High-heat-resistance halogen-free flame-retardant nylon material and preparation method thereof

Abstract

The invention belongs to the technical field of nylon materials, and particularly relates to a high-heat-resistance halogen-free flame-retardant nylon material and a preparation method thereof. According to the invention, PA6 and PA66 base materials are compounded by utilizing the high heat resistance of PA66 and the processability advantage of PA6, and the heat deformation temperature of the material is improved through the synergistic effect of the modified glass fiber reinforcing agent and the antioxidant, so that the heat-resistant requirements of high-end scenes such as new energy automobile battery components and high-temperature electronic components are met. Halogen flame retardants are completely abandoned, the modified halogen-free flame retardant is adopted, the flame retardant effect is achieved, meanwhile, no harmful halogen hydride gas or dioxin is released during combustion, and the material still keeps excellent rigidity and toughness on the basis of high flame retardance and high heat resistance and is suitable for popularization and application. The problem that the mechanical property of a traditional halogen-free flame retardant is reduced due to high addition amount is solved.

Description

Technical Field

[0001] This invention belongs to the field of nylon material technology, specifically relating to a high heat-resistant, halogen-free flame-retardant nylon material and its preparation method. Background Technology

[0002] Nylon and polyamide (PA) materials are widely used in electronics, automotive, aerospace and other fields due to their excellent mechanical properties, wear resistance, chemical resistance and good processing performance. However, traditional nylon materials have the disadvantages of low limiting oxygen index (LOI) and easy combustion. During combustion, they release a large amount of toxic fumes and corrosive hydrogen halide gases, posing a serious threat to personal safety and the environment.

[0003] Currently, the main methods for improving the flame retardant properties of nylon include adding halogenated flame retardants (such as brominated polystyrene and decabromodiphenyl ether) and halogen-free flame retardants (such as red phosphorus, metal hydroxides, and nitrogen-phosphorus flame retardants). While halogenated flame retardants are highly efficient, they produce toxic gases (such as dioxins) during combustion and have been restricted by regulations such as the EU RoHS. Halogen-free flame retardants, on the other hand, require high dosages, have poor compatibility with the matrix, and exhibit poor heat resistance, leading to a significant reduction in the toughness and strength of the composite material, and a decrease in flame retardant efficiency at high temperatures. Furthermore, the heat distortion temperature (HDT) of existing halogen-free flame-retardant nylon materials is typically below 150°C, making it difficult to meet the dual requirements of high-end applications (such as new energy vehicle battery components and high-temperature electronic components) for both heat resistance (HDT > 200°C) and flame retardancy (UL94 V-0 rating).

[0004] Therefore, it is urgent to develop a nylon material that combines high heat resistance, excellent halogen-free flame retardancy, and good overall performance. Summary of the Invention

[0005] The purpose of this invention is to address existing problems by providing a high heat-resistant, halogen-free flame-retardant nylon material and its preparation method.

[0006] This invention is achieved through the following technical solution: A high heat-resistant, halogen-free, flame-retardant nylon material is composed of the following components in parts by weight: 30-40 parts of nylon PA6, 10-20 parts of nylon PA66, 20-40 parts of modified glass fiber, 10-20 parts of modified flame retardant, 2-4 parts of toughening agent, 0.08-0.12 parts of antioxidant 1098, 0.15-0.25 parts of antioxidant 9228, 0.2-0.4 parts of stabilizer, 0.2-0.4 parts of flow modifier, and 0.4-0.6 parts of calcium stearate.

[0007] Furthermore, the preparation of the modified glass fiber includes the following steps: (1) After drying the 568H glass fiber at 100~110℃ for 2~3h, place it in a low-temperature oxygen plasma for 5~10min; (2) The plasma-treated glass fiber was immersed in a 2.5-3.5 wt% γ-aminopropyltriethoxysilane ethanol solution and stirred at 65-75°C and 200-300 rpm for 4-5 h. After the reaction was completed, it was washed 3-4 times with anhydrous ethanol and then vacuum dried at 100-110°C for 6-7 h to obtain aminated glass fiber. (3) The above-mentioned aminated glass fiber was dispersed in toluene at a solid-liquid ratio of 1g:15~20mL, and then 1.2 times the molar amount of glycidyl methacrylate (GMA) relative to KH550 was added. Under N2 protection, the mixture was stirred at 90℃ and 200~300rpm for 8~9h. After the reaction was completed, the unreacted GMA was thoroughly washed with toluene to remove it. Finally, the mixture was vacuum dried at 80~90℃ to constant weight to obtain the modified glass fiber.

