight of the precursor solution is added, stirring is carried out at 50-60℃ and 200-400 rpm for 30-50 min, then standing is carried out for 3-5 h, filtration is carried out, water washing is carried out until neutral, drying is carried out, to obtain nano-TiO2 modified glass fiber; 10-20 parts by weight of nano-TiO2 modified glass fiber and 0.5-1 part by weight of (3-glycidoxypropyl) methyl diethoxysilane are added into 50-70 parts by weight of 40-50 wt% aqueous ethanol solution, stirring is carried out at 70-75℃ and 80-150 rpm for 40-60 min, filtration is carried out, drying is carried out, to obtain silane-modified glass fiber;

[0018] Mix 40-50 parts by weight of 55-65 wt% concentrated nitric acid and 1-10 parts by weight of 92-98 wt% concentrated sulfuric acid, then add 2-8 parts by weight of polyphenylene sulfide, react at 50-60℃, 50-100 rpm for 1-2 h, after the reaction is completed, add to 100-200 parts by weight of 70-85 wt% methanol aqueous solution for precipitation, filter, dry, to obtain nitro grafted polyphenylene sulfide; Mix 1-3 parts by weight of sodium borohydride, 0.3-0.8 parts by weight of copper chloride with 40-60 parts by weight of N-methyl pyrrolidone, then add 2-5 parts by weight of nitro grafted polyphenylene sulfide, react at 55-65℃, 50-100 rpm for 0.5-2 h, after the reaction is completed, add to 100-200 parts by weight of 70-85 wt% methanol aqueous solution for precipitation, filter, dry, to obtain amino grafted polyphenylene sulfide; Mix 1-3 parts by weight of amino grafted polyphenylene sulfide with 70-150 parts by weight of N-methyl pyrrolidone, then add 4-6 parts by weight of silane modified glass fiber, react at 60-70℃, 50-100 rpm for 10-15 h, after the reaction is completed, recover N-methyl pyrrolidone by distillation under reduced pressure, dry, to obtain functionalized glass fiber.

[0019] Preferably, the reinforcing aid is a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and / or a methyl methacrylate-butadiene-styrene terpolymer.

[0020] The present application also adds a specific combination of reinforcing aids in the polyphenylene sulfide composite formula, which synergistically improves the wear resistance and high temperature resistance of the material.

[0021] The fluorinated segment of the vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer forms a rigid network at high temperatures, its low surface energy reduces the friction coefficient and inhibits thermal oxidative degradation, while the core-shell structure of the methyl methacrylate-butadiene-styrene terpolymer (butadiene rubber phase dispersed in a rigid styrene-methyl methacrylate matrix) enhances toughness through a silver crack shear band energy dissipation mechanism, the polarity matching of the vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and the polyphenylene sulfide promotes uniform dispersion of the fluorocarbon segment in the matrix, forming physical crosslinking points to limit high temperature sliding of the molecular chain, improving high temperature resistance, while the benzene ring structure of the methyl methacrylate-butadiene-styrene terpolymer produces π-π stacking effect with the phenylene sulfide unit, enhancing the interfacial bonding force; during wear, the fluorinated surface of the vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer migrates preferentially to the friction interface to form a self-lubricating transfer film, while the elastic phase of the methyl methacrylate-butadiene-styrene terpolymer reduces micro-crack initiation through deformation buffering, the two synergistically reduce the wear rate, this dual-phase reinforcing system breaks through the performance bottleneck of single component in high temperature wear scenarios through rigid-flexible complementarity and interfacial chemical synergy.

[0022] Further, the reinforcing aid is a mixture of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and methyl methacrylate-butadiene-styrene terpolymer in a weight ratio of 2-4:1.

[0023] Preferably, the compatibilizer is at least one of ethylene-acrylate-maleic anhydride copolymer, maleic anhydride grafted ethylene-octene copolymer and polyolefin grafted glycidyl methacrylate.

[0024] Further, the compatibilizer is ethylene-acrylate-maleic anhydride copolymer.

[0025] Preferably, the nucleating agent is at least one of talc, calcium carbonate, magnesium carbonate, white carbon black and mica powder.

[0026] Further, the nucleating agent is talc.

[0027] Preferably, the lubricant is at least one of pentaerythritol stearate, ethylene bis-stearamide, glyceryl stearate, polyvinyl alcohol and liquid paraffin.

