PA66 nylon composite material for automobile seat and preparation method of PA66 nylon composite material

Abstract

The invention discloses a PA66 nylon composite material for an automobile seat and a preparation method of the PA66 nylon composite material, and relates to the technical field of composite materials. The invention discloses a PA66 nylon composite material for automobile seats. The composite material is prepared from the following raw materials in parts by weight: 80-100 parts of PA66 resin, 15-25 parts of modified glass fibers, 8-12 parts of modified montmorillonite, 6-10 parts of a toughening agent, 10-15 parts of a flame retardant, 4-6 parts of an antistatic agent, 3-5 parts of an antibacterial agent, 2-4 parts of a self-repairing agent, 1-3 parts of a lubricant, 5-8 parts of nano silicon dioxide, 3-5 parts of graphene, 4-7 parts of hollow glass beads, 1-2 parts of a nucleating agent, 1-2 parts of a chain extender and 3-5 parts of a compatilizer. The PA66 nylon composite material for the automobile seat is excellent in comprehensive performance and has the characteristics of high strength, heat resistance, flame retardance, antibacterial property and the like; the raw materials are subjected to multi-step modification, so that the synergistic interaction is obvious; the preparation process is simple and beneficial to industrial production; environment-friendly raw materials are selected, so that the service life of the seat is prolonged, wastes are reduced, and multiple requirements of the automobile industry are met.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials, in particular to a PA66 nylon composite material for automobile seats and a preparation method thereof. Background Art

[0002] As the automotive industry continues to develop, car seats, as key components in vehicles, have a profound impact on the driving experience and safety. PA66 nylon, with its excellent mechanical strength, wear resistance, and chemical stability, has become a key choice for car seat materials. However, existing PA66 nylon composites for car seats still have many limitations in practical applications.

[0003] From a mechanical perspective, car seats are subject to frequent pressure, friction, and impact during daily use. Conventional PA66 nylon composites lack the required tensile, flexural, and impact strength, making them susceptible to deformation and breakage, shortening their service life. For example, prolonged use and frequent adjustments to the seat position can gradually damage the seat structure, compromising functionality and comfort.

[0004] In terms of thermal performance, the ambient temperature inside a car varies greatly. During high temperatures in summer, the heat deformation temperature and Vicat softening point of traditional PA66 nylon composite materials are low, making them prone to softening and deformation. This not only affects the appearance and dimensional stability of the seat, but may also have an adverse effect on the structural strength of the seat, reducing its safety and reliability.

[0005] Furthermore, with increasing demands for increased hygiene and functional diversity in automotive interiors, PA66 nylon composites are increasingly lacking in performance in areas such as antibacterial, antistatic, and self-healing properties. The relatively enclosed interior of a vehicle is prone to bacterial growth, and the inadequate antibacterial properties of conventional materials make it difficult to maintain a hygienic interior. In dry environments, static electricity generated by the material can cause discomfort to drivers and passengers, potentially posing a safety hazard. Furthermore, the material lacks self-healing capabilities, and even minor damage can gradually expand, further degrading its performance.

[0006] Therefore, it is urgent to develop a PA66 nylon composite material for automotive seats with excellent comprehensive performance to meet the ever-increasing performance requirements of the automotive industry and provide drivers and passengers with more comfortable, safe and durable seat products. Summary of the Invention

[0007] In view of the deficiencies in the prior art, the present invention provides a PA66 nylon composite material for automobile seats and a preparation method thereof, which solves the above-mentioned problems.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solutions: A PA66 nylon composite material for automobile seats comprises the following raw materials in parts by weight: 80-100 parts of PA66 resin, 15-25 parts of modified glass fiber, 8-12 parts of modified montmorillonite, 6-10 parts of a toughening agent, 10-15 parts of a flame retardant, 4-6 parts of an antistatic agent, 3-5 parts of an antibacterial agent, 2-4 parts of a self-healing agent, 1-3 parts of a lubricant, 5-8 parts of nano-silica, 3-5 parts of graphene, 4-7 parts of hollow glass microspheres, 1-2 parts of a nucleating agent, 1-2 parts of a chain extender, and 3-5 parts of a compatibilizer.

[0009] Furthermore, the modified glass fiber comprises the following specific steps: A1. Immerse the glass fiber in an ethanol solution containing 5% KH550 by mass and stir at 300 r / min for 1 hour. Transfer the mixed solution to a three-necked flask and reflux at 70°C for 3 hours with continuous stirring. After the reaction, filter and separate the glass fiber, rinse it with anhydrous ethanol four times, and then dry it in a vacuum oven at 70°C to constant weight. Immerse the dried silanized glass fiber in a dopamine solution and stir at 300 r / min for 12 hours. During the reaction, the solution must be kept in contact with air. After the reaction, rinse the glass fiber with deionized water four times and dry it again in a vacuum oven at 70°C. The glass fiber with a polydopamine coating was immersed in a cyclodextrin derivative solution with a concentration of 1 mg / mL and stirred at 300 r / min for 6 hours. After the reaction was completed, the glass fiber was rinsed with deionized water four times and finally vacuum-dried at 70°C to obtain the first modified glass fiber. The dopamine solution was prepared by dissolving 0.6 g of dopamine hydrochloride in 200 mL of Tris-HCl buffer solution with a pH value of 9.0. The amount ratio of the glass fiber, the ethanol solution containing 5% KH550, the dopamine solution, and the cyclodextrin derivative solution was 20 g:200 g:200 mL:160 mL. In ethanol, the ethoxy groups of γ-aminopropyltriethoxysilane undergo hydrolysis upon contact with water, forming silanols. The glass fiber surface is abundant with hydroxyl groups. Under heating and stirring, these silanols react with the hydroxyl groups on the glass fiber surface through a condensation reaction, forming a stable silanol bond and introducing a terminal amino group. This chemical bond formation changes the chemical properties of the glass fiber surface from hydrophilic to organophilic, significantly enhancing its affinity with organic polymers like PA66 resin and laying the foundation for subsequent improved interfacial adhesion. Dopamine undergoes oxidative self-polymerization in a weakly alkaline Tris-HCl buffer, forming a highly adhesive polydopamine layer that bonds to the silanized -NH2 via Michael addition or Schiff base reactions. The hydroxyl groups of cyclodextrin covalently bond to the reactive groups of polydopamine through esterification or etherification, forming a supramolecular host structure and a cyclodextrin derivative graft.

