High-temperature-resistant composite material for automobile wire and preparation method thereof
By cross-linking modified nitrile rubber and white carbon black, combined with surface treatment technology, an automotive wire composite material with high heat resistance, flame retardancy and antibacterial properties was prepared, which solved the problem of performance degradation of existing materials in high temperature and oily environments, and achieved multiple performance improvements of the material.
Patent Information
- Application Number
- CN202510908341.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-02
- Publication Date
- 2025-09-26
AI Technical Summary
Existing automotive wire insulation materials are prone to performance degradation in high temperature and oily environments, resulting in insulation failure and decreased mechanical strength. They also have insufficient flame retardancy, easily produce toxic gases when burned, and lack antibacterial properties.
Through multi-component collaborative design and process optimization, a high-temperature resistant composite material for automotive wires is prepared. Modified nitrile rubber, modified silica, hydrogenated silicone oil and chloroplatinic acid are cross-linked to form a highly stable three-dimensional network structure, enhancing the material's heat resistance. The silica surface treatment gives the material flame retardant and antibacterial properties.
The material's heat resistance, anti-aging performance, flame retardancy and antibacterial properties are significantly improved, extending the service life of wires and improving safety.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of materials, and in particular to a high-temperature resistant composite material for automotive electric wires and a preparation method thereof. Background Art
[0002] The insulation materials commonly used for automotive wiring are primarily polyolefin polymers, such as polyethylene, cross-linked polyethylene, or polypropylene. These are widely used due to their excellent dielectric properties, easy processability, and low cost. However, polyolefin materials have significant drawbacks in terms of oil and heat resistance. For example, prolonged exposure to oily contaminants or high temperatures within the engine compartment can lead to performance degradation, resulting in insulation failure or a decrease in mechanical strength. Against this backdrop, nitrile rubber (NBR) has become a key raw material for automotive wiring due to its excellent oil resistance, making it particularly suitable for cable protective layers in oily environments.
[0003] The high acrylonitrile content in the molecular structure of nitrile rubber makes it extremely resistant to mineral oils, fuel oils, and other substances. It also has excellent wear resistance and bonding properties, effectively extending the service life of wires in complex working conditions. However, nitrile rubber also has significant limitations: it has poor heat resistance and is prone to thermal decomposition or aging in high-temperature environments; it has insufficient flame retardancy and easily produces toxic gases when burned. Furthermore, imparting antimicrobial properties to the material can not only inhibit the growth of bacteria and fungi, reducing the risk of insulation degradation caused by microbial metabolites, but also extend the material's service life.
[0004] To make up for these shortcomings, the development of composite materials with high temperature resistance, flame retardancy, anti-aging and antibacterial functions through multi-component collaborative design and process optimization has become a key direction for the development of automotive wire insulation materials to meet the higher requirements of modern automobiles for lightweight, safety and environmental adaptability. Summary of the Invention
[0005] The object of the present invention is to provide a high-temperature resistant composite material for automotive wires and a preparation method thereof, so as to solve the problems existing in the prior art.
[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:
[0007] A method for preparing a high-temperature resistant composite material for automotive wires, comprising the following steps:
[0008] (1) reacting 2-allyl-1,3,5-triazine-2,4,6-triamine and cyanoacetyl urea to obtain a functional monomer;
[0009] (2) reacting the epoxidized nitrile rubber and the functional monomer to obtain a modified nitrile rubber;
[0010] (3) reacting pretreated silica and 4-propylenethiosemicarbazide to obtain pre-modified silica;
[0011] (4) reacting pre-modified silica, diphenyl ammonium phosphate, and zinc chloride to obtain modified silica;
[0012] (5) The following components: modified nitrile rubber, modified white carbon black, hydrogenated silicone oil, chloroplatinic acid, and vinyltrimethoxysilane are mixed and hot-pressed to obtain a high-temperature resistant composite material for automotive wires.
[0013] As an optimization, the preparation method of the functional monomer in step (1) is: mix 2-allyl-1,3,5-triazine-2,4,6-triamine, cyanamide, triethyl orthoformate, and dioxane, heat to 95-105° C. and reflux for 7-9 hours to obtain the functional monomer.
[0014] As an optimization, the molar ratio of the 2-allyl-1,3,5-triazine-2,4,6-triamine, cyanoacetyl urea, and triethyl orthoformate is 1:(1.2-1.4):(3.0-3.4); the mass of the dioxane is 10-12 times that of cyanoacetyl urea.
[0015] As an optimization, the preparation method of the modified nitrile rubber in step (2) is as follows: tert-butyl hydroperoxide and molybdenum trioxide are mixed, activated at 65-75°C for 2-3h, and after the activation, reacted with the nitrile rubber in a rheometer for 30-40min at a rheometer speed of 30-40r / min to obtain epoxidized nitrile rubber; epoxidized nitrile rubber, functional monomer, N,N-dimethylformamide, and triethylamine are mixed, heated to 100-110°C and reacted for 6-8h to obtain modified nitrile rubber.
[0016] As an optimization, the mass ratio of the nitrile rubber, tert-butyl hydroperoxide, and molybdenum trioxide is 1:(0.4-0.6):(0.003-0.004); the mass ratio of the epoxidized nitrile rubber, functional monomer, N,N-dimethylformamide, and triethylamine is 1:(0.1-0.2):(10-15):(0.3-0.5).
[0017] As an optimization, after ultrasonically dispersing silica, anhydrous ethanol and pure water for 30-40 minutes, hydrochloric acid was used to adjust the pH to 3-4, 3-(4-formylphenoxy)propyltrimethoxysilane was added, and the mixture was reacted at 70-80°C for 8-10 hours to obtain pretreated silica; the pretreated silica, 4-propylenethiosemicarbazide and methanol were ultrasonically mixed, the temperature was raised to 60-65°C, and the mixture was refluxed for 1-2 hours to obtain pre-modified silica.
[