[0008] Furthermore, in step (1), the low-temperature plasma treatment is set to a vacuum of 5 Pa, an oxygen flow rate of 20-25 sccm, and a power of 150 W.

[0009] Furthermore, the preparation of the modified flame retardant includes the following steps: 1) Dissolve citric acid and chitosan in a 1.5wt% dilute acetic acid aqueous solution at a mass ratio of 2:1, with the citric acid concentration being 5wt%. Stir at 60~65℃ until completely dissolved to obtain a citric acid-chitosan solution. 2) Disperse PL-502 flame retardant powder in deionized water at a solid-liquid ratio of 1g:8~10mL, add 3% polyvinyl alcohol (PVA 1788) by mass of PL-502, and stir at 200~300rpm for 30~40min to obtain a suspension. 3) Add 20% of the citric acid-chitosan solution by mass of PL-502 to the suspension at a rate of 1-1.5 mL / min. Raise the temperature of the system to 80-85℃, add 5% of sodium phytate by mass of PL-502, and stir at 300-400 rpm for 3-5 hours. 4) Adjust the pH to 7.0 with 10wt% sodium hydroxide solution, let stand for 30-35 minutes, filter, wash with deionized water and ethanol 3-4 times in sequence, and vacuum dry at 60-65℃ for 10-12 hours.

[0010] Furthermore, the toughening agent is a maleic anhydride-grafted ethylene-octene copolymer.

[0011] Furthermore, the toughening agent is Jia Yi Rong CMG5805.

[0012] Furthermore, the stabilizer is a copper heat stabilizer.

[0013] Furthermore, the stabilizer is Clariant Seed.

[0014] Furthermore, the flow modifier is a lubricating flow aid.

[0015] Furthermore, the flow modifier is CYD-C603A.

[0016] A method for preparing a high heat-resistant, halogen-free, flame-retardant nylon material includes the following steps: S1. Weigh out the appropriate weight parts of nylon PA6, nylon PA66, modified glass fiber, modified flame retardant, toughening agent, antioxidant 1098, antioxidant 9228, stabilizer, flow modifier, and calcium stearate for later use. S2. Vacuum dry nylon PA6 and nylon PA66 at 80~100℃ for 4~6 hours; S3. Add the dried nylon PA6, nylon PA66, modified flame retardant, toughening agent, antioxidant 1098, antioxidant 9228, stabilizer, flow modifier, and calcium stearate to a high-speed mixer in sequence, and mix at 80~100℃ and 800~1500rpm for 5~10min to obtain a premix. S4. The premix and modified glass fiber are added through the main feed port and side feed port of the twin-screw extruder, respectively, for melt blending and extrusion. S5. After water cooling and pelletizing, the extruded material is used to obtain high heat-resistant halogen-free flame-retardant nylon material.

[0017] Furthermore, in step S4, the temperatures of each zone of the twin-screw extruder are set as follows: Zone 1: 190~210℃, Zone 2: 220~240℃, Zone 3: 230~245℃, Zone 4: 230~250℃, Zone 5: 240~260℃, and the screw speed is 300~600rpm.

[0018] The present invention has the following advantages over the prior art: 1. This invention utilizes the high heat resistance of PA66 and the processability advantages of PA6 to compound PA6 and PA66 substrates. By enhancing the rigidity of modified fibers and the synergistic effect of antioxidants, the heat distortion temperature of the material is improved. This invention completely abandons halogen-based flame retardants and uses modified halogen-free flame retardants. While achieving flame retardant effect, no harmful hydrogen halide gas or dioxins are released during combustion. Moreover, the material maintains excellent rigidity and toughness on the basis of high flame retardancy and high heat resistance, solving the problem of decreased mechanical properties caused by high addition amount of traditional halogen-free flame retardants.