[0010] A2. Immerse the glass fiber after the first modification in a 12.5 mg / mL azobenzene derivative solution, react under 365 nm ultraviolet light, and react for 3 hours. After the reaction, rinse the glass fiber with dichloromethane four times and then dry it at room temperature; immerse the glass fiber grafted with the azobenzene derivative in a 0.1 mol / L nanosilver particle solution, stir at 400 r / min for 4 hours, then separate the glass fiber by centrifugation, wash it with deionized water four times, and vacuum dry it at 70°C; immerse the glass fiber loaded with nanosilver particles in a 5 mg / mL magnetic ferroferric oxide nanoparticle dispersion, react for 3 hours under ultrasound assistance, rinse the glass fiber with toluene four times, and finally vacuum dry it at 70°C to obtain a secondary modified glass fiber; the amount ratio of the azobenzene derivative solution, the nanosilver particle solution, and the magnetic ferroferric oxide nanoparticle dispersion is 200 mL:240 mL:200 mL; After grafting azobenzene derivatives, light-responsive microscopic domains are formed on the surface of the glass fiber. With light stimulation, the size, shape, and distribution of these domains change dynamically, affecting the porosity and pore size distribution within the composite material, thereby regulating properties such as air permeability. After loading silver nanoparticles onto the surface of the glass fiber, the surface roughness and chemical composition are changed, creating a microscopic environment that is not conducive to bacterial adhesion and growth. The introduction of magnetic nanoparticles forms magnetic microdomains in the composite material, changing the stress field distribution within the material.

[0011] A3. The second modified glass fiber was evenly sprayed into a 65% polytetrafluoroethylene emulsion through a spray device to evenly cover the surface of the glass fiber with the polytetrafluoroethylene emulsion, and then the glass fiber was placed in an oven at 200°C for thermal curing for 3 hours; the glass fiber coated with polytetrafluoroethylene was immersed in a 12.5% ​​polydithiocarbamate solution and stirred at 300 r / min for 7 hours. After the reaction was completed, the glass fiber was rinsed with tetrahydrofuran 4 times and vacuum dried at 70°C; the self-healing polymer was placed in a 12.5% ​​polydithiocarbamate solution and stirred at 300 r / min for 7 hours. The glass fiber coated with the biomimetic mineralization solution was immersed in a biomimetic mineralization solution and slowly reacted at room temperature for 5 days. The solution was replaced every other day during the reaction. After the reaction, the glass fiber was rinsed with deionized water 4 times and vacuum-dried at 70°C to obtain a modified glass fiber. The biomimetic mineralization solution was prepared by dissolving 6.66g of CaCl2, 6.36g of Na2CO3, and 3g of polyacrylic acid in 400mL of deionized water. The amount ratio of polytetrafluoroethylene emulsion, polydithiocarbamate solution, and biomimetic mineralization solution was 100g:200mL:400mL. After the second modification, the glass fiber is sprayed with a polytetrafluoroethylene emulsion, which is thermally cured at 200°C. The polytetrafluoroethylene forms a low-friction, wear-resistant coating on the glass fiber surface. It is then immersed in a polydithiocarbamate solution. The active groups in the polydithiocarbamate react with groups in the polytetrafluoroethylene coating or on the glass fiber surface to form a polymer coating with self-healing capabilities. The dynamic covalent bonds within the coating can break and reorganize when the material is damaged. Finally, it is immersed in a biomimetic mineralization solution. The calcium ions, carbonate ions, and polyacrylic acid in the solution chemically react on the glass fiber surface, forming a structure similar to biomineralization, which enhances the mechanical properties and biocompatibility of the glass fiber.

[0012] Furthermore, the modified montmorillonite comprises the following specific steps: B1. A 5% mass fraction montmorillonite suspension was added to a three-necked flask, and a 0.2 mol / L hexadecyltrimethylammonium bromide solution was slowly added dropwise under stirring at 300 r / min. After the addition was completed, the stirring reaction was continued for 3 hours; a 6% mass fraction polyethylene glycol solution was slowly added to the reaction system, and the stirring reaction was continued for 2 hours; a 0.08 mol / L nanoclay expander solution was slowly added dropwise, and the reaction was continued for 4 hours. After the reaction was completed, the montmorillonite was separated by high-speed centrifugation, washed with deionized water 4 times, and then dried in a vacuum oven at 80°C to constant weight to obtain the first modified montmorillonite; the dosage ratio of montmorillonite suspension, hexadecyltrimethylammonium bromide solution, polyethylene glycol solution, and nanoclay expander solution was 400 g:243 mL:67 g:125 mL; Montmorillonite forms a colloidal dispersion in water. The cationic head of cetyltrimethylammonium bromide adsorbs onto the surface of the montmorillonite sheets, compressing the thickness of the double layer and reducing the electrostatic repulsion between particles. This allows the montmorillonite sheets to aggregate more tightly while simultaneously widening the interlayer spacing. The ether oxygen of the polyethylene glycol binds to the siloxane surface of the montmorillonite via hydrogen bonds, further widening the interlayer structure and creating a "bridging" effect, reducing van der Waals forces and enhancing dispersibility.

