A high content glass fiber composite based on nanocoated glass fibers and hyperbranched coupling

Abstract

This invention relates to a high-content glass fiber composite material based on nano-coated glass fiber and hyperbranched coupling, belonging to the technical field of glass fiber products. The high-content glass fiber composite material uses glass fiber as a skeleton, with a nano-layer coated on the surface of the glass fiber to form a cross-linked network with a hyperbranched coupling agent, resulting in a high-content glass fiber composite material. The nano-layer, by weight, comprises 35-45 parts tetraethyl orthosilicate, 1-3 parts quercetin, 1-4 parts kaempferol, 6-12 parts carbon nanotubes, 5-15 parts lignin, 3-6 parts chlorogenic acid, 20-25 parts ethanol, and 18-32 parts deionized water. The nano-layer coating on the surface of the glass fiber forms anchor points on the outer surface of the glass fiber, forming a cross-linked network with the hyperbranched coupling agent, exhibiting strong tensile strength. When subjected to compressive load, the nano-coated glass fiber can effectively disperse pressure, preventing material deformation and damage.

Description

Technical Field

[0001] This invention belongs to the field of glass fiber product technology, specifically relating to a high-content glass fiber composite material based on nano-coated glass fiber and hyperbranched coupling. Background Technology

[0002] Glass fiber is a high-performance inorganic non-metallic material with advantages such as good insulation, strong heat resistance, good corrosion resistance, and high mechanical strength. However, it is brittle and has poor wear resistance.

[0003] To change this situation, glass fiber is usually combined with a resin matrix. The toughness mainly comes from the resin matrix. The composite material prepared by simply combining glass fiber and resin matrix may break rather than undergo plastic deformation when subjected to violent impact or impact from a sharp object after hardening. When it breaks, it may produce sharp fragments. These fragments are not only sharp and dangerous, but also carry a large amount of fine glass fiber dust. This dust can irritate the respiratory tract and skin, causing itching and allergies. Summary of the Invention

[0004] The purpose of this invention is to provide a high-content glass fiber composite material based on nano-coated glass fiber and hyperbranched coupling in order to solve the above-mentioned problems.

[0005] The present invention achieves the above objectives through the following technical solution: This invention provides a high-content glass fiber composite material based on nano-coated glass fiber and hyperbranched coupling. The high-content glass fiber composite material uses glass fiber as a skeleton, and after coating the surface of the glass fiber with a nano-layer, a cross-linking network is formed between the glass fiber and the hyperbranched coupling agent to obtain the high-content glass fiber composite material. The nanolayers are prepared by weight of 35-45 parts tetraethyl orthosilicate, 1-3 parts quercetin, 1-4 parts kaempferol, 6-12 parts carbon nanotubes, 5-15 parts lignin, 3-6 parts chlorogenic acid, 20-25 parts ethanol and 18-32 parts deionized water.

[0006] As a further optimization of the present invention, the preparation process of the nano-coating layer on the surface of the glass fiber is as follows: (a) Tetraethyl orthosilicate, carbon nanotubes, ethanol and deionized water are mixed and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, lignin is added and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, inorganic silica sol is obtained. (ii) Add quercetin, kaempferol and chlorogenic acid to the inorganic silica sol, heat to 30-40℃, stir at 125r / min for 20min to obtain an organic dispersion; (iii) Mix the inorganic silica sol and the organic dispersion at a stirring speed of 550 r / min, and after uniform mixing, stir at 350 r / min for 2-4 h at a temperature of 40-50℃ to obtain the preform; (iv) The preform is sealed and left to stand at 25℃ for 18-24 hours to obtain the coating solution; (v) The glass fiber is cleaned and then calcined at a high temperature of 450-550℃ to obtain pretreated glass fiber; (vi) Immerse the pretreated glass fiber into the sol at a speed of 5-8 mm / s, stay for 30-45s, and then pull it out steadily at a speed of 1-5 mm / s to form a uniform liquid film on the surface of the glass fiber. (vii) Place the pulled-out glass fiber in the air for 30-45 minutes, during which the humidity is controlled at 95% and the temperature is controlled at 20℃; (viii) After the placement time is over, the glass fiber is heat-treated to obtain glass fiber with a nano-layer coating.