[0028] Further, the lubricant is a mixture of pentaerythritol stearate and ethylene bis-stearamide in a weight ratio of 1-3:3.

[0029] Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 616 and antioxidant 1076.

[0030] Further, the antioxidant is antioxidant 1010.

[0031] The application further provides a preparation method of the polyphenylene sulfide composite material.

[0032] The polyphenylene sulfide, functionalized glass fiber, reinforcing aid, compatibilizer, nucleating agent, lubricant and antioxidant are weighed according to the raw material formula, mixed in a high-speed mixer, then added into a twin-screw extruder for melt blending, extruded and granulated to obtain the polyphenylene sulfide composite material.

[0033] Preferably, the rotation speed of the high-speed mixer is 400-600 rpm and the mixing time is 7-15 min.

[0034] Preferably, the twin-screw extrusion process is as follows: the extrusion temperature is 270-340℃ and the screw rotation speed is 200-500 rpm.

[0035] Furthermore, the twin-screw extrusion process is as follows: Zone 1 temperature 275-285℃, Zone 2 temperature 285-295℃, Zone 3 temperature 285-295℃, Zone 4 temperature 325-335℃, Zone 5 temperature 325-335℃, Zone 6 temperature 295-305℃, and screw speed 300-400 rpm.

[0036] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0037] 1. This invention provides a method for preparing polyphenylene sulfide composite materials. By adding specific functionalized glass fibers and reinforcing agents to polyphenylene sulfide resin, wherein the functionalized glass fibers are obtained by reacting amino-grafted polyphenylene sulfide with silane-modified glass fibers, and the reinforcing agents are vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and / or methyl methacrylate-butadiene-styrene terpolymer, the material not only has good mechanical properties and high temperature resistance, but also further improves the toughness and wear resistance of the material, thereby expanding the application range of polyphenylene sulfide composite materials.

[0038] 2. This invention incorporates self-made functionalized glass fibers. The surface of the glass fibers is etched with hydrochloric acid to form a micro-nano-scale rough structure and loaded with nano-TiO2 particles. These high-hardness particles are physically interlocked with the matrix, enhancing load transfer efficiency. 3-Epoxypropoxypropylmethyldiethoxysilane and amino-grafted polyphenylene sulfide form a covalent bond bridging network between the fiber and the matrix, significantly improving interfacial bonding, inhibiting crack propagation, and promoting energy dissipation. The amino-grafted polyphenylene sulfide and the matrix form a continuous phase through chain entanglement and co-crystallization effects, blurring the interfacial phase region. During dynamic friction, the chemically bonded interface reduces the generation of abrasive particles caused by fiber-matrix debonding. Nano-TiO2 accelerates frictional heat diffusion, avoiding localized heating that leads to adhesive wear. This allows the composite material to absorb energy when subjected to impact, and during wear, the hard protective layer and stable interface inhibit material loss, achieving a simultaneous improvement in toughness and wear resistance.

[0039] 3、The present application uses vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and / or methyl methacrylate-butadiene-styrene terpolymer as reinforcing aids, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer has extremely high chemical stability and thermal stability due to the fluorine atoms in its molecular chain, can effectively improve the high temperature resistance of the composite material, and its surface energy is low, the friction coefficient is small, which helps to improve the wear resistance of the reinforcing material, and the methyl methacrylate-butadiene-styrene terpolymer has good elasticity, can form a micro-dispersed phase inside the material, absorb and disperse external stress, prevent crack propagation, thereby further increasing the wear resistance of the material, and the two polymers can build a more uniform and stable microstructure inside the material through synergistic effect, optimize stress distribution, improve melting temperature, so that the composite material has more excellent wear resistance and high temperature resistance while maintaining high strength. DETAILED DESCRIPTION

[0040] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0041] Polyphenylene sulfide, brand: NHU 1170C, manufacturer: Zhejiang Xinhucheng Special Material Co., Ltd.

[0042] Glass fiber, single filament diameter: 11 μm, length: 4.5 mm, manufacturer: Taian Yilin New Material Co., Ltd.

[0043] Vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer, brand: Viton AL-600, manufacturer: DuPont Company, USA.

[0044] Methyl methacrylate-butadiene-styrene terpolymer, brand: EXL-2690, manufacturer: Rohm & Haas Company, USA.

[0045] Ethylene-acrylate-maleic anhydride copolymer, brand: Grafting rate 1.3%, manufacturer: Arkema Company, France.