[0019] 2. This invention uses KH550 silane coupling agent for surface treatment of glass fibers. After hydrolysis, the silanol groups of KH550 undergo a condensation reaction with the silanol groups on the glass fiber surface, forming strong covalent bonds. This introduces the amino functional groups at the other end of the coupling agent to the glass fiber surface, successfully preparing aminated glass fibers. Subsequently, the aminated glass fibers undergo a nucleophilic ring-opening reaction with glycidyl methacrylate (GMA), grafting GMA molecules onto the fiber surface in a covalent manner. During the composite material processing, the polar ester groups in the grafted GMA molecular chains can form strong hydrogen bonds with the amide groups of the nylon matrix, which is the main factor improving interfacial compatibility. At the same time, its flexible molecular chain structure can locally diffuse and entangle with nylon molecules, forming an effective flexible interfacial transition layer, significantly reducing interfacial stress concentration. This strong interfacial bonding enables efficient transfer of external force from the nylon matrix to the high-strength glass fibers, comprehensively improving the tensile strength, flexural strength, and impact toughness of the composite material. In addition, the good interfacial bonding also fully utilizes the rigid support of the fiber, effectively suppressing the thermal deformation of the matrix at high temperatures and directly increasing the thermal deformation temperature of the material.

[0020] 3. This invention uses a combination of bio-based additives such as sodium phytate and PL-502 halogen-free flame retardant to improve flame retardant efficiency through their synergistic effect. As a nitrogen-phosphorus flame retardant, PL-502 releases phosphorus-based free radicals during combustion, which can capture active free radicals in the gas phase, inhibiting the combustion chain reaction and promoting the dehydration and char formation of the matrix. Sodium phytate, as an auxiliary flame retardant, forms a phosphorus-phosphorus synergy with PL-502, enhancing the char formation catalysis effect while stabilizing the char layer structure. The citric acid-chitosan composite system crosslinks at high temperatures to form a tough char layer skeleton, which, together with PL-502 and sodium phytate, forms a dense, heat-insulating, expanded char layer, effectively blocking heat and oxygen transfer. Regarding compatibility improvement, PL-502 is initially coated with PVA1788, and then a secondary coating is formed using a citric acid-chitosan composite system. This double coating structure significantly improves the dispersibility and compatibility of the flame retardant in the nylon matrix, avoids interface defects caused by flame retardant agglomeration, and fundamentally solves the problems of poor compatibility and decreased mechanical properties of traditional halogen-free flame retardants. Detailed Implementation

[0021] Nylon PA6 (Jiangsu Haiyang 2500A); Nylon PA66 (Pingdingshan Shenma EPR24); Fiberglass (Jushi Fiberglass 568H); Flame retardant (Puli New Materials PL-502); Toughening agent (Jiayirong CMG5805); Antioxidant (Tianjin Lianlong 1098); Antioxidant (Beijing Jiyi Chemical 9228); Stabilizer (Clariant Seed); Flow modifier (CYD-C603A); Calcium stearate (Italian Faji).

[0022] To further explain the present invention, the following specific embodiments are described. Example