[0007] As a further optimization of the present invention, the specific method for heat treatment of glass fiber is as follows: first, the temperature is raised from 20°C to 450-550°C at a rate of 10°C / min, held for 30 minutes, and then cooled to 25°C at a rate of 5°C / min.

[0008] As a further optimization of the present invention, the raw materials for preparing the hyperbranched coupling agent, by weight, include: 60-80 parts epoxy resin, 5-10 parts dioctyl adipate, 2-3 parts titanium dioxide powder, and 4-8 parts tea polyphenols.

[0009] As a further optimization of the present invention, the preparation process of the hyperbranched coupling agent is as follows: the epoxy resin is preheated at 55°C, dioctyl adipate is added at a stirring speed of 125 r / min, and stirring is continued for 30 min. Titanium dioxide powder is added, and stirring is carried out at 350 r / min for 50 min. Tea polyphenols are added and stirring is carried out at 120 r / min for 20 min. After stirring, the mixture is transferred to a vacuum mixer and degassed at -0.095 MPa for 15-30 min to obtain the hyperbranched coupling agent.

[0010] As a further optimization of the present invention, the mass ratio between the nano-coated glass fiber and the hyperbranched coupling agent is 0.5-0.7:1.

[0011] As a further optimization of the present invention, the formation process of the cross-linked network is as follows: (a) Dissolve the hyperbranched coupling agent in N,N-dimethylformamide to obtain a hyperbranched coupling solution; (ii) The glass fiber coated with nanolayer is immersed in hyperbranched coupling solution and pulled out steadily at a speed of 3 mm / s. After being pulled out, the temperature is first raised from 20℃ to 100-120℃ at a rate of 1℃ / min and kept at that temperature for 30 min. Then, it is cooled to 25℃ at a rate of 5℃ / min to form a cross-linked network, thus obtaining a high-content glass fiber composite material.

[0012] As a further optimization of the present invention, the mass ratio of hyperbranched coupling agent to N,N-dimethylformamide is 1:50.

[0013] The beneficial effects of the present invention are as follows: The surface of the glass fiber is coated with a nano-layer, which forms anchor points on the outer surface of the glass fiber and forms a cross-linking network with the hyperbranched coupling agent, exhibiting strong tensile strength. When subjected to compressive load, the glass fiber coated with the nano-layer can effectively disperse the pressure and prevent the material from deforming and breaking. When subjected to bending load, it can withstand a large degree of bending without breaking, exhibiting high bending strength. When subjected to shear force, it can resist the damage of shear force. The high-fiberglass composite material prepared in this invention exhibits minimal changes in shape and size after immersion in humid environments or water, allowing for long-term outdoor use and making it suitable for use in some outdoor products. Furthermore, it maintains its rigidity and load-bearing capacity at higher temperatures without softening or deforming, enabling the products to operate continuously within a high temperature range and broadening its application areas. Detailed Implementation

[0014] The present application will now be described in further detail. It should be noted that the specific embodiments are only used to further illustrate the present application and should not be construed as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application based on the above content.

[0015] Unless otherwise specified, all methods used in this invention are conventional methods known to those skilled in the art, and all reagents and materials used are commercially available products.