[0046] Talc, fineness: 2000 mesh, manufacturer: Qingdao Luminous Talc Co., Ltd.

[0047] Example 1

[0048] The present embodiment provides a polyphenylene sulfide composite material, which comprises the following raw materials in parts by weight:

[0049] 140 parts by weight of polyphenylene sulfide, 45 parts by weight of functionalized glass fiber, 15 parts by weight of reinforcing aid, 5 parts by weight of compatibilizer, 2 parts by weight of nucleating agent, 1.5 parts by weight of lubricant, 1.5 parts by weight of antioxidant.

[0050] The reinforcing aid is a mixture of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and methyl methacrylate-butadiene-styrene terpolymer in a weight ratio of 3:1. The compatibilizer is an ethylene-acrylate-maleic anhydride copolymer. The nucleating agent is talc. The lubricant is a mixture of pentaerythritol stearate and ethylene bis-stearamide in a weight ratio of 2:3. The antioxidant is antioxidant 1010.

[0051] The preparation method of the functionalized glass fiber comprises the following steps:

[0052] Mix 10 parts by weight of titanium tetraisopropylate with 50 parts by weight of 85wt% aqueous ethanol solution, and add 8 parts by weight of 12wt% nitric acid dropwise under stirring at 25℃ and 300rpm, the dropwise adding time being 15min, and continue stirring for 25min after the dropwise adding is completed, to obtain a precursor solution; mix 10 parts by weight of glass fiber with 50 parts by weight of 1.8wt% hydrochloric acid, and stir at 65℃ and 300rpm for 4h, filter, and dry to obtain pretreated glass fiber; mix 10 parts by weight of pretreated glass fiber with 60 parts by weight of anhydrous ethanol, and then add 30 parts by weight of the precursor solution, stir at 55℃ and 300rpm for 40min, and then stand for 4h, filter, wash with water until neutral, and dry to obtain nano-TiO2 modified glass fiber; mix 15 parts by weight of nano-TiO2 modified glass fiber and 0.75 parts by weight of (3-glycidoxypropyl) methyl diethoxysilane in 60 parts by weight of 45wt% aqueous ethanol solution, and stir at 72℃ and 100rpm for 50min, filter, and dry to obtain silane-modified glass fiber;

[0053] 45 parts by weight of 60 wt% concentrated nitric acid and 5 parts by weight of 95 wt% concentrated sulfuric acid were mixed, and then 5 parts by weight of polyphenylene sulfide were added. The mixture was reacted at 55 °C and 80 rpm for 1.5 h. After the reaction, the mixture was added to 150 parts by weight of 80 wt% methanol aqueous solution to precipitate, filtered, and dried to obtain nitro-grafted polyphenylene sulfide. 2 parts by weight of sodium borohydride, 0.5 parts by weight of copper chloride, and 50 parts by weight of N-methylpyrrolidone were mixed, and then 3 parts by weight of nitro-grafted polyphenylene sulfide were added. The mixture was reacted at 60 °C and 80 rpm for 1 h. After the reaction, the mixture was added to 150 parts by weight of 80 wt% methanol aqueous solution to precipitate, filtered, and dried to obtain amino-grafted polyphenylene sulfide. 2 parts by weight of amino-grafted polyphenylene sulfide were mixed with 100 parts by weight of N-methylpyrrolidone, and then 5 parts by weight of silane-modified glass fiber were added. The mixture was reacted at 65 °C and 80 rpm for 12 h. After the reaction, N-methylpyrrolidone was recovered by vacuum distillation and dried to obtain functionalized glass fiber.

[0054] This embodiment provides a method for preparing a polyphenylene sulfide composite material, including the following steps:

[0055] According to the raw material formula, polyphenylene sulfide, functionalized glass fiber, reinforcing agents, compatibilizers, nucleating agents, lubricants, and antioxidants are weighed out, then added to a high-speed mixer and mixed at 500 rpm for 10 minutes. The mixture is then added to a twin-screw extruder for melt blending, extrusion granulation, and the resulting polyphenylene sulfide composite material is obtained. The twin-screw extrusion process is as follows: zone 1 temperature 280℃, zone 2 temperature 290℃, zone 3 temperature 290℃, zone 4 temperature 330℃, zone 5 temperature 330℃, zone 6 temperature 300℃, and screw speed 350 rpm.