[0023] A method for preparing a high heat-resistant, halogen-free, flame-retardant nylon material includes the following steps: S1. Weigh out the following amounts: 30 parts of nylon PA6, 10 parts of nylon PA66, 23 parts of modified glass fiber, 12 parts of modified flame retardant, 2 parts of toughening agent (CMG5805), 0.08 parts of antioxidant 1098, 0.15 parts of antioxidant 9228, 0.2 parts of stabilizer (Clariant Seed), 0.2 parts of flow modifier (CYD-C603A), and 0.4 parts of calcium stearate for later use. S2. Vacuum dry nylon PA6 and nylon PA66 at 80℃ for 4 hours; S3. Add the dried nylon PA6, nylon PA66, modified flame retardant, toughening agent, antioxidant 1098, antioxidant 9228, stabilizer, flow modifier, and calcium stearate to a high-speed mixer in sequence, and mix at 80°C and 800 rpm for 5 minutes to obtain a premix. S4. The premix and modified glass fiber are added through the main feed port and side feed port of the twin-screw extruder, respectively, for melt blending and extrusion. The temperature settings for each zone of the twin-screw extruder are as follows: Zone 1: 190℃, Zone 2: 220℃, Zone 3: 230℃, Zone 4: 230℃, Zone 5: 240℃, and the screw speed is 300 rpm. S5. After water cooling and pelletizing, the extruded material is used to obtain high heat-resistant halogen-free flame-retardant nylon material. The preparation of the modified glass fiber includes the following steps: (1) After drying the 568H glass fiber at 100℃ for 2 hours, place it in a low-temperature oxygen plasma with a vacuum of 5Pa, an oxygen flow rate of 20sccm, a power of 150W, and a treatment time of 5min. (2) The plasma-treated glass fiber was immersed in a 2.5wt% γ-aminopropyltriethoxysilane ethanol solution and stirred at 200rpm for 4h at 65℃. After the reaction was completed, it was washed three times with anhydrous ethanol and then vacuum dried at 100℃ for 6h to obtain aminated glass fiber. (3) The above-mentioned aminated glass fiber was dispersed in toluene at a solid-liquid ratio of 1g:15mL, and then 1.2 times the molar amount of glycidyl methacrylate (GMA) relative to KH550 was added. Under N2 protection, the mixture was stirred at 90℃ and 200rpm for 8h. After the reaction was completed, the unreacted GMA was thoroughly washed with toluene to remove it. Finally, the mixture was vacuum dried at 80℃ to constant weight to obtain the modified glass fiber. The preparation of the modified flame retardant includes the following steps: 1) Dissolve citric acid and chitosan in a 1.5wt% dilute acetic acid aqueous solution at a mass ratio of 2:1, with the citric acid concentration being 5wt%. Stir at 60℃ until completely dissolved to obtain a citric acid-chitosan solution. 2) Disperse PL-502 flame retardant powder in deionized water at a solid-liquid ratio of 1g:8mL, add 3% polyvinyl alcohol (PVA 1788) by mass of PL-502, and stir at 200rpm for 30min to obtain a suspension. 3) Add 20% of the citric acid-chitosan solution by mass of PL-502 to the suspension at a rate of 1 mL / min. Raise the temperature of the system to 80°C, add 5% of sodium phytate by mass of PL-502, and stir at 300 rpm for 3 hours. 4) Adjust the pH to 7.0 with 10wt% sodium hydroxide solution, let stand for 30 min, filter, wash three times with deionized water and ethanol in sequence, and dry under vacuum at 60℃ for 10 h. Example

[0024] A method for preparing a high heat-resistant, halogen-free, flame-retardant nylon material includes the following steps: S1. Weigh out the following amounts: 35 parts of nylon PA6, 15 parts of nylon PA66, 30 parts of modified glass fiber, 15 parts of modified flame retardant, 3 parts of toughening agent (CMG5805), 0.1 parts of antioxidant 1098, 0.2 parts of antioxidant 9228, 0.3 parts of stabilizer (Clariant Seed), 0.3 parts of flow modifier (CYD-C603A), and 0.5 parts of calcium stearate for later use. S2. Vacuum dry nylon PA6 and nylon PA66 at 90℃ for 5 hours; S3. Add the dried nylon PA6, nylon PA66, modified flame retardant, toughening agent, antioxidant 1098, antioxidant 9228, stabilizer, flow modifier, and calcium stearate to a high-speed mixer in sequence, and mix at 90℃ and 1200rpm for 8 minutes to obtain a premix. S4. The premix and modified glass fiber are added through the main feed port and side feed port of the twin-screw extruder, respectively, for melt blending and extrusion. The temperature settings for each zone of the twin-screw extruder are as follows: Zone 1: 200℃, Zone 2: 230℃, Zone 3: 240℃, Zone 4: 240℃, Zone 5: 250℃, and the screw speed is 400 rpm. S5. After water cooling and pelletizing, the extruded material is used to obtain high heat-resistant halogen-free flame-retardant nylon material. The preparation of the modified glass fiber includes the following steps: (1) After drying the 568H glass fiber at 105℃ for 2.5h, place it in a low-temperature oxygen plasma with a vacuum of 5Pa, an oxygen flow rate of 22sccm, a power of 150W, and a treatment time of 8min. (2) The plasma-treated glass fiber was immersed in a 3wt% γ-aminopropyltriethoxysilane ethanol solution and stirred at 70°C and 250 rpm for 4.5 h. After the reaction was completed, it was washed three times with anhydrous ethanol and then vacuum dried at 105°C for 6.5 h to obtain aminated glass fiber. (3) The above-mentioned aminated glass fiber was dispersed in toluene at a solid-liquid ratio of 1g:18mL, and then 1.2 times the molar amount of glycidyl methacrylate (GMA) relative to KH550 was added. Under N2 protection, the mixture was stirred at 90℃ and 250rpm for 8.5h. After the reaction was completed, the unreacted GMA was thoroughly washed with toluene to remove it. Finally, the mixture was vacuum dried at 85℃ to constant weight to obtain the modified glass fiber. The preparation of the modified flame retardant includes the following steps: 1) Dissolve citric acid and chitosan in a 1.5wt% dilute acetic acid aqueous solution at a mass ratio of 2:1, with the citric acid concentration being 5wt%. Stir at 62℃ until completely dissolved to obtain a citric acid-chitosan solution. 2) Disperse PL-502 flame retardant powder in deionized water at a solid-liquid ratio of 1g:9mL, add 3% polyvinyl alcohol (PVA 1788) by mass of PL-502, and stir at 250rpm for 35min to obtain a suspension. 3) Add 20% of the citric acid-chitosan solution by mass of PL-502 to the suspension at a dropping rate of 1.2 mL / min. Raise the temperature of the system to 82℃, add 5% of sodium phytate by mass of PL-502, and stir at 350 rpm for 4 hours. 4) Adjust the pH to 7.0 with 10wt% sodium hydroxide solution, let stand for 32 min, filter, wash with deionized water and ethanol three times in sequence, and dry under vacuum at 62℃ for 11 h. Example

