Heat-resistant high-strength nylon composite material and preparation method thereof
The preparation of micro-nanostructured composite fillers through electrostatic self-assembly solves the problems of thermal deformation and interface failure of traditional nylon materials at high temperatures, improves the strength and heat resistance of nylon composite materials, and reduces economic costs.
Patent Information
- Application Number
- CN202511103916.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-07
- Publication Date
- 2025-09-12
AI Technical Summary
Traditional nylon materials have low thermal deformation temperature and poor heat resistance in high-temperature environments. In addition, glass fiber reinforced nylon materials are subject to severe wear during processing and their interfaces are prone to failure, resulting in a decrease in mechanical properties.
A micro-nanostructured composite filler is formed by electrostatic self-assembly of nano-inorganic particles and micron-inorganic fibers, and has epoxy functional groups on the surface. The heat-resistant and high-strength nylon composite material is prepared by electrostatic self-assembly to optimize the interface wetting effect between the filler and the matrix.
It significantly improves the strength and heat resistance of nylon composite materials, reduces economic costs, and maintains stable performance in high temperature environments.
Smart Images
Figure CN120623767A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a heat-resistant high-strength nylon composite material and a preparation method thereof, belonging to the technical field of polymer materials. Background Art
[0002] With its excellent mechanical properties, chemical corrosion resistance and good processing performance, the application scope of nylon materials has gradually expanded from the traditional chemical fiber textile industry to multiple fields such as automobiles, electrical equipment, aerospace, and military industry. In recent years, as new energy vehicles have evolved towards high voltage and long driving range, lightweight materials need to maintain stable performance in high temperature environments of 80-150°C. However, compared with other engineering plastics, traditional nylon materials have the shortcomings of low heat deformation temperature and poor heat resistance, which makes it difficult to meet the heat resistance requirements of components such as battery pack housings and motor end covers. In the existing technology, common glass fiber reinforced nylon materials are made by adding a certain amount of glass fiber to nylon resin. This type of composite material saves a lot of metal and energy in production applications. Although this method can increase the heat deformation temperature of nylon materials, there are problems such as large wear during processing and easy failure of the interface in high temperature environments, resulting in a decrease in mechanical properties.
[0003] Research has shown that the interfacial bonding strength between fillers and matrices is a key factor in improving composite material performance. Composites prepared through traditional physical blending are prone to interfacial debonding at high temperatures due to poor filler-matrix compatibility. Therefore, the development of composite fillers with micro-nanostructures can optimize the interfacial wetting between the filler and matrix, significantly improving the strength and heat resistance of nylon composites. Summary of the Invention
[0004] In view of the problems existing in the above-mentioned prior art, the present invention provides a heat-resistant and high-strength nylon composite material and a preparation method thereof, which effectively improves the strength and heat resistance of the nylon composite material.
[0005] In order to achieve the above object, the present invention adopts a heat-resistant and high-strength nylon composite material, which comprises the following raw materials in parts by weight: 75-90 parts of nylon and 10-25 parts of composite filler;
[0006] The composite filler is a composite filler with a micro-nano structure, which is formed by electrostatic self-assembly of nano-inorganic particles and micro-inorganic fibers, and the zeta potential of the nano-inorganic particles and the micro-inorganic fibers are opposite;
[0007] The composite filler is surface-modified by a silane coupling agent, and has epoxy functional groups on the surface.
[0008] As an improvement, the nylon is at least one of nylon 6 and nylon 66.
[0009] As an improvement, the particle size of the nano inorganic particles is 200-500 nm, and the nano inorganic particles are at least one of nano montmorillonite, nano kaolin, and nano alumina.
[0010] As an improvement, the diameter of the micron inorganic fiber is 1-5 μm, and the micron inorganic fiber is at least one of sepiolite fiber, palygorskite fiber, basalt fiber, and brucite fiber.
[0011] As an improvement, the composite filler includes 1-2 parts of nano inorganic particles and 98-99 parts of micron inorganic fibers, based on weight.