[0056] Example 2

[0057] This embodiment provides a polyphenylene sulfide composite material, which, by weight, comprises the following raw materials:

[0058] 130 parts by weight of polyphenylene sulfide, 40 parts by weight of functionalized glass fiber, 10 parts by weight of reinforcing agent, 3 parts by weight of compatibilizer, 1 part by weight of nucleating agent, 1 part by weight of lubricant, and 1 part by weight of antioxidant.

[0059] The reinforcing agent is a mixture of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and methyl methacrylate-butadiene-styrene terpolymer in a weight ratio of 2:1. The compatibilizer is an ethylene-acrylate-maleic anhydride copolymer. The nucleating agent is talc. The lubricant is a mixture of pentaerythritol stearate and ethylene bis-stearamide in a weight ratio of 1:3. The antioxidant is antioxidant 1010.

[0060] The preparation method of the functionalized glass fiber is the same as that in Example 1.

[0061] The embodiment provides a preparation method of a polyphenylene sulfide composite material, and the method comprises the following steps:

[0062] The polyphenylene sulfide, the functionalized glass fiber, the reinforcing aid, the compatilizer, the nucleating agent, the lubricant and the antioxidant are weighed according to a raw material formula, then are added into a high-speed mixer and mixed at 400 rpm for 7 min, and then are added into a double-screw extruder to be melt blended, extruded and granulated, so that the polyphenylene sulfide composite material is obtained. The double-screw extrusion process is as follows: the temperature of a first zone is 275 DEG C, the temperature of a second zone is 285 DEG C, the temperature of a third zone is 285 DEG C, the temperature of a fourth zone is 325 DEG C, the temperature of a fifth zone is 325 DEG C, the temperature of a sixth zone is 295 DEG C, and the screw rotation speed is 300 rpm.

[0063] Example 3

[0064] The embodiment provides a polyphenylene sulfide composite material, and the polyphenylene sulfide composite material comprises the following raw materials in parts by weight:

[0065] 150 parts by weight of polyphenylene sulfide, 50 parts by weight of functionalized glass fiber, 20 parts by weight of reinforcing aid, 6 parts by weight of compatilizer, 3 parts by weight of nucleating agent, 2 parts by weight of lubricant and 2 parts by weight of antioxidant.

[0066] The reinforcing aid is a mixture of a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and a methyl methacrylate-butadiene-styrene terpolymer, and the weight ratio of the two is 4:1. The compatilizer is an ethylene-acrylate-maleic anhydride copolymer. The nucleating agent is talcum powder. The lubricant is a mixture of pentaerythritol stearate and ethylene bis-stearamide, and the weight ratio of the two is 3:3. The antioxidant is antioxidant 1010.

[0067] The preparation method of the functionalized glass fiber is the same as that in the embodiment 1.

[0068] The embodiment provides a preparation method of a polyphenylene sulfide composite material, and the method comprises the following steps:

[0069] The polyphenylene sulfide, the functionalized glass fiber, the reinforcing aid, the compatilizer, the nucleating agent, the lubricant and the antioxidant are weighed according to a raw material formula, then are added into a high-speed mixer and mixed at 600 rpm for 15 min, and then are added into a double-screw extruder to be melt blended, extruded and granulated, so that the polyphenylene sulfide composite material is obtained. The double-screw extrusion process is as follows: the temperature of a first zone is 285 DEG C, the temperature of a second zone is 295 DEG C, the temperature of a third zone is 295 DEG C, the temperature of a fourth zone is 335 DEG C, the temperature of a fifth zone is 335 DEG C, the temperature of a sixth zone is 305 DEG C, and the screw rotation speed is 400 rpm.

[0070] Comparative Example 1

[0071] The difference between the present comparative example and Example 1 is that the preparation method of the functionalized glass fiber is different, specifically as follows: the preparation method of the functionalized glass fiber comprises the following steps:

[0072] 10 parts by weight of glass fiber was mixed with 50 parts by weight of 1.8wt% hydrochloric acid, stirred at 65℃, 300rpm for 4h, filtered, washed with water to neutral, dried to obtain pretreated glass fiber; 15 parts by weight of pretreated glass fiber, 0.75 parts by weight of (3-epoxypropoxypropyl) methyl diethoxysilane was added to 60 parts by weight of 45wt% ethanol aqueous solution, stirred at 72℃, 100rpm for 50min, filtered, dried to obtain silane modified glass fiber;