[0016] Example 1 The preparation process of the nano-coating layer on the surface of glass fiber is as follows: 35 parts of tetraethyl orthosilicate, 6 parts of carbon nanotubes, 20 parts of ethanol and 18 parts of deionized water were mixed and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, 5 parts of lignin were added and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, inorganic silica sol was obtained. Add 1 part quercetin, 1 part kaempferol and 3 parts chlorogenic acid to inorganic silica sol, heat to 30°C, stir at 125 r / min for 20 min to obtain organic dispersion; Inorganic silica sol and organic dispersion were mixed at a stirring speed of 550 r / min and then stirred at 350 r / min for 2 h at 40℃ to obtain the preform. The preform was sealed and left to stand for 18 hours at 25°C to obtain the coating solution; The glass fiber is cleaned and then calcined at 450℃ to obtain pretreated glass fiber. The pretreated glass fiber was immersed in the sol at a speed of 5 mm / s, held for 30 seconds, and then pulled out steadily at a speed of 1 mm / s, forming a uniform liquid film on the surface of the glass fiber. The pulled-out glass fiber was placed in the air for 30 minutes, during which the humidity was controlled at 95% and the temperature at 20℃. After the placement time was over, the glass fiber was first heated from 20°C to 450°C at a rate of 10°C / min, held at that temperature for 30 minutes, and then cooled to 25°C at a rate of 5°C / min to obtain glass fiber with a nano-layer coating. The preparation process of hyperbranched coupling agents is as follows: Preheat 60 parts of epoxy resin at 55℃, add 5 parts of dioctyl adipate at a stirring speed of 125r / min, continue stirring for 30min, add 2 parts of titanium dioxide powder, stir at 350r / min for 50min, add 4 parts of tea polyphenols and stir at 120r / min for 20min, after stirring, transfer to a vacuum mixer, degas at -0.095 MPa for 15min to obtain hyperbranched coupling agent; The formation process of cross-linked networks is as follows: The hyperbranched coupling agent was dissolved in N,N-dimethylformamide (the mass ratio of hyperbranched coupling agent to N,N-dimethylformamide was 1:50) to obtain a hyperbranched coupling solution. The glass fibers coated with nanolayers were immersed in a hyperbranched coupling solution (the mass ratio of the glass fibers coated with nanolayers to the hyperbranched coupling agent was 0.5:1), and then steadily pulled out at a speed of 3 mm / s. After being pulled out, the temperature was first raised from 20°C to 100°C at a rate of 1°C / min and held for 30 min. Then, it was cooled to 25°C at a rate of 5°C / min to form a cross-linked network, thus obtaining a high-content glass fiber composite material.

[0017] Example 2 The preparation process of the nano-coating layer on the surface of glass fiber is as follows: 45 parts of tetraethyl orthosilicate, 12 parts of carbon nanotubes, 25 parts of ethanol and 32 parts of deionized water were mixed and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, 15 parts of lignin were added and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, inorganic silica sol was obtained. Add 3 parts quercetin, 4 parts kaempferol and 6 parts chlorogenic acid to inorganic silica sol, heat to 40℃, stir at 125 r / min for 20 min to obtain organic dispersion; Inorganic silica sol and organic dispersion were mixed at a stirring speed of 550 r / min and then stirred at 350 r / min for 4 h at 50 °C to obtain the preform. The preform was sealed and left to stand for 24 hours at 25°C to obtain the coating solution; The glass fiber is cleaned and then calcined at 550℃ to obtain pretreated glass fiber. The pretreated glass fiber was immersed in the sol at a speed of 8 mm / s, held for 45 seconds, and then pulled out steadily at a speed of 5 mm / s, forming a uniform liquid film on the surface of the glass fiber. The pulled-out glass fiber was placed in the air for 45 minutes, during which the humidity was controlled at 95% and the temperature at 20℃. After the placement time was over, the glass fiber was first heated from 20°C to 550°C at a rate of 10°C / min, held at that temperature for 30 minutes, and then cooled to 25°C at a rate of 5°C / min to obtain glass fiber with a nano-layer coating. The preparation process of hyperbranched coupling agents is as follows: 80 parts of epoxy resin were preheated at 55℃, and 10 parts of dioctyl adipate were added at a stirring speed of 125 r / min. The mixture was stirred for 30 min, then 3 parts of titanium dioxide powder were added and stirred at 350 r / min for 50 min. Finally, 8 parts of tea polyphenols were added and stirred at 120 r / min for 20 min. After stirring, the mixture was transferred to a vacuum mixer and degassed at -0.095 MPa for 30 min to obtain a hyperbranched coupling agent. The formation process of cross-linked networks is as follows: The hyperbranched coupling agent was dissolved in N,N-dimethylformamide (the mass ratio of hyperbranched coupling agent to N,N-dimethylformamide was 1:50) to obtain a hyperbranched coupling solution. The glass fibers coated with nanolayers were immersed in a hyperbranched coupling solution (the mass ratio of the glass fibers coated with nanolayers to the hyperbranched coupling agent was 0.7:1), and then steadily pulled out at a speed of 3 mm / s. After being pulled out, the temperature was first raised from 20°C to 120°C at a rate of 1°C / min and held for 30 min. Then, it was cooled to 25°C at a rate of 5°C / min to form a cross-linked network, thus obtaining a high-content glass fiber composite material.