[0013] B2. A 5% mass fraction of montmorillonite suspension was added to a three-necked flask. Under stirring at 300 r / min, aluminum hypophosphite and a 12% mass fraction of nitrogen-phosphorus intumescent flame retardant solution were added in sequence. After stirring evenly, a 5% mass fraction of silane coupling agent solution was slowly added dropwise. After the addition was completed, the reaction system was heated under reflux under microwave assistance for 3 hours. After the reaction was completed, the montmorillonite was separated by filtration, washed with toluene 4 times, and then dried in a vacuum oven at 80°C to constant weight to obtain a modified montmorillonite with a multi-component synergistic flame retardant and mechanically reinforced network. The dosage ratio of montmorillonite suspension, aluminum hypophosphite, nitrogen-phosphorus intumescent flame retardant solution, and silane coupling agent solution was 400 g: 3.4 g: 34 g: 32 g. Aluminum hypophosphite and a nitrogen-phosphorus intumescent flame retardant solution are added to a montmorillonite suspension, interacting with the montmorillonite through chemical bonds or physical adsorption. Adding a silane coupling agent solution allows the silane coupling agent to react with the hydroxyl groups on the montmorillonite surface and the active groups in the flame retardant. Under microwave-assisted heating and reflux conditions, a multi-component synergistic flame-retardant and mechanically reinforcing network is constructed, enhancing the flame retardancy and mechanical properties of the montmorillonite in the composite.

[0014] B3. Immerse the montmorillonite after the second modification in a quaternary ammonium salt carbon nanotube solution with a concentration of 0.8 mg / mL, stir at 300 r / min for 6 hours, and after the reaction is completed, separate the montmorillonite by centrifugation, wash with deionized water 4 times, and vacuum dry at 60°C; immerse the montmorillonite loaded with the quaternary ammonium salt carbon nanotube solution in a silver nitrate solution with a concentration of 0.425 mg / mL, stir at 300 r / min for 4 hours, and after the reaction is completed, separate the montmorillonite by centrifugation, wash with deionized water The montmorillonite was washed 4 times and vacuum dried at 60°C; the silver ion-treated montmorillonite was immersed in a 10% by mass polyacrylic acid-based antibacterial polymer solution and stirred at 300 r / min for 8 hours. After the reaction, the montmorillonite was rinsed 4 times with deionized water and vacuum dried at 70°C to obtain a modified montmorillonite integrated with an intelligent antibacterial and environmentally responsive antistatic system; the dosage ratio of the quaternized carbon nanotube solution, the silver nitrate solution, and the polyacrylic acid-based antibacterial polymer solution was 250 mL: 200 mL: 40 g; Because quaternized carbon nanotubes form conductive pathways in the composite material, when static electricity is generated on the surface of the material, the charge can be quickly conducted through the conductive network of the quaternized carbon nanotubes, rapidly reducing the electrostatic potential on the surface of the material and achieving an antistatic effect. The antibacterial properties of silver ions are also related to electrochemical processes. When silver ions interact with bacterial cell membranes or intracellular biomacromolecules, redox reactions occur, destroying the physiological functions of bacteria. After the pH-responsive antibacterial polymer is fixed on the surface of montmorillonite, the conformation of its molecular chain and the exposure of its active sites are affected by the pH value. From the perspective of polymer physics and chemistry, in an acidic environment, the acidic groups in the polymer molecules are protonated, and the molecular chains undergo conformational changes such as curling or stretching, exposing more antibacterial active sites and enhancing the antibacterial effect.

[0015] Furthermore, the toughening agent is one of ethylene-octene copolymer, thermoplastic polyurethane elastomer, and methyl methacrylate-butadiene-styrene copolymer.

[0016] Furthermore, the flame retardant is one of polyphosphate melamine, decabromodiphenylethane, and magnesium hydroxide; the antistatic agent is one of dodecyltrimethylammonium chloride, polyethylene glycol, and carbon nanotubes.

[0017] Furthermore, the antibacterial agent is one of nanosilver antibacterial agent and chitosan antibacterial agent.

[0018] Furthermore, the self-healing agent is one of poly(dithiolane-3-one) microcapsules, polyurethane shape memory polymers, and poly(ethylene glycol) diacrylate-borate polymers.

[0019] Furthermore, the lubricant is one of zinc stearate, ethylene bisstearamide, and silicone oil; and the nucleating agent is one of NA-11, dibenzylidene sorbitol, and talc.

[0020] Furthermore, the chain extender is one of 1,4-butanediol diglycidyl ether, adipic acid dihydrazide, and diphenylmethane diisocyanate; the compatibilizer is one of maleic anhydride grafted polypropylene, ethylene-butyl acrylate-glycidyl methacrylate copolymer, and styrene-ethylene-butylene-styrene block copolymer grafted maleic anhydride.

[0021] A method for preparing a PA66 nylon composite material for automobile seats, specifically comprising the following steps: S1. Weigh each raw material by weight, slowly add the modified glass fiber to a high-speed mixer, start stirring, pre-stir at 500r / min for 3 minutes, then add modified montmorillonite, continue stirring for 3 minutes, and then add toughening agent, flame retardant, antistatic agent, antibacterial agent, self-repairing agent, lubricant, nano-silica, graphene, hollow glass microspheres, nucleating agent, chain extender, compatibilizer in sequence. After each raw material is added, stir for 2 minutes to make the newly added raw material and the mixed material preliminarily mixed. After completing the addition of all raw materials, adjust the mixer speed to 1200r / min, mix and stir for 20 minutes to form a uniform premix. S2. Add PA66 resin to a twin-screw extruder and heat it to 260°C to melt it. Then add the premix to the twin-screw extruder through a feeder and extrude it together. The screw speed is 450 r / min. The extruded material is cut into pellets by a water-cooled strand pelletizer to obtain a PA66 nylon composite material for automotive seats.