[0073] 45 parts by weight of 60wt% concentrated nitric acid and 5 parts by weight of 95wt% concentrated sulfuric acid were mixed, then 5 parts by weight of polyphenylene sulfide was added, and reacted at 55℃, 80rpm for 1.5h, after the reaction was completed, it was added to 150 parts by weight of 80wt% methanol aqueous solution for precipitation, filtered, dried to obtain nitro grafted polyphenylene sulfide; 2 parts by weight of sodium borohydride, 0.5 parts by weight of copper chloride were mixed with 50 parts by weight of N-methyl pyrrolidone, then 3 parts by weight of nitro grafted polyphenylene sulfide was added, and reacted at 60℃, 80rpm for 1h, after the reaction was completed, it was added to 150 parts by weight of 80wt% methanol aqueous solution for precipitation, filtered, dried to obtain amino grafted polyphenylene sulfide; 2 parts by weight of amino grafted polyphenylene sulfide was mixed with 100 parts by weight of N-methyl pyrrolidone, then 5 parts by weight of silane modified glass fiber was added, and reacted at 65℃, 80rpm for 12h, after the reaction was completed, N-methyl pyrrolidone was recovered by distillation under reduced pressure, and dried to obtain functionalized glass fiber.

[0074] Comparative Example 2

[0075] The difference between the present comparative example and Example 1 is that the preparation method of the functionalized glass fiber is different, specifically as follows: the preparation method of the functionalized glass fiber comprises the following steps:

[0076] 10 parts by weight of titanium tetraisopropylate was mixed with 50 parts by weight of 85wt% ethanol aqueous solution, 8 parts by weight of 12wt% nitric acid was added dropwise under the condition of stirring at 25℃, 300rpm, the dropwise time was 15min, after the dropwise was completed, the stirring was continued for 25min to obtain a precursor solution; 10 parts by weight of glass fiber was mixed with 50 parts by weight of 1.8wt% hydrochloric acid, stirred at 65℃, 300rpm for 4h, filtered, dried to obtain pretreated glass fiber; 10 parts by weight of pretreated glass fiber was mixed with 60 parts by weight of anhydrous ethanol, then 30 parts by weight of the precursor solution was added, stirred at 55℃, 300rpm for 40min, then stood for 4h, filtered, washed with water to neutral, dried to obtain nano TiO2 modified glass fiber;

[0077] Mix 45 parts by weight of 60 wt% concentrated nitric acid and 5 parts by weight of 95 wt% concentrated sulfuric acid, then add 5 parts by weight of polyphenylene sulfide, react at 55°C, 80 rpm for 1.5 h, after the reaction is completed, add to 150 parts by weight of 80 wt% methanol aqueous solution to precipitate, filter, dry, to obtain nitro grafted polyphenylene sulfide; mix 2 parts by weight of sodium borohydride, 0.5 parts by weight of copper chloride with 50 parts by weight of N-methyl pyrrolidone, then add 3 parts by weight of nitro grafted polyphenylene sulfide, react at 60°C, 80 rpm for 1 h, after the reaction is completed, add to 150 parts by weight of 80 wt% methanol aqueous solution to precipitate, filter, dry, to obtain amino grafted polyphenylene sulfide; mix 2 parts by weight of amino grafted polyphenylene sulfide with 100 parts by weight of N-methyl pyrrolidone, then add 5 parts by weight of nano TiO2 modified glass fiber, react at 65°C, 80 rpm for 12 h, after the reaction is completed, recover N-methyl pyrrolidone by distillation under reduced pressure, dry, to obtain functionalized glass fiber.

[0078] Comparative Example 3

[0079] The difference between this comparative example and Example 1 is that the preparation method of the functionalized glass fiber is different, which is as follows: the preparation method of the functionalized glass fiber comprises the following steps:

[0080] Mix 10 parts by weight of titanium isopropylate with 50 parts by weight of 85 wt% ethanol aqueous solution, drop 8 parts by weight of 12 wt% nitric acid under the condition of stirring at 25°C, 300 rpm, the drop time is 15 min, continue to stir for 25 min after the drop is completed, to obtain a precursor solution; mix 10 parts by weight of glass fiber with 50 parts by weight of 1.8 wt% hydrochloric acid, stir at 65°C, 300 rpm for 4 h, filter, dry, to obtain pretreated glass fiber; mix 10 parts by weight of pretreated glass fiber with 60 parts by weight of anhydrous ethanol, then add 30 parts by weight of the precursor solution, stir at 55°C, 300 rpm for 40 min, then stand for 4 h, filter, wash with water until neutral, dry, to obtain nano TiO2 modified glass fiber; add 15 parts by weight of nano TiO2 modified glass fiber, 0.75 parts by weight of (3-glycidoxypropyl) methyl diethoxysilane to 60 parts by weight of 45 wt% ethanol aqueous solution, stir at 72°C, 100 rpm for 50 min, filter, dry, to obtain silane modified glass fiber;