[0025] A method for preparing a high heat-resistant, halogen-free, flame-retardant nylon material includes the following steps: S1. Weigh out the following amounts: 40 parts Nylon PA6, 20 parts Nylon PA66, 40 parts modified glass fiber, 20 parts modified flame retardant, 4 parts toughening agent (CMG5805), 0.12 parts antioxidant 1098, 0.25 parts antioxidant 9228, 0.4 parts stabilizer (Clariant Seed), 0.4 parts flow modifier (CYD-C603A), and 0.6 parts calcium stearate for later use. S2. Vacuum dry nylon PA6 and nylon PA66 at 100℃ for 6 hours; S3. Add the dried nylon PA6, nylon PA66, modified flame retardant, toughening agent, antioxidant 1098, antioxidant 9228, stabilizer, flow modifier, and calcium stearate to a high-speed mixer in sequence, and mix at 100℃ and 1500rpm for 10min to obtain a premix. S4. The premix and modified glass fiber are added through the main feed port and side feed port of the twin-screw extruder, respectively, for melt blending and extrusion. The temperature settings for each zone of the twin-screw extruder are as follows: Zone 1: 210℃, Zone 2: 240℃, Zone 3: 245℃, Zone 4: 250℃, Zone 5: 260℃, and the screw speed is 600 rpm. S5. After water cooling and pelletizing, the extruded material is used to obtain high heat-resistant halogen-free flame-retardant nylon material. The preparation of the modified glass fiber includes the following steps: (1) After drying the Jushi glass fiber 568H at 110℃ for 3h, place it in a low-temperature oxygen plasma, set the vacuum degree to 5Pa, the oxygen flow rate to 25sccm, the power to 150W, and the treatment time to 10min. (2) The plasma-treated glass fiber was immersed in a 3.5 wt% γ-aminopropyltriethoxysilane ethanol solution and stirred at 300 rpm for 5 h at 75 °C. After the reaction was completed, it was washed 4 times with anhydrous ethanol and then vacuum dried at 110 °C for 7 h to obtain aminated glass fiber. (3) The above-mentioned aminated glass fiber was dispersed in toluene at a solid-liquid ratio of 1g:20mL, and then 1.2 times the molar amount of glycidyl methacrylate (GMA) relative to KH550 was added. Under N2 protection, the mixture was stirred at 90℃ and 300rpm for 9h. After the reaction was completed, the unreacted GMA was thoroughly washed with toluene to remove it. Finally, the mixture was vacuum dried at 90℃ to constant weight to obtain the modified glass fiber. The preparation of the modified flame retardant includes the following steps: 1) Dissolve citric acid and chitosan in a 1.5wt% dilute acetic acid aqueous solution at a mass ratio of 2:1, with the citric acid concentration being 5wt%. Stir at 65℃ until completely dissolved to obtain a citric acid-chitosan solution. 2) Disperse PL-502 flame retardant powder in deionized water at a solid-liquid ratio of 1g:10mL, add 3% polyvinyl alcohol (PVA 1788) by mass of PL-502, and stir at 300rpm for 40min to obtain a suspension. 3) Add 20% of the citric acid-chitosan solution by mass of PL-502 to the suspension at a rate of 1.5 mL / min. Raise the temperature of the system to 85°C, add 5% of sodium phytate by mass of PL-502, and stir at 400 rpm for 5 h. 4) Adjust the pH to 7.0 with 10wt% sodium hydroxide solution, let stand for 35 min, filter, wash with deionized water and ethanol 4 times in sequence, and dry under vacuum at 65℃ for 12 h.