[0018] Example 3 The preparation process of the nano-coating layer on the surface of glass fiber is as follows: 35 parts of tetraethyl orthosilicate, 6 parts of carbon nanotubes, 20 parts of ethanol and 18 parts of deionized water were mixed and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, 5 parts of lignin were added and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, inorganic silica sol was obtained. Add 1 part quercetin, 1 part kaempferol and 3 parts chlorogenic acid to inorganic silica sol, heat to 30°C, stir at 125 r / min for 20 min to obtain organic dispersion; Inorganic silica sol and organic dispersion were mixed at a stirring speed of 550 r / min and then stirred at 350 r / min for 2 h at 40℃ to obtain the preform. The preform was sealed and left to stand for 18 hours at 25°C to obtain the coating solution; The glass fiber is cleaned and then calcined at 450℃ to obtain pretreated glass fiber. The pretreated glass fiber was immersed in the sol at a speed of 5 mm / s, held for 30 seconds, and then pulled out steadily at a speed of 1 mm / s, forming a uniform liquid film on the surface of the glass fiber. The pulled-out glass fiber was placed in the air for 30 minutes, during which the humidity was controlled at 95% and the temperature at 20℃. After the placement time was over, the glass fiber was first heated from 20°C to 450°C at a rate of 10°C / min, held at that temperature for 30 minutes, and then cooled to 25°C at a rate of 5°C / min to obtain glass fiber with a nano-layer coating. The preparation process of hyperbranched coupling agents is as follows: Preheat 60 parts of epoxy resin at 55℃, add 5 parts of dioctyl adipate at a stirring speed of 125r / min, continue stirring for 30min, add 2 parts of titanium dioxide powder, stir at 350r / min for 50min, add 4 parts of tea polyphenols and stir at 120r / min for 20min, after stirring, transfer to a vacuum mixer, degas at -0.095 MPa for 15min to obtain hyperbranched coupling agent; The formation process of cross-linked networks is as follows: The hyperbranched coupling agent was dissolved in N,N-dimethylformamide (the mass ratio of hyperbranched coupling agent to N,N-dimethylformamide was 1:50) to obtain a hyperbranched coupling solution. The glass fibers coated with nanolayers were immersed in a hyperbranched coupling solution (the mass ratio of the glass fibers coated with nanolayers to the hyperbranched coupling agent was 0.7:1), and then steadily pulled out at a speed of 3 mm / s. After being pulled out, the temperature was first raised from 20°C to 100°C at a rate of 1°C / min and held for 30 min. Then, it was cooled to 25°C at a rate of 5°C / min to form a cross-linked network, thus obtaining a high-content glass fiber composite material.