[0022] The present invention provides a PA66 nylon composite material for automobile seats and a preparation method thereof, which has the following beneficial effects: 1. The PA66 nylon composite material for automotive seats prepared by the present invention has high mechanical properties of tensile strength, flexural strength, and impact strength through multi-step modification of glass fiber and montmorillonite and the rational addition of various functional additives. It is not easily damaged when subjected to various external forces and can effectively ensure the stability of the seat structure. It has high heat deformation temperature and Vicat softening point, good thermal performance, and can maintain shape stability even in high-temperature environments. At the same time, the material has excellent electrical insulation, and the volume resistivity and surface resistivity meet the requirements; excellent flame retardancy and a high oxygen index can slow the spread of fire in the event of a fire; outstanding antibacterial properties, with a high antibacterial rate against Escherichia coli and Staphylococcus aureus, can maintain seat hygiene; good wear resistance, low wear, and a high self-repair rate extend the service life of the seat. These properties enable the material to meet the stringent requirements of automotive seats in terms of safety, comfort, and durability.

[0023] 2. The three-stage modification of glass fiber utilizes technologies such as silanization, dopamine self-polymerization, supramolecular assembly, integrated optoelectronic and electromagnetic functionalization, and biomimetic hierarchical structure construction to significantly enhance its interfacial bonding with PA66 resin. The fiber also possesses multiple optoelectronic and electromagnetic functions, improving the overall performance of the material. The modification of montmorillonite involves precise control of interlayer nanochannels, the construction of a multi-component synergistic flame-retardant and mechanically reinforced network, and the integration of intelligent antimicrobial and environmentally responsive antistatic systems. This effectively improves the dispersion of montmorillonite in the composite material, enhances its synergy with other components, and further enhances the composite material's flame retardant, mechanical, antimicrobial, and antistatic properties.

[0024] 3. In terms of raw material selection, this invention utilizes environmentally friendly materials whenever possible, minimizing negative environmental impacts. For example, some additives used are biodegradable or low-toxic, reducing the risk of environmental pollution during production and use. Furthermore, by optimizing material properties, the service life of the car seat is extended and waste generated by premature material failure is reduced. This conforms to current trends in green environmental protection, achieving high performance while also taking environmental protection into account.

[0025] 4. In the process of material research and development and preparation, the present invention fully considers cost factors. On the one hand, the raw materials selected, such as PA66 resin, modified glass fiber, modified montmorillonite and various additives, are widely available and relatively stable in price. While ensuring the high performance of the material, the raw material procurement cost is effectively controlled. On the other hand, the preparation process is simple and efficient, and conventional high-speed mixers, twin-screw extruders and water-cooled strand pelletizers and other equipment are used to reduce the purchase and maintenance costs of special equipment. In addition, by optimizing the raw material formula and preparation process, the production efficiency of the material is improved, the energy consumption and scrap rate per unit product are reduced, and the production cost is further saved. In the long run, the excellent comprehensive performance of the composite material extends the service life of car seats, reduces the frequency of seat replacement, and reduces the after-sales costs of car manufacturers, bringing good economic benefits to the company and enhancing the competitiveness of the product in the market. DETAILED DESCRIPTION

[0026] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0027] Example 1: Preparation of modified glass fiber, the specific steps are as follows: A1. Immerse 20 g of glass fiber in 200 g of ethanol solution containing 5% KH550 and stir at 300 r / min for 1 hour. Transfer the mixed solution to a three-necked flask and reflux at 70°C for 3 hours with continuous stirring. After the reaction, filter and separate the glass fiber, rinse it with anhydrous ethanol 4 times, and then dry it in a vacuum oven at 70°C to constant weight. Dissolve 0.6 g of dopamine hydrochloride in 200 mL of Tris-HCl buffer solution with a pH value of 9.0 and place the dried silanized glass fiber in a flask. Immerse in a dopamine solution and stir at 300 r / min for 12 hours. During the reaction, the solution must be kept in contact with air. After the reaction is completed, rinse the glass fiber with deionized water four times and dry it again in a vacuum oven at 70°C. Immerse the glass fiber with polydopamine coating in 160 mL of a cyclodextrin derivative solution with a concentration of 1 mg / mL and stir at 300 r / min for 6 hours. After the reaction is completed, rinse the glass fiber with deionized water four times and finally dry it in a vacuum oven at 70°C to obtain the glass fiber after the first modification. A2. Immersing the first modified glass fiber in 200 mL of a 12.5 mg / mL azobenzene derivative solution, reacting under 365 nm ultraviolet light for 3 hours, and then rinsing the glass fiber four times with dichloromethane after completion of the reaction. Immersing the glass fiber grafted with an azobenzene derivative in 240 mL of a nanosilver particle solution, stirring at 400 r / min for 4 hours, and then separating the glass fiber by centrifugation. The glass fiber was washed four times with deionized water, and the product was vacuum dried at 70° C. The glass fiber loaded with nanosilver particles was immersed in 200 mL of a magnetic ferroferric oxide nanoparticle dispersion, reacted for 3 hours under ultrasound assistance, and after completion of the reaction, the glass fiber was rinsed four times with toluene. Finally, vacuum dried at 70° C. to obtain a secondary modified glass fiber. A3. The second modified glass fiber was evenly sprayed into 100 g of 65% polytetrafluoroethylene emulsion through a spray device to evenly cover the surface of the glass fiber with polytetrafluoroethylene emulsion, and then the glass fiber was placed in an oven at 200°C for thermal curing for 3 hours; the glass fiber coated with polytetrafluoroethylene was immersed in 200 mL of 12.5% ​​polydithiocarbamate solution and stirred at 300 r / min for 7 hours. After the reaction, the glass fiber was rinsed with tetrahydrofuran 4 times and vacuum dried at 70°C; the glass fiber with self-healing polymer coating was immersed in 400 mL of biomimetic mineralization solution and slowly reacted at room temperature for 5 days. The solution was replaced every other day during the reaction. After the reaction, the glass fiber was rinsed with deionized water 4 times and vacuum dried at 70°C to obtain modified glass fiber; the biomimetic mineralization solution was prepared by dissolving 6.66 g CaCl2, 6.36 g Na2CO3, and 3 g polyacrylic acid in 400 mL of deionized water.