[0012] The second aspect of the present invention further provides a method for preparing the heat-resistant high-strength nylon composite material, comprising the following steps:
[0013] (1) Ultrasonic dispersion of nano-inorganic particles in water, then adding micron inorganic fibers, stirring at room temperature, filtering and drying to obtain a composite filler with a micro-nano structure;
[0014] (2) mixing water, ethanol, and a silane coupling agent to obtain a hydrolyzate, stirring the hydrolyzate and the composite filler obtained in step (1) in a high-speed mixer, and drying to obtain a composite filler having epoxy functional groups on its surface;
[0015] (3) The nylon and the composite filler treated in step (2) are mixed evenly, dried, and then put into a twin-screw extruder for extrusion and granulation to obtain the heat-resistant and high-strength nylon composite material.
[0016] As an improvement, in step (2), the molar ratio of water to the silane coupling agent is (1-3):1, and the volume ratio of ethanol to the silane coupling agent is (1-3):1.
[0017] As an improvement, the silane coupling agent is KH560.
[0018] As an improvement, in step (2), water, ethanol and silane coupling agent are mixed and then uniformly stirred at 30-40° C. for 0.3-1 h to obtain a hydrolyzed solution.
[0019] As an improvement, in step (3), the nylon and the composite filler are dried at 100-110° C. for 1-3 h and then mixed evenly.
[0020] Compared to existing technologies, this invention utilizes a simple physical adsorption method to electrostatically self-assemble nanoparticles and micron-sized inorganic fibers into a composite filler with a micro-nanostructure. The nanoparticles adhere to the surface of the micron-sized inorganic fibers, creating an anchoring effect that effectively optimizes interfacial wetting with the matrix and facilitates stress transfer. The micron-sized inorganic fibers provide skeletal support, while the nanoparticles fill the interfiber gaps, acting as a nano-barrier. This effectively prevents molecular chain slippage in the matrix, significantly slowing thermal decomposition, while promoting uniform heat diffusion within the composite material, thereby simultaneously enhancing the strength and heat resistance of the nylon composite. Furthermore, due to the high natural abundance of inorganic fillers, they can also reduce economic costs and improve economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Figure 1 This is a scanning electron microscope image of the composite filler with micro-nano structure prepared in Example 1 of the present invention;
[0022] Figure 2 This is a scanning electron microscope image of a cross section of the heat-resistant and high-strength nylon composite material prepared in Example 2 of the present invention;
[0023] Figure 3 This is a scanning electron microscope image of the cross section of the nylon / micron inorganic fiber composite material prepared in Comparative Example 2 of the present invention. DETAILED DESCRIPTION
[0024] The following embodiments are further descriptions of the present invention to illustrate the technical content of the present invention, but the essential content of the present invention is not limited to the following embodiments. Ordinary technicians in this field can and should know that any simple changes or replacements based on the essential spirit of the present invention should fall within the scope of protection required by the present invention.
[0025] Example 1
[0026] A method for preparing a heat-resistant high-strength nylon composite material comprises the following steps:
[0027] (1) 1 g of nano-montmorillonite (particle size of 200-500 nm) was ultrasonically dispersed in 200 g of water. After ultrasonication for 5 min, 99 g of sepiolite fiber (cross-sectional diameter of 1-5 μm) was added. The mixture was stirred at room temperature for 2 h, subjected to simple physical adsorption, and then filtered and dried to obtain a composite filler with a micro-nano structure.
[0028] (2) Pour 2.288 g of water, 7.347 g of ethanol, and 10 g of KH560 into a beaker, and stir evenly at 35° C. for 0.5 h to obtain a hydrolyzate. Place the hydrolyzate and the composite filler prepared in step (1) into a high-speed mixer, stir and mix for 0.5 h, and then take out and dry to obtain a composite filler with epoxy functional groups on the surface;
[0029] (3) 1200 g of nylon 6 and 300 g of the composite filler with epoxy functional groups on its surface obtained in step (2) were placed in an oven and dried at 105°C for 2 h. The mixture was then evenly mixed and placed in a twin-screw extruder for blending, extrusion and granulation to obtain the heat-resistant, high-strength nylon composite material. The temperature of the twin-screw extruder in zones 1 to 3 was 235°C, the temperature in zones 4 to 6 was 240°C, the temperature in zones 7 to 9 was 235°C, the die head temperature was 230°C, and the screw speed was 400 r / min.