[0081] Mix 2 parts by weight of polyphenylene sulfide with 100 parts by weight of N-methyl pyrrolidone, then add 5 parts by weight of silane modified glass fiber, react at 65°C, 80 rpm for 12 h, after the reaction is completed, recover N-methyl pyrrolidone by distillation under reduced pressure, dry, to obtain functionalized glass fiber.

[0082] Comparative Example 4

[0083] The difference between the present comparative example and Example 1 is that the preparation method of the functionalized glass fiber is different, specifically as follows: the preparation method of the functionalized glass fiber comprises the following steps:

[0084] 10 parts by weight of glass fiber was mixed with 50 parts by weight of 1.8wt% hydrochloric acid, stirred at 65℃, 300rpm for 4h, filtered, washed with water to neutral, dried to obtain pretreated glass fiber;

[0085] 2 parts by weight of polyphenylene sulfide was mixed with 100 parts by weight of N-methyl pyrrolidone, then 5 parts by weight of pretreated glass fiber was added, and reacted at 65℃, 80rpm for 12h. After the reaction, N-methyl pyrrolidone was recovered by distillation under reduced pressure, and dried to obtain functionalized glass fiber.

[0086] Comparative Example 5

[0087] The difference between the present comparative example and Example 1 is that the reinforcing aid is different, and the reinforcing aid is a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer.

[0088] Comparative Example 6

[0089] The difference between the present comparative example and Example 1 is that the reinforcing aid is different, and the reinforcing aid is a methyl methacrylate-butadiene-styrene terpolymer.

[0090] Performance test

[0091] The polyphenylene sulfide composite materials prepared in Examples 1-3 and Comparative Examples 1-6 were injection molded into samples by an injection molding machine, and the following performance tests were performed. Among them, the tensile strength was determined according to the method in GB / T 1040.2-2022 "Determination of tensile properties of plastics Part 2: Test conditions for molded and extruded plastics", 1B dumbbell test sample, 10 groups in parallel for each example, and the average value was taken. The notched impact strength was determined according to the method in GB / T 1843-2008 "Determination of impact strength of plastics by means of a cantilever beam", the test sample was A type notch, 10 groups in parallel for each example, and the average value was taken. The wear resistance was determined according to the method in GB / T 3960-2016 "Plastics - Method of sliding friction and wear testing", the load was 300N, the friction rate was 2m / s, the friction time was 120min, 10 groups in parallel for each example, and the average value was taken. The melting temperature was determined according to the method in GB / T 19466.3-2004 "Differential scanning calorimetry (DSC) for plastics Part 3: Determination of melting and crystallization temperatures and heat of fusion", 10 groups in parallel for each example, and the average value was taken. The results are shown in Table 1.

[0092] Table 1: Performance test results of polyphenylene sulfide composite materials

[0093]

[0094]

[0095] From the performance test results, it can be seen that the polyphenylene sulfide composite materials prepared in Examples 1-3 have excellent tensile strength, notched impact strength, wear resistance and high temperature resistance, and in particular, the polyphenylene sulfide composite material prepared in Example 1 has the best comprehensive performance, because the application uses specific functionalized glass fibers and reinforcing aids to ensure that the polyphenylene sulfide composite material has good mechanical properties (tensile strength) and high temperature resistance (melting temperature), while further improving the toughness (notched impact strength) and wear resistance of the composite material. By comparing Examples 1 and Comparative Examples 1-4, it can be seen that because the functionalized glass fibers prepared in Comparative Examples 1-4 are not prepared by a specific method, the notched impact strength, wear resistance, tensile strength and other test results of the polyphenylene sulfide composite material are significantly worse than those of Example 1. By comparing Examples 1 and Comparative Examples 5-6, it can be seen that because Comparative Examples 5-6 do not use a reinforcing aid composed of a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and a methyl methacrylate-butadiene-styrene terpolymer, the wear resistance and high temperature resistance of the polyphenylene sulfide composite material are worse than those of Example 1. In summary, the above test results further prove the importance of the technical solutions defined in the application to its technical effects.