[0028] Example 2, preparing modified montmorillonite, the specific steps are as follows: B1. 400 g of a 5% montmorillonite suspension was added to a three-necked flask, and 243 mL of a 0.2 mol / L hexadecyltrimethylammonium bromide solution was slowly added dropwise at 300 r / min stirring. After the addition was complete, the reaction was continued with stirring for 3 hours. 67 g of a 6% polyethylene glycol solution was slowly added to the reaction system, and the reaction was stirred for 2 hours. 125 mL of a 0.08 mol / L nanoclay expansion agent solution was slowly added dropwise, and the reaction was continued for 4 hours under stirring. After the reaction was completed, the montmorillonite was separated by high-speed centrifugation, washed 4 times with deionized water, and then dried in a vacuum oven at 80°C to constant weight to obtain the first modified montmorillonite. B2. 400 g of a 5% by mass montmorillonite suspension was added to a three-necked flask. Under stirring at 300 r / min, 3.4 g of aluminum hypophosphite and 34 g of a 12% by mass nitrogen-phosphorus intumescent flame retardant solution were added in sequence. After stirring evenly, 32 g of a 5% by mass silane coupling agent solution was slowly added dropwise. After the addition was completed, the reaction system was heated under reflux under microwave assistance for 3 hours. After the reaction was completed, the montmorillonite was separated by filtration, washed with toluene 4 times, and then dried in a vacuum oven at 80°C to constant weight to obtain a modified montmorillonite with a multi-component synergistic flame retardant and mechanically reinforced network construction; B3. The montmorillonite after the second modification was immersed in 250 mL of a quaternary ammonium salt carbon nanotube solution with a concentration of 0.8 mg / mL, stirred at 300 r / min for 6 hours. After the reaction was completed, the montmorillonite was separated by centrifugation, washed with deionized water 4 times, and vacuum dried at 60°C; the montmorillonite loaded with the quaternary ammonium salt carbon nanotube solution was immersed in 200 mL of a silver nitrate solution with a concentration of 0.425 mg / mL, stirred at 300 r / min for 4 hours. After the reaction was completed, the montmorillonite was separated by centrifugation, washed with deionized water 4 times, and vacuum dried at 60°C; the montmorillonite treated with silver ions was immersed in 40 g of a polyacrylic acid-based antibacterial polymer solution with a mass fraction of 10%, stirred at 300 r / min for 8 hours. After the reaction was completed, the montmorillonite was rinsed with deionized water 4 times and vacuum dried at 70°C to obtain a modified montmorillonite integrated with an intelligent antibacterial and environmentally responsive antistatic system.

[0029] Example 3: Preparation of PA66 nylon composite material for automobile seats, the specific steps are as follows: S1, weigh each raw material by weight, slowly add 15 parts of modified glass fiber obtained in Example 1 into a high-speed mixer, start stirring, pre-stir at 500r / min for 3 minutes, then add 8 parts of modified montmorillonite obtained in Example 2, continue stirring for 3 minutes, then add 6 parts of ethylene-octene copolymer, 10 parts of polyphosphate melamine, 4 parts of dodecyltrimethylammonium chloride, 3 parts of nano-silver antibacterial agent, 2 parts of poly (dithiolane-3-one) microcapsules, 1 part of zinc stearate, 5 parts of nano-silicon dioxide, 3 parts of graphene, 4 parts of hollow glass microspheres, 1 part of nucleating agent NA-11, 1 part of 1,4-butanediol diglycidyl ether, and 3 parts of maleic anhydride grafted polypropylene. After each raw material is added, stir for 2 minutes to preliminarily mix the newly added raw material with the mixed material. After completing the addition of all raw materials, adjust the mixer speed to 1200r / min, mix and stir for 20 minutes to form a uniform premix; S2. Add 80 parts of PA66 resin into a twin-screw extruder and heat it to 260°C to melt it. Then add the premix into the twin-screw extruder through a feeder and extrude it together. The screw speed is 450 r / min. The extruded material is cut into pellets by a water-cooled strand pelletizer to obtain a PA66 nylon composite material for automotive seats.