[0030] The Zeta potential test results of the nano-montmorillonite (Guangzhou Yifeng Chemical Technology Co., Ltd.) and sepiolite fiber (Hebei Lingshou Jinchang Minerals Co., Ltd.) used in Example 1 are shown in Table 1.
[0031] Table 1 Zeta potential of nano-montmorillonite and sepiolite fibers
[0032]
[0033] Table 1 shows that in aqueous solution, the zeta potential (Zp) of sepiolite fibers is positive, while that of nano-montmorillonite is negative. Electrophoretic mobility (Mob) measures the speed at which charged particles move in an electric field. The signs represent the charge polarity of the two particles. Opposite charge polarity indicates that the electrostatic interaction between them is primarily attractive, demonstrating the feasibility of loading nano-inorganic particles onto the surface of micron-sized inorganic fibers through electrostatic attraction to form micro-nanostructured composite fillers.
[0034] Figure 1 This is a scanning electron microscope image of a composite filler with a micro-nano structure obtained by physical adsorption. It can be seen that the nano-montmorillonite particles are anchored on the surface of micron-sized sepiolite fibers to form an inorganic composite filler with a micro-nano structure.
[0035] Example 2
[0036] A method for preparing a heat-resistant high-strength nylon composite material comprises the following steps:
[0037] (1) 1.5 g of nano-montmorillonite was ultrasonically dispersed in 200 g of water. After ultrasonication for 5 min, 98.5 g of sepiolite fiber was added and stirred at room temperature for 2 h. Simple physical adsorption was performed and then filtered and dried to obtain a composite filler with a micro-nano structure.
[0038] (2) Pour 2.288 g of water, 7.347 g of ethanol, and 10 g of KH560 into a beaker, and stir evenly at 35° C. for 0.5 h to obtain a hydrolyzate. Place the hydrolyzate and the composite filler prepared in step (1) into a high-speed mixer, stir and mix for 0.5 h, and then take out and dry to obtain a composite filler with epoxy functional groups on the surface;
[0039] (3) 1200 g of nylon 6 and 300 g of the composite filler with epoxy functional groups on its surface obtained in step (2) were placed in an oven and dried at 105°C for 2 h. The mixture was then evenly mixed and placed in a twin-screw extruder for blending, extrusion and granulation to obtain the heat-resistant, high-strength nylon composite material. The temperature of the twin-screw extruder in zones 1 to 3 was 235°C, the temperature in zones 4 to 6 was 240°C, the temperature in zones 7 to 9 was 235°C, the die head temperature was 230°C, and the screw speed was 400 r / min.
[0040] Figure 2 The scanning electron microscope image of the cross section of the heat-resistant and high-strength nylon composite material shows that the composite filler is deeply embedded in the matrix and has better compatibility with the matrix, which is conducive to the transfer of stress and improves the thermal and mechanical properties of the composite material.
[0041] Example 3
[0042] A method for preparing a heat-resistant high-strength nylon composite material comprises the following steps:
[0043] (1) 2 g of nano-montmorillonite was ultrasonically dispersed in 200 g of water. After ultrasonication for 5 min, 98 g of sepiolite fiber was added and stirred at room temperature for 2 h for simple physical adsorption. The mixture was then filtered and dried to obtain a composite filler with a micro-nano structure.