[0096] The above is the preferred embodiment of the application. It should be noted that for those skilled in the art, without departing from the principles of the application, several improvements and refinements can be made, and these improvements and refinements should also be considered within the scope of protection of the application.

Claims

1. A polyphenylene sulfide composite material, characterized in that, The ingredients are included by weight as follows: 130-150 parts polyphenylene sulfide, 40-50 parts functionalized glass fiber, 10-20 parts reinforcing agent, 3-6 parts compatibilizer, 1-3 parts nucleating agent, 1-2 parts lubricant, 1-2 parts antioxidant; wherein the reinforcing agent is a terpolymer of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene and / or a terpolymer of methyl methacrylate-butadiene-styrene. Methods for preparing functionalized glass fibers include: Tetraisopropyl titanate was mixed with an aqueous ethanol solution, and nitric acid was added dropwise under stirring to obtain a precursor solution. The weight ratio of tetraisopropyl titanate, aqueous ethanol solution, and nitric acid was 7-15:40-60:5-10. Glass fiber was mixed with hydrochloric acid, heated and stirred, filtered, and dried to obtain pretreated glass fiber. Pretreated glass fibers were mixed with anhydrous ethanol, a precursor solution was added, and the mixture was heated and stirred. The mixture was allowed to stand, filtered, and dried to obtain nano-TiO2 modified glass fibers. Nano-TiO2 modified glass fibers and (3-epoxypropoxypropyl)methyldiethoxysilane were added to an aqueous ethanol solution, heated and stirred, filtered, and dried to obtain silane modified glass fibers. Concentrated nitric acid and concentrated sulfuric acid were mixed, polyphenylene sulfide was added, the mixture was heated to react, precipitated, filtered, and dried to obtain nitro-grafted polyphenylene sulfide; sodium borohydride, copper chloride, and N-methylpyrrolidone were mixed, nitro-grafted polyphenylene sulfide was added, the mixture was heated to react, precipitated, filtered, and dried to obtain amino-grafted polyphenylene sulfide; amino-grafted polyphenylene sulfide was mixed with N-methylpyrrolidone, silane was added to modify glass fibers, the mixture was heated to react, vacuum distilled, and dried to obtain functionalized glass fibers; The weight ratio of pretreated glass fiber to precursor solution is 7-15:20-40; the weight ratio of nano-TiO2 modified glass fiber to (3-epoxypropoxypropyl)methyldiethoxysilane is 10-20:0.5-1. The weight ratio of concentrated nitric acid, concentrated sulfuric acid, and polyphenylene sulfide is 40-50:1-10:2-8; the weight ratio of sodium borohydride, copper chloride, and nitro-grafted polyphenylene sulfide is 1-3:0.3-0.8:2-5; and the weight ratio of amino-grafted polyphenylene sulfide to silane-modified glass fiber is 1-3:4-6. The compatibilizer is at least one of ethylene-acrylate-maleic anhydride copolymer, maleic anhydride-grafted ethylene-octene copolymer, and polyolefin-grafted glycidyl methacrylate; the nucleating agent is at least one of talc, calcium carbonate, magnesium carbonate, silica, and mica.

2. The polyphenylene sulfide composite material according to claim 1, characterized in that, The reinforcing agent is a mixture of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer and methyl methacrylate-butadiene-styrene terpolymer in a weight ratio of 2-4:

1.

3. The polyphenylene sulfide composite material according to claim 1, characterized in that, The lubricant is at least one of pentaerythritol stearate, ethylene bis-stearamide, glyceryl stearate, polyvinyl alcohol, and liquid paraffin.

4. The polyphenylene sulfide composite material according to claim 3, characterized in that, The lubricant is a mixture of pentaerythritol stearate and ethylene bis-stearamide in a weight ratio of 1-3:

3.

5. The polyphenylene sulfide composite material according to claim 1, characterized in that, The antioxidant is at least one of antioxidant 1010, antioxidant 616, and antioxidant 1076.

6. The method for preparing the polyphenylene sulfide composite material according to any one of claims 1-5, characterized in that, Includes the following steps: Weigh out polyphenylene sulfide, functionalized glass fiber, reinforcing agent, compatibilizer, nucleating agent, lubricant and antioxidant according to the raw material formula, then add them to a high-speed mixer for mixing, then add them to a twin-screw extruder for melt blending, and extrusion granulation to obtain the polyphenylene sulfide composite material.

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