[0019] Comparative Example 1 The preparation process of the nano-coating layer on the surface of glass fiber is as follows: 35 parts of tetraethyl orthosilicate, 6 parts of carbon nanotubes, 20 parts of ethanol and 18 parts of deionized water were mixed and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, 5 parts of lignin were added and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, inorganic silica sol was obtained. Add 1 part quercetin, 1 part kaempferol and 3 parts chlorogenic acid to inorganic silica sol, heat to 30°C, stir at 125 r / min for 20 min to obtain organic dispersion; Inorganic silica sol and organic dispersion were mixed at a stirring speed of 550 r / min and then stirred at 350 r / min for 2 h at 40℃ to obtain the preform. The preform was sealed and left to stand for 18 hours at 25°C to obtain the coating solution; The glass fiber is cleaned and then calcined at 450℃ to obtain pretreated glass fiber. The pretreated glass fiber was immersed in the sol at a speed of 5 mm / s, held for 30 seconds, and then pulled out steadily at a speed of 1 mm / s, forming a uniform liquid film on the surface of the glass fiber. The pulled-out glass fiber was placed in the air for 30 minutes, during which the humidity was controlled at 95% and the temperature at 20℃. After the placement time was over, the glass fiber was first heated from 20°C to 450°C at a rate of 10°C / min, held at that temperature for 30 minutes, and then cooled to 25°C at a rate of 5°C / min to obtain glass fiber with a nano-layer coating. The preparation process of hyperbranched coupling agents is as follows: Preheat 60 parts of epoxy resin at 55℃, add 5 parts of dioctyl adipate at a stirring speed of 125r / min, continue stirring for 30min, add 2 parts of titanium dioxide powder, stir at 350r / min for 50min, add 4 parts of tea polyphenols and stir at 120r / min for 20min, after stirring, transfer to a vacuum mixer, degas at -0.095 MPa for 15min to obtain hyperbranched coupling agent; The formation process of cross-linked networks is as follows: The hyperbranched coupling agent was dissolved in N,N-dimethylformamide (the mass ratio of hyperbranched coupling agent to N,N-dimethylformamide was 1:50) to obtain a hyperbranched coupling solution. The glass fibers coated with nanolayers were immersed in a hyperbranched coupling solution (the mass ratio of the glass fibers coated with nanolayers to the hyperbranched coupling agent was 0.4:1), and then steadily pulled out at a speed of 3 mm / s. After being pulled out, the temperature was first raised from 20°C to 100°C at a rate of 1°C / min and held for 30 min. Then, it was cooled to 25°C at a rate of 5°C / min to form a cross-linked network, thus obtaining a high-content glass fiber composite material.

[0020] Comparative Example 2 The preparation process of the nano-coating layer on the surface of glass fiber is as follows: 35 parts of tetraethyl orthosilicate, 6 parts of carbon nanotubes, 20 parts of ethanol and 18 parts of deionized water were mixed and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, 5 parts of lignin were added and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, inorganic silica sol was obtained. Add 1 part quercetin, 1 part kaempferol and 3 parts chlorogenic acid to inorganic silica sol, heat to 30°C, stir at 125 r / min for 20 min to obtain organic dispersion; Inorganic silica sol and organic dispersion were mixed at a stirring speed of 550 r / min and then stirred at 350 r / min for 2 h at 40℃ to obtain the preform. The preform was sealed and left to stand for 18 hours at 25°C to obtain the coating solution; The glass fiber is cleaned and then calcined at 450℃ to obtain pretreated glass fiber. The pretreated glass fiber was immersed in the sol at a speed of 5 mm / s, held for 30 seconds, and then pulled out steadily at a speed of 1 mm / s, forming a uniform liquid film on the surface of the glass fiber. The pulled-out glass fiber was placed in the air for 30 minutes, during which the humidity was controlled at 95% and the temperature at 20℃. After the placement time was over, the glass fiber was first heated from 20°C to 450°C at a rate of 10°C / min, held at that temperature for 30 minutes, and then cooled to 25°C at a rate of 5°C / min to obtain glass fiber with a nano-layer coating. The preparation process of hyperbranched coupling agents is as follows: Preheat 60 parts of epoxy resin at 55℃, add 5 parts of dioctyl adipate at a stirring speed of 125r / min, continue stirring for 30min, add 2 parts of titanium dioxide powder, stir at 350r / min for 50min, add 4 parts of tea polyphenols and stir at 120r / min for 20min, after stirring, transfer to a vacuum mixer, degas at -0.095 MPa for 15min to obtain hyperbranched coupling agent; The formation process of cross-linked networks is as follows: The hyperbranched coupling agent was dissolved in N,N-dimethylformamide (the mass ratio of hyperbranched coupling agent to N,N-dimethylformamide was 1:50) to obtain a hyperbranched coupling solution. The glass fibers coated with nanolayers were immersed in a hyperbranched coupling solution (the mass ratio of the glass fibers coated with nanolayers to the hyperbranched coupling agent was 0.8:1), and then steadily pulled out at a speed of 3 mm / s. After being pulled out, the temperature was first raised from 20°C to 100°C at a rate of 1°C / min and held for 30 min. Then, it was cooled to 25°C at a rate of 5°C / min to form a cross-linked network, thus obtaining a high-content glass fiber composite material.