[0044] (2) Pour 2.288 g of water, 7.347 g of ethanol, and 10 g of KH560 into a beaker, and stir evenly at 35° C. for 0.5 h to obtain a hydrolyzate. Place the hydrolyzate and the composite filler prepared in step (1) into a high-speed mixer, stir and mix for 0.5 h, and then take out and dry to obtain a composite filler with epoxy functional groups on the surface;
[0045] (3) 1200 g of nylon 6 and 300 g of the composite filler with epoxy functional groups on its surface obtained in step (2) were placed in an oven and dried at 105°C for 2 h. The mixture was then evenly mixed and placed in a twin-screw extruder for blending, extrusion and granulation to obtain the heat-resistant, high-strength nylon composite material. The temperature of the twin-screw extruder in zones 1 to 3 was 235°C, the temperature in zones 4 to 6 was 240°C, the temperature in zones 7 to 9 was 235°C, the die head temperature was 230°C, and the screw speed was 400 r / min.
[0046] Comparative Example 1
[0047] A method for preparing nylon material comprises the following steps: placing 1 kg of nylon 6 in an oven at 85°C for 2 hours, pouring it into an injection molding machine for injection molding, setting the processing temperature to 240°C and the injection molding pressure to 60 Bar.
[0048] Comparative Example 2
[0049] A method for preparing a nylon / micron inorganic fiber composite material comprises the following steps:
[0050] (1) Pour 2.288 g of water, 7.374 g of ethanol, and 10 g of KH560 into a beaker and stir evenly at 35 °C for 0.5 h to obtain a hydrolyzate. The hydrolyzate and 100 g of sepiolite fiber are placed in a high-speed mixer and stirred for 0.5 h before being taken out and dried to obtain a filler with epoxy functional groups on the surface.
[0051] (2) 1200 g of nylon 6 and 300 g of a filler with epoxy functional groups on its surface were placed in an oven and dried at 105°C for 2 h. The mixture was then evenly mixed and placed in a twin-screw extruder for blending, extrusion and granulation to obtain the nylon / micron inorganic fiber composite material. The temperature of the twin-screw extruder in zones 1 to 3 was 235°C, the temperature in zones 4 to 6 was 240°C, the temperature in zones 7 to 9 was 235°C, the die head temperature was 230°C, and the screw speed was 400 r / min.
[0052] Figure 3 The scanning electron microscope image of the cross section of the prepared nylon / micron inorganic fiber composite material shows that the bonding force between the micron inorganic fiber and the nylon matrix is not strong, holes appear between the interfaces, and stress concentration points are easily generated, which is not conducive to performance improvement.
[0053] The composite materials obtained in the above embodiments and comparative examples were subjected to performance tests. In accordance with the national standard GB / T 1634.1-2019, the composite materials were subjected to a heat deformation temperature test, with the sample size being 80 mm × 10 mm × 4 mm, the bending stress being 0.45 MPa, the standard deflection being 0.34 mm, the heating rate being 120 ° C / h, the temperature being raised to 27 ° C, maintained for 5 min, and then continued to be heated to 180 ° C; in accordance with the national standard GB / T 1633-2000, the composite materials were subjected to a Vicat softening temperature test, with the sample size being 40 mm × 10 mm × 4 mm, the load being 5000 g (including the weight of the rod), the needle penetration depth being 1 mm ± 0.01 mm, the heating rate being 120 ° C / h, the temperature being raised to 27 ° C, maintained for 5 min, and then continued to be heated to 210 ° C; in accordance with the national standard GB / T1040-2006, the composite materials were subjected to a tensile performance test, with the sample size being 80 mm × 10 mm×4 mm, the tensile rate is 50 mm / min; the bending performance test of the composite material is carried out in accordance with the national standard GB / T9341-2008, the sample size is 80 mm×10 mm×4 mm, and the bending rate is 2 mm / min.
[0054] The results are shown in Tables 2 and 3 below.
[0055] Table 2 Mechanical properties of the composite materials of various embodiments and comparative examples
[0056]
[0057] Table 3 Thermal properties of the composite materials of various embodiments and comparative examples
[0058]
[0059] From the analysis of Tables 2 and 3, it can be seen that when the nano-inorganic particles are 1.5 parts by weight and the micron inorganic fibers are 98.5 parts by weight, the mechanical properties and thermal properties of the prepared composite material are greatly improved after the composite filler is blended and extruded with nylon.