[0030] Example 4: Preparation of PA66 nylon composite material for automobile seats, the specific steps are as follows: S1, take each raw material by weight, 25 parts of modified glass fibers obtained in Example 1 are slowly added to a high-speed mixer, stirring is started, and pre-stirred at 500r / min for 3 minutes, followed by addition of 12 parts of modified montmorillonite obtained in Example 2, and stirring is continued for 3 minutes, followed by sequential addition of 10 parts of thermoplastic polyurethane elastomers, 15 parts of decabromodiphenyl ethanes, 6 parts of polyethylene glycols, 5 parts of chitosan antibacterial agents, 4 parts of polyurethane shape memory polymers, 3 parts of ethylene bisstearamides, 8 parts of nano-silica, 5 parts of graphene, 7 parts of hollow glass microspheres, 2 parts of dibenzylidene sorbitol, 2 parts of adipic acid dihydrazides, 5 parts of ethylene-butyl acrylate-glycidyl methacrylate copolymers, and after each addition of a raw material, stirring for 2 minutes to uniformly mix the newly added raw material and the mixed material, and after completing the addition of all raw materials, the mixer speed is adjusted to 1200r / min, and mixed and stirred for 20 minutes to form a uniform premix; S2. Add 100 parts of PA66 resin into a twin-screw extruder and heat it to 260°C to melt it. Then add the premix into the twin-screw extruder through a feeder and blend and extrude it at a screw speed of 450 r / min. Cut the extruded material into pellets through a water-cooled strand pelletizer to obtain a PA66 nylon composite material for automotive seats.

[0031] Example 5: Preparation of PA66 nylon composite material for automobile seats, the specific steps are as follows: S1, weigh each raw material by weight, 20 parts of modified glass fibers obtained in Example 1 are slowly added to a high-speed mixer, stirring is started, and pre-stirred at 500r / min for 3 minutes, followed by addition of 10 parts of modified montmorillonite obtained in Example 2, and stirring is continued for 3 minutes, followed by the sequential addition of 8 parts of methyl methacrylate-butadiene-styrene copolymer, 12 parts of magnesium hydroxide, 5 parts of carbon nanotubes, 4 parts of chitosan antibacterial agents, 3 parts of poly (ethylene glycol) diacrylate-borate polymer, 2 parts of silicone oil, 6 parts of nano-silica, 4 parts of graphene, 5 parts of hollow glass microspheres, 1 part of talc, 1 part of diphenylmethane diisocyanate, and 4 parts of styrene-ethylene-butylene-styrene block copolymer grafted maleic anhydride, and after each addition of a raw material, stirring for 2 minutes to uniformly mix the newly added raw material and the mixed material, and after completing the addition of all raw materials, the mixer speed is adjusted to 1200r / min, and mixed and stirred for 20 minutes to form a uniform premix; S2. Add 90 parts of PA66 resin into a twin-screw extruder and heat it to 260°C to melt it. Then add the premix into the twin-screw extruder through a feeder and blend and extrude it at a screw speed of 450 r / min. Cut the extruded material into pellets through a water-cooled strand pelletizer to obtain a PA66 nylon composite material for automotive seats.

[0032] Comparative Example 1: Preparation of PA66 nylon composite material for automobile seats, the specific steps are as follows: The remaining steps remained unchanged, except that the modified glass fiber in Example 4 was replaced by glass fiber without any treatment to prepare a PA66 nylon composite material for automobile seats.

[0033] Comparative Example 2: Preparation of PA66 nylon composite material for automobile seats, the specific steps are as follows: The remaining steps remained unchanged, except that the modified montmorillonite in Example 4 was replaced by montmorillonite without any treatment to prepare a PA66 nylon composite material for automobile seats.

[0034] Test indicators Test Method Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 tensile strength According to GB / T1040.2-2006 standard, the test was carried out using a universal material testing machine with a tensile speed of 50 mm / min. 115MPa 135MPa 130MPa 90MPa 100MPa Bending strength According to GB / T9341-2008 standard, the test was carried out on a universal material testing machine with a span of 40 mm and a loading speed of 2 mm / min. 170MPa 200MPa 190MPa 140MPa 150MPa Impact strength According to GB / T1043.1-2008 standard, the cantilever beam impact tester was used, the notch type was A, and the impact energy was 2.75J. <![CDATA[55kJ / m 2 ]]> <![CDATA[75kJ / m 2 ]]> <![CDATA[70kJ / m 2 ]]> <![CDATA[40kJ / m 2 ]]> <![CDATA[45kJ / m 2 ]]> Heat deformation temperature According to GB / T1634.2-2004 standard, the test was carried out at a load of 0.45 MPa and a heating rate of 120°C / h. 175℃ 195℃ 190℃ 150℃ 160℃ Vicat softening point According to GB / T1633-2000 standard, the test was carried out at a heating rate of 50℃ / h and a load of 10N. 205℃ 225℃ 220℃ 190℃ 200℃ Volume resistivity Use high resistance meter to test according to GB / T1410-2006 standard <![CDATA[8.0×10 14 Ohm cm]]> <![CDATA[1.5×10 15 Ohm cm]]> <![CDATA[1.3×10 15 Ohm cm]]> <![CDATA[5.0×10 14 Ohm cm]]> <![CDATA[6.0×10 14 Ohm cm]]> Surface resistivity Use surface resistance tester to test according to GB / T1692-2008 standard <![CDATA[9.0×10 8 Oh]]> <![CDATA[6.0×10 8 Oh]]> <![CDATA[7.0×10 8 Oh]]> <![CDATA[1.0×10 9 Oh]]> <![CDATA[1.2×10 9 Oh]]> Oxygen index According to GB / T2406.2-2009 standard, test on oxygen index meter 28% 34% 33% 25% 26% Antibacterial rate (Escherichia coli) According to GB / T21510-2008 standard, the test is carried out using the film method 93% 98% 97% 70% 75% Antibacterial rate (Staphylococcus aureus) According to GB / T21510-2008 standard, the test is carried out using the film method 94% 98% 97% 72% 76% Wear According to GB / T3960-1983 standard, the test was carried out on an abrasion testing machine using a rubber grinding wheel, a load of 10N, and a wear stroke of 40m. 50mg 35mg 40mg 60mg 55mg Self-repair rate The samples were made into standard specimens, scratched artificially, and placed under certain conditions. The scratch repair was observed under a microscope and the self-repair rate was calculated. 78% 85% 83% 10% 15% Comparing the performance test results of Examples 3, 4, and 5 with Comparative Examples 1 and 2, it can be seen that the various performance properties of the Examples are significantly better. In terms of mechanical properties, the tensile, flexural, and impact strengths are higher; in terms of thermal properties, the heat deformation temperature and Vicat softening point are higher; in terms of electrical properties, the volume and surface resistivities are more in line with the requirements; the oxygen index of the flame retardant performance is higher; the antibacterial rate of the antibacterial performance is higher; and the wear resistance of the wear resistance is lower and the self-repair rate is higher. This shows that the modified glass fiber and montmorillonite raw materials of the present invention have a significant effect on improving the performance of the composite material. The prepared composite material has good overall performance and can better meet the use requirements of automobile seats.