[0021] Comparative Example 3 The preparation process of the nano-coating layer on the surface of glass fiber is as follows: 35 parts of tetraethyl orthosilicate, 6 parts of carbon nanotubes, 20 parts of ethanol and 18 parts of deionized water were mixed and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, 5 parts of lignin were added and ultrasonically treated with 350W power for 30 minutes. After ultrasonic treatment, inorganic silica sol was obtained. Add 1 part quercetin, 1 part kaempferol and 3 parts chlorogenic acid to inorganic silica sol, heat to 30°C, stir at 125 r / min for 20 min to obtain organic dispersion; Inorganic silica sol and organic dispersion were mixed at a stirring speed of 550 r / min and then stirred at 350 r / min for 2 h at 40℃ to obtain the preform. The preform was sealed and left to stand for 18 hours at 25°C to obtain the coating solution; The glass fiber is cleaned and then calcined at 450℃ to obtain pretreated glass fiber. The pretreated glass fiber was immersed in the sol at a speed of 5 mm / s, held for 30 seconds, and then pulled out steadily at a speed of 1 mm / s, forming a uniform liquid film on the surface of the glass fiber. The pulled-out glass fiber was placed in the air for 30 minutes, during which the humidity was controlled at 95% and the temperature at 20℃. After the placement time was over, the glass fiber was first heated from 20°C to 450°C at a rate of 10°C / min, held at that temperature for 30 minutes, and then cooled to 25°C at a rate of 5°C / min to obtain glass fiber with a nano-layer coating. The preparation process of hyperbranched coupling agents is as follows: Preheat 60 parts of polyurethane resin at 55℃, add 5 parts of dioctyl adipate at a stirring speed of 125r / min, continue stirring for 30min, add 2 parts of titanium dioxide powder, stir at 350r / min for 50min, add 4 parts of tea polyphenols and stir at 120r / min for 20min, after stirring, transfer to a vacuum mixer, degas at -0.095 MPa for 15min to obtain hyperbranched coupling agent; The formation process of cross-linked networks is as follows: The hyperbranched coupling agent was dissolved in N,N-dimethylformamide (the mass ratio of hyperbranched coupling agent to N,N-dimethylformamide was 1:50) to obtain a hyperbranched coupling solution. The glass fibers coated with nanolayers were immersed in a hyperbranched coupling solution (the mass ratio of the glass fibers coated with nanolayers to the hyperbranched coupling agent was 0.7:1), and then steadily pulled out at a speed of 3 mm / s. After being pulled out, the temperature was first raised from 20°C to 100°C at a rate of 1°C / min and held for 30 min. Then, it was cooled to 25°C at a rate of 5°C / min to form a cross-linked network, thus obtaining a high-content glass fiber composite material.

[0022] Comparative Example 4 The preparation process of hyperbranched coupling agents is as follows: Preheat 60 parts of epoxy resin at 55℃, add 5 parts of dioctyl adipate at a stirring speed of 125r / min, continue stirring for 30min, add 2 parts of titanium dioxide powder, stir at 350r / min for 50min, add 4 parts of tea polyphenols and stir at 120r / min for 20min, after stirring, transfer to a vacuum mixer, degas at -0.095 MPa for 15min to obtain hyperbranched coupling agent; The formation process of cross-linked networks is as follows: The hyperbranched coupling agent was dissolved in N,N-dimethylformamide (the mass ratio of hyperbranched coupling agent to N,N-dimethylformamide was 1:50) to obtain a hyperbranched coupling solution. Glass fibers were immersed in a hyperbranched coupling solution (the mass ratio of glass fiber to hyperbranched coupling agent was 0.7:1) and steadily pulled out at a speed of 3 mm / s. After pulling out, the temperature was first raised from 20°C to 100°C at a rate of 1°C / min and held for 30 min, then cooled to 25°C at a rate of 5°C / min. A cross-linked network was formed, resulting in a high-content glass fiber composite material.