[0060] This is primarily due to the micro-nanostructure formed by the adsorption of nanoparticles onto the surface of micron-sized inorganic fibers. On the one hand, the nanoparticles adsorbed on the fiber surface create a physical barrier that effectively hinders or deflects the propagation path of microcracks within the composite material. On the other hand, they increase the surface roughness of the fiber, expanding the effective contact interface with the PA6 matrix and promoting uniform stress transfer across the interface, thereby significantly improving the material's mechanical properties. Furthermore, the anchoring effect of the nanoparticles on the micron-sized fiber surface inhibits the slippage of the matrix's molecular chains, reducing thermal resistance and accelerating the uniform diffusion of heat within the material, further enhancing the thermal stability of the nylon composite.
[0061] In contrast, when using only micron-sized inorganic fibers, the improvement in the performance of the composite material mainly depends on its own rigidity and lacks the above-mentioned micro-nano synergistic effect, so the performance improvement is limited.
[0062] The above description is only a preferred embodiment and is not intended to limit the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A heat-resistant and high-strength nylon composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 75-90 parts of nylon and 10-25 parts of composite filler; The composite filler is a composite filler with a micro-nano structure, which is formed by electrostatic self-assembly of nano-inorganic particles and micro-inorganic fibers, and the zeta potential of the nano-inorganic particles and the micro-inorganic fibers are opposite; The composite filler is surface-modified by a silane coupling agent, and has epoxy functional groups on the surface.
2. The heat-resistant and high-strength nylon composite material according to claim 1, characterized in that: The nylon is at least one of nylon 6 and nylon 66.
3. The heat-resistant and high-strength nylon composite material according to claim 1, characterized in that: The particle size of the nano inorganic particles is 200-500 nm, and the nano inorganic particles are at least one of nano montmorillonite, nano kaolin, and nano alumina.
4. The heat-resistant and high-strength nylon composite material according to claim 1, characterized in that: The diameter of the micron inorganic fiber is 1-5 μm, and the micron inorganic fiber is at least one of sepiolite fiber, palygorskite fiber, basalt fiber, and brucite fiber.
5. The heat-resistant and high-strength nylon composite material according to claim 1, characterized in that: In parts by weight, the composite filler comprises 1-2 parts of nano inorganic particles and 98-99 parts of micron inorganic fibers.
6. A method for preparing the heat-resistant and high-strength nylon composite material according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Ultrasonic dispersion of nano-inorganic particles in water, then adding micron inorganic fibers, stirring at room temperature, filtering and drying to obtain a composite filler with a micro-nano structure; (2) mixing water, ethanol, and a silane coupling agent to obtain a hydrolyzate, stirring the hydrolyzate and the composite filler obtained in step (1) in a high-speed mixer, and drying to obtain a composite filler having epoxy functional groups on its surface; (3) The nylon and the composite filler treated in step (2) are mixed evenly, dried, and then put into a twin-screw extruder for extrusion and granulation to obtain the heat-resistant and high-strength nylon composite material.
7. The method for preparing a heat-resistant and high-strength nylon composite material according to claim 6, characterized in that: In the step (2), the molar ratio of water to the silane coupling agent is (1-3):1, and the volume ratio of ethanol to the silane coupling agent is (1-3):
1.
8. The method for preparing a heat-resistant and high-strength nylon composite material according to claim 6 or 7, characterized in that: The silane coupling agent is KH560.
9. The method for preparing a heat-resistant and high-strength nylon composite material according to claim 6, characterized in that: In the step (2), water, ethanol and silane coupling agent are mixed and uniformly stirred at 30-40° C. for 0.3-1 h to obtain a hydrolyzed solution.
10. The method for preparing a heat-resistant and high-strength nylon composite material according to claim 6, characterized in that: In the step (3), the nylon and the composite filler are dried at 100-110° C. for 1-3 h and then mixed evenly.