[0035] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A PA66 nylon composite material for automobile seats, characterized by: It contains the following raw materials in parts by weight: 80-100 parts of PA66 resin, 15-25 parts of modified glass fiber, 8-12 parts of modified montmorillonite, 6-10 parts of toughening agent, 10-15 parts of flame retardant, 4-6 parts of antistatic agent, 3-5 parts of antibacterial agent, 2-4 parts of self-healing agent, 1-3 parts of lubricant, 5-8 parts of nano-silica, 3-5 parts of graphene, 4-7 parts of hollow glass microspheres, 1-2 parts of nucleating agent, 1-2 parts of chain extender, and 3-5 parts of compatibilizer.

2. The PA66 nylon composite material for automobile seats according to claim 1, characterized in that: The modified glass fiber comprises the following specific steps: A1. Immerse the glass fiber in an ethanol solution containing 5% KH550 by mass and stir at 300 r / min for 1 hour. Transfer the mixed solution to a three-necked flask and reflux at 70°C for 3 hours with continuous stirring. After the reaction, filter and separate the glass fiber, rinse it with anhydrous ethanol four times, and then dry it in a vacuum oven at 70°C to constant weight. Immerse the dried silanized glass fiber in a dopamine solution and stir at 300 r / min for 12 hours. During the reaction, the solution must be kept in contact with air. After the reaction, rinse the glass fiber with deionized water four times and dry it again in a vacuum oven at 70°C. The glass fiber with a polydopamine coating was immersed in a cyclodextrin derivative solution with a concentration of 1 mg / mL and stirred at 300 r / min for 6 hours. After the reaction was completed, the glass fiber was rinsed with deionized water four times and finally vacuum-dried at 70°C to obtain the first modified glass fiber. The dopamine solution was prepared by dissolving 0.6 g of dopamine hydrochloride in 200 mL of Tris-HCl buffer solution with a pH value of 9.

0. The amount ratio of the glass fiber, the ethanol solution containing 5% KH550, the dopamine solution, and the cyclodextrin derivative solution was 20 g:200 g:200 mL:160 mL. A2. Immerse the glass fiber after the first modification in a 12.5 mg / mL azobenzene derivative solution, react under 365 nm ultraviolet light, and react for 3 hours. After the reaction, rinse the glass fiber with dichloromethane four times and then dry it at room temperature; immerse the glass fiber grafted with the azobenzene derivative in a 0.1 mol / L nanosilver particle solution, stir at 400 r / min for 4 hours, then separate the glass fiber by centrifugation, wash it with deionized water four times, and vacuum dry it at 70°C; immerse the glass fiber loaded with nanosilver particles in a 5 mg / mL magnetic ferroferric oxide nanoparticle dispersion, react for 3 hours under ultrasound assistance, rinse the glass fiber with toluene four times, and finally vacuum dry it at 70°C to obtain a secondary modified glass fiber; the amount ratio of the azobenzene derivative solution, the nanosilver particle solution, and the magnetic ferroferric oxide nanoparticle dispersion is 200 mL:240 mL:200 mL; A3. The second modified glass fiber was evenly sprayed into a 65% polytetrafluoroethylene emulsion through a spray device to evenly cover the surface of the glass fiber with the polytetrafluoroethylene emulsion, and then the glass fiber was placed in an oven at 200°C for thermal curing for 3 hours; the glass fiber coated with polytetrafluoroethylene was immersed in a 12.5% ​​polydithiocarbamate solution and stirred at 300 r / min for 7 hours. After the reaction was completed, the glass fiber was rinsed with tetrahydrofuran 4 times and vacuum dried at 70°C; the self-healing polymer was placed in a 12.5% ​​polydithiocarbamate solution and stirred at 300 r / min for 7 hours. The glass fiber coated with the biomimetic mineralization solution was immersed in a biomimetic mineralization solution and slowly reacted at room temperature for 5 days. The solution was replaced every other day during the reaction. After the reaction, the glass fiber was rinsed with deionized water 4 times and vacuum-dried at 70°C to obtain a modified glass fiber. The biomimetic mineralization solution was prepared by dissolving 6.66g CaCl2, 6.36g Na2CO3, and 3g polyacrylic acid in 400mL deionized water. The dosage ratio of polytetrafluoroethylene emulsion, polydithiocarbamate solution, and biomimetic mineralization solution was 100g:200mL:400mL.