[0023] Performance testing The tensile properties of high-glass fiber composite materials prepared by the methods in Examples 1-3 and Comparative Examples 1-4 were tested according to the test methods in GB / T 1447-2005 "Test Method for Tensile Properties of Fiber Reinforced Plastics". The bending properties of high-glass fiber composite materials prepared by the methods in Examples 1-3 and Comparative Examples 1-4 were tested according to the test methods in GB / T 1449-2005 "Test Method for Bending Properties of Fiber Reinforced Plastics". The compressive properties of high-glass fiber composites prepared by the methods in Examples 1-3 and Comparative Examples 1-4 were tested according to the test methods in GB / T 1448-2005 "Test Method for Compression Properties of Fiber Reinforced Plastics". The shear strength of the high-glass fiber composite materials prepared by the methods in Examples 1-3 and Comparative Examples 1-4 was tested according to the test methods in GB / T 1450.1-2005 "Test Method for Interlaminar Shear Strength of Fiber Reinforced Plastics". The impact toughness of high-fiber composite materials prepared by the methods in Examples 1-3 and Comparative Examples 1-4 was tested according to the test methods in GB / T 1451-2005 "Test Method for Impact Toughness of Fiber Reinforced Plastics in Simply Supported Beams".

[0024] The test results are shown in Table 1. Table 1 As shown in Table 1, the high-content glass fiber composite materials prepared by the methods in Examples 1-3 exhibit better mechanical performance than those in Comparative Examples 1-4 in mechanical testing. The nano-coated glass fibers have high tensile strength and can withstand large tensile forces without breaking. When these nano-coated glass fibers are uniformly distributed in the material, they act like closely arranged steel bars, providing strong support for the material. When subjected to compressive loads, the nano-coated glass fibers can effectively disperse the pressure, preventing the material from deforming and breaking. When subjected to bending loads, the material can withstand a large degree of bending without breaking, exhibiting high bending strength. Due to the tight bond between the fiber and the hyperbranched coupling agent and the inherent properties of the nano-coated glass fibers, the nano-coated glass fibers exhibit strong shear resistance. When subjected to shear force, the interface between the nano-coated glass fibers and the hyperbranched coupling agent can effectively transfer shear stress, enabling the entire material to resist shear failure.

[0025] The water absorption of high-glass fiber composite materials prepared by the methods in Examples 1-3 and Comparative Examples 1-4 was tested according to the test methods in GB / T 1462-2005 "Test Method for Water Absorption of Fiber Reinforced Plastics". The heat distortion temperature of the high-content glass fiber composite materials prepared by the methods in Examples 1-3 and Comparative Examples 1-4 was tested according to the test method in GB / T 1634.2-2004 "Determination of Deformation Temperature of Plastics under Load".

[0026] The test results are shown in Table 2. Table 2 As can be seen from Table 2, the high-content glass fiber composite materials prepared by the methods of Examples 1-3 have less water absorption. Compared with Comparative Examples 1-4, it can be seen that this is related to the amount of glass fiber added and the type of resin used. The high-content glass fiber composite materials prepared by the methods of Examples 1-3 also have better heat distortion temperature performance than the high-content glass fiber composite materials prepared by the methods of Comparative Examples 1-4. It can be seen that the heat distortion temperature of Comparative Example 2 is close to that of Examples 1-3, but it is still lower than that of Examples 1-3. It can be seen that simply increasing the glass fiber content cannot improve the performance of high-content glass fiber composite materials.