[0026] Comparative Example 1 Compared with Example 2, Comparative Example 1 replaced the modified glass fiber with unmodified glass fiber, using Jushi Glass Fiber 568H directly, while the other steps were the same as in Example 2.

[0027] Comparative Example 2 Compared with Example 2, Comparative Example 2 replaced the modified flame retardant with an unmodified flame retardant and used PL-502 powder directly. The other steps were the same as in Example 2.

[0028] Comparative Example 3 Compared with Example 2, Comparative Example 3 omits antioxidant 9228, but the other steps are the same as in Example 2.

[0029] Performance testing Impact test specimens and heat distortion temperature test specimens, both measuring 80 mm × 10 mm × 4 mm, were injection molded on an injection molding machine. Impact testing was performed using a notched prototyping machine to prepare type A notches according to GB / T 1843-1996 standard, with the test conducted at 23℃ and 50% relative humidity. Tensile strength was tested according to GB / T 1040.2-2006 standard at a rate of 50 mm / min. Flexural strength / modulus was tested according to GB / T 9341-2008 standard at a rate of 2 mm / min. Surface heat distortion temperature testing was conducted according to GB / T 1634-2004 standard, with a heating rate of 120℃ / h and a load of 0.45 MPa. Flame retardant specimens were also injection molded on the injection molding machine, with specimen dimensions of 180 mm × 10 mm × 1.6 mm and 180 mm × 10 mm × 3.2 mm. Vertical burning tests were conducted in accordance with UL94 standards.

[0030] The test results are shown in Table 1 below.

[0031] Table 1 Tensile strength (MPa) Bending strength (MPa) Flexural modulus (MPa) <![CDATA[Notch impact strength (KJ / m 2 )]]> Flame retardant rating (0.8mm) Heat distortion temperature (°C) Example 1 130 195 8100 12.0 UL94 V-0 210 Example 2 136 211 8500 13.5 UL94 V-0 215 Example 3 135 213 8300 14.2 UL94 V-0 220 Comparative Example 1 108 172 6800 9.2 UL94 V-0 175 Comparative Example 2 115 185 7500 10.5 UL94 V-1 190 Comparative Example 3 132 205 8300 12.8 UL94 V-0 213 As shown in Table 1 above, Comparative Example 1 uses unmodified glass fiber, which lacks the polar ester functional groups and flexible molecular chains introduced by GMA modification. This results in poor interfacial compatibility and adhesion with the nylon matrix, leading to decreased mechanical properties. Furthermore, the unmodified glass fiber provides insufficient rigid support to the matrix, causing a decrease in heat distortion temperature. Comparative Example 2 uses unmodified PL-502. Unmodified PL-502 powder easily agglomerates in the nylon matrix, forming stress defect points, leading to decreased material mechanical properties. Poor dispersibility also causes uneven heat transfer, further reducing the heat distortion temperature. The unmodified flame retardant cannot form a dense char layer, causing the flame retardant rating to drop from V-0 to V-1. Comparative Example 3 omits antioxidant 9228, resulting in accelerated thermal oxidative aging and a decreased heat distortion temperature. While the short-term mechanical property decline is not significant, performance degradation will intensify with long-term use.

[0032] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A high heat-resistant, halogen-free, flame-retardant nylon material, characterized in that, It is composed of the following components in parts by weight: 0-40 parts of nylon PA63, 10-20 parts of nylon PA66, 20-40 parts of modified glass fiber, 10-20 parts of modified flame retardant, 2-4 parts of toughening agent, 0.08-0.12 parts of antioxidant 1098, 0.15-0.25 parts of antioxidant 9228, 0.2-0.4 parts of stabilizer, 0.2-0.4 parts of flow modifier, and 0.4-0.6 parts of calcium stearate.