3. The PA66 nylon composite material for automobile seats according to claim 1, characterized in that: The modified montmorillonite comprises the following specific steps: B1. A 5% mass fraction montmorillonite suspension was added to a three-necked flask, and a 0.2 mol / L hexadecyltrimethylammonium bromide solution was slowly added dropwise under stirring at 300 r / min. After the addition was completed, the stirring reaction was continued for 3 hours; a 6% mass fraction polyethylene glycol solution was slowly added to the reaction system, and the stirring reaction was continued for 2 hours; a 0.08 mol / L nanoclay expander solution was slowly added dropwise, and the reaction was continued for 4 hours. After the reaction was completed, the montmorillonite was separated by high-speed centrifugation, washed with deionized water 4 times, and then dried in a vacuum oven at 80°C to constant weight to obtain the first modified montmorillonite; the dosage ratio of montmorillonite suspension, hexadecyltrimethylammonium bromide solution, polyethylene glycol solution, and nanoclay expander solution was 400 g:243 mL:67 g:125 mL; B2. A 5% mass fraction of montmorillonite suspension was added to a three-necked flask. Under stirring at 300 r / min, aluminum hypophosphite and a 12% mass fraction of nitrogen-phosphorus intumescent flame retardant solution were added in sequence. After stirring evenly, a 5% mass fraction of silane coupling agent solution was slowly added dropwise. After the addition was completed, the reaction system was heated under reflux under microwave assistance for 3 hours. After the reaction was completed, the montmorillonite was separated by filtration, washed with toluene 4 times, and then dried in a vacuum oven at 80°C to constant weight to obtain a modified montmorillonite with a multi-component synergistic flame retardant and mechanically reinforced network. The dosage ratio of montmorillonite suspension, aluminum hypophosphite, nitrogen-phosphorus intumescent flame retardant solution, and silane coupling agent solution was 400 g: 3.4 g: 34 g: 32 g. B3. Immerse the montmorillonite after the second modification in a quaternary ammonium salt carbon nanotube solution with a concentration of 0.8 mg / mL, stir at 300 r / min for 6 hours, and after the reaction is completed, separate the montmorillonite by centrifugation, wash with deionized water 4 times, and vacuum dry at 60°C; immerse the montmorillonite loaded with the quaternary ammonium salt carbon nanotube solution in a silver nitrate solution with a concentration of 0.425 mg / mL, stir at 300 r / min for 4 hours, and after the reaction is completed, separate the montmorillonite by centrifugation, wash with deionized water The reaction mixture was washed 4 times and vacuum dried at 60°C; the silver ion-treated montmorillonite was immersed in a 10% by mass polyacrylic acid-based antibacterial polymer solution and stirred at 300 r / min for 8 hours. After the reaction was completed, the montmorillonite was rinsed 4 times with deionized water and vacuum dried at 70°C to obtain a modified montmorillonite integrated with an intelligent antibacterial and environmentally responsive antistatic system; the usage ratio of the quaternized carbon nanotube solution, silver nitrate solution, and polyacrylic acid-based antibacterial polymer solution was 250 mL: 200 mL: 40 g.

4. The PA66 nylon composite material for automobile seats according to claim 1, characterized in that: The toughening agent is one of ethylene-octene copolymer, thermoplastic polyurethane elastomer, and methyl methacrylate-butadiene-styrene copolymer.

5. The PA66 nylon composite material for automobile seats according to claim 1, characterized in that: The flame retardant is one of polyphosphate melamine, decabromodiphenylethane, and magnesium hydroxide; the antistatic agent is one of dodecyltrimethylammonium chloride, polyethylene glycol, and carbon nanotubes.

6. The PA66 nylon composite material for automobile seats according to claim 1, characterized in that: The antibacterial agent is one of a nano silver antibacterial agent and a chitosan antibacterial agent.

7. The PA66 nylon composite material for automobile seats according to claim 1, characterized in that: The self-repairing agent is one of poly(dithiolane-3-one) microcapsules, polyurethane shape memory polymers, and poly(ethylene glycol) diacrylate-borate polymers.

8. The PA66 nylon composite material for automobile seats according to claim 1, characterized in that: The lubricant is one of zinc stearate, ethylene bisstearamide, and silicone oil; the nucleating agent is one of NA-11, dibenzylidene sorbitol, and talc.

9. The PA66 nylon composite material for automobile seats according to claim 1, characterized in that: The chain extender is one of 1,4-butanediol diglycidyl ether, adipic acid dihydrazide, and diphenylmethane diisocyanate; the compatibilizer is one of maleic anhydride grafted polypropylene, ethylene-butyl acrylate-glycidyl methacrylate copolymer, and styrene-ethylene-butylene-styrene block copolymer grafted maleic anhydride.

10. A method for preparing a PA66 nylon composite material for automobile seats, comprising the following steps: S1. Weigh each raw material by weight, slowly add the modified glass fiber to a high-speed mixer, start stirring, pre-stir at 500r / min for 3 minutes, then add modified montmorillonite, continue stirring for 3 minutes, and then add toughening agent, flame retardant, antistatic agent, antibacterial agent, self-repairing agent, lubricant, nano-silica, graphene, hollow glass microspheres, nucleating agent, chain extender, compatibilizer in sequence. After each raw material is added, stir for 2 minutes to make the newly added raw material and the mixed material preliminarily mixed. After completing the addition of all raw materials, adjust the mixer speed to 1200r / min, mix and stir for 20 minutes to form a uniform premix. S2. Add PA66 resin to a twin-screw extruder and heat it to 260°C to melt it. Then add the premix to the twin-screw extruder through a feeder and extrude it together. The screw speed is 450 r / min. The extruded material is cut into pellets by a water-cooled strand pelletizer to obtain a PA66 nylon composite material for automotive seats.