[0027] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A high-content glass fiber composite material based on nano-coated glass fiber and hyperbranched coupling, characterized in that, The high-content glass fiber composite material uses glass fiber as a skeleton, and after coating the surface of the glass fiber with a nano-layer, a cross-linking network is formed between the glass fiber and the hyperbranched coupling agent to obtain the high-content glass fiber composite material. The nanolayers are prepared by weight of 35-45 parts tetraethyl orthosilicate, 1-3 parts quercetin, 1-4 parts kaempferol, 6-12 parts carbon nanotubes, 5-15 parts lignin, 3-6 parts chlorogenic acid, 20-25 parts ethanol and 18-32 parts deionized water. The raw materials for preparing the hyperbranched coupling agent, by weight, include: 60-80 parts epoxy resin, 5-10 parts dioctyl adipate, 2-3 parts titanium dioxide powder, and 4-8 parts tea polyphenols. The preparation process of the hyperbranched coupling agent is as follows: the epoxy resin is preheated at 55°C, dioctyl adipate is added at a stirring speed of 125 r / min and stirred continuously for 30 min, titanium dioxide powder is added and stirred at 350 r / min for 50 min, tea polyphenols are added and stirred at 120 r / min for 20 min, after stirring is completed, the mixture is transferred to a vacuum mixer and degassed at -0.095 MPa for 15-30 min to obtain the hyperbranched coupling agent.

2. The high-content glass fiber composite material based on nano-coated glass fiber and hyperbranched coupling according to claim 1, characterized in that, The preparation process of the nano-coating layer on the surface of the glass fiber is as follows: (a) Tetraethyl orthosilicate, carbon nanotubes, ethanol and deionized water are mixed and ultrasonically treated with 350W power for 30min. After ultrasonic treatment, lignin is added and ultrasonically treated with 350W power for 30min. After ultrasonic treatment, inorganic silica sol is obtained. (ii) Add quercetin, kaempferol and chlorogenic acid to the inorganic silica sol, heat to 30-40℃, stir at 125r / min for 20min to obtain an organic dispersion; (iii) Mix the inorganic silica sol and the organic dispersion at a stirring speed of 550 r / min, and after uniform mixing, stir at 350 r / min for 2-4 h at a temperature of 40-50℃ to obtain the preform; (iv) The preform is sealed and left to stand at 25℃ for 18-24 hours to obtain the coating solution; (v) The glass fiber is cleaned and then calcined at a high temperature of 450-550℃ to obtain pretreated glass fiber; (vi) Immerse the pretreated glass fiber into the coating solution at a speed of 5-8 mm / s, stay for 30-45s, and then pull it out steadily at a speed of 1-5 mm / s to form a uniform liquid film on the surface of the glass fiber. (vii) Place the pulled-out glass fiber in the air for 30-45 minutes, during which the humidity is controlled at 95% and the temperature is controlled at 20℃; (viii) After the placement time is over, the glass fiber is heat-treated to obtain glass fiber with a nano-layer coating.

3. The high-content glass fiber composite material based on nano-coated glass fiber and hyperbranched coupling according to claim 2, characterized in that, The specific method for heat treatment of the glass fiber is as follows: first, the temperature is raised from 20°C to 450-550°C at a rate of 10°C / min, held for 30 minutes, and then cooled to 25°C at a rate of 5°C / min.

4. The high-content glass fiber composite material based on nano-coated glass fiber and hyperbranched coupling according to claim 3, characterized in that, The mass ratio of the glass fiber coated with the nanolayer to the hyperbranched coupling agent is 0.5-0.7:

1.

5. The high-content glass fiber composite material based on nano-coated glass fiber and hyperbranched coupling according to claim 4, characterized in that, The formation process of the cross-linked network is as follows: (a) Dissolve the hyperbranched coupling agent in N,N-dimethylformamide to obtain a hyperbranched coupling solution; (ii) The glass fiber coated with nanolayer is immersed in hyperbranched coupling solution and pulled out steadily at a speed of 3 mm / s. After being pulled out, the temperature is first raised from 20℃ to 100-120℃ at a rate of 1℃ / min and kept at that temperature for 30 min. Then, it is cooled to 25℃ at a rate of 5℃ / min to form a cross-linked network, thus obtaining a high-content glass fiber composite material.

6. The high-content glass fiber composite material based on nano-coated glass fiber and hyperbranched coupling according to claim 5, characterized in that, The mass ratio of the hyperbranched coupling agent to N,N-dimethylformamide is 1:50.

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