2. The high heat-resistant halogen-free flame-retardant nylon material according to claim 1, characterized in that, The preparation of the modified glass fiber includes the following steps: (1) After drying the 568H glass fiber at 100~110℃ for 2~3h, place it in a low-temperature oxygen plasma for 5~10min; (2) The plasma-treated glass fiber was immersed in a 2.5-3.5 wt% γ-aminopropyltriethoxysilane ethanol solution and stirred at 65-75°C and 200-300 rpm for 4-5 h. After the reaction was completed, it was washed 3-4 times with anhydrous ethanol and then vacuum dried at 100-110°C for 6-7 h to obtain aminated glass fiber. (3) The above-mentioned aminated glass fiber was dispersed in toluene at a solid-liquid ratio of 1g:15~20mL, and then 1.2 times the molar amount of glycidyl methacrylate relative to KH550 was added. Under N2 protection, the mixture was stirred at 90℃ and 200~300rpm for 8~9h. After the reaction was completed, the unreacted GMA was thoroughly washed with toluene to remove it. Finally, the mixture was vacuum dried at 80~90℃ to constant weight to obtain the modified glass fiber.

3. The high heat-resistant halogen-free flame-retardant nylon material according to claim 2, characterized in that, In step (1), the low-temperature plasma treatment is set to a vacuum of 5 Pa, an oxygen flow rate of 20-25 sccm, and a power of 150 W.

4. The high heat-resistant halogen-free flame-retardant nylon material according to claim 1, characterized in that, The preparation of the modified flame retardant includes the following steps: 1) Dissolve citric acid and chitosan in a 1.5wt% dilute acetic acid aqueous solution at a mass ratio of 2:1, with the citric acid concentration being 5wt%. Stir at 60~65℃ until completely dissolved to obtain a citric acid-chitosan solution. 2) Disperse PL-502 flame retardant powder in deionized water at a solid-liquid ratio of 1g:8~10mL, add 3% polyvinyl alcohol by mass of PL-502, and stir at 200~300rpm for 30~40min to obtain a suspension. 3) Add 20% of the citric acid-chitosan solution by mass of PL-502 to the suspension at a rate of 1-1.5 mL / min. Raise the temperature of the system to 80-85℃, add 5% of sodium phytate by mass of PL-502, and stir at 300-400 rpm for 3-5 hours. 4) Adjust the pH to 7.0 with 10wt% sodium hydroxide solution, let stand for 30-35 minutes, filter, wash with deionized water and ethanol 3-4 times in sequence, and vacuum dry at 60-65℃ for 10-12 hours.

5. The high heat-resistant halogen-free flame-retardant nylon material according to claim 1, characterized in that, The toughening agent is a maleic anhydride-grafted ethylene-octene copolymer.

6. The high heat-resistant halogen-free flame-retardant nylon material according to claim 1, characterized in that, The stabilizer is a copper heat stabilizer.

7. The high heat-resistant halogen-free flame-retardant nylon material according to claim 1, characterized in that, The flow modifier is a lubricating flow aid.

8. A method for preparing a high heat-resistant halogen-free flame-retardant nylon material as described in any one of claims 1 to 7, characterized in that, Includes the following steps: S1. Weigh out the appropriate weight parts of nylon PA6, nylon PA66, modified glass fiber, modified flame retardant, toughening agent, antioxidant 1098, antioxidant 9228, stabilizer, flow modifier, and calcium stearate for later use. S2. Vacuum dry nylon PA6 and nylon PA66 at 80~100℃ for 4~6 hours; S3. Add the dried nylon PA6, nylon PA66, modified flame retardant, toughening agent, antioxidant 1098, antioxidant 9228, stabilizer, flow modifier, and calcium stearate to a high-speed mixer in sequence, and mix at 80~100℃ and 800~1500rpm for 5~10min to obtain a premix. S4. The premix and modified glass fiber are added through the main feed port and side feed port of the twin-screw extruder, respectively, for melt blending and extrusion. S5. After water cooling and pelletizing, the extruded material is used to obtain high heat-resistant halogen-free flame-retardant nylon material.

9. The method for preparing a high heat-resistant halogen-free flame-retardant nylon material according to claim 8, characterized in that, In step S4, the temperature settings for each zone of the twin-screw extruder are as follows: Zone 1: 190~210℃, Zone 2: 220~240℃, Zone 3: 230~245℃, Zone 4: 230~250℃, Zone 5: 240~260℃, and the screw speed is 300~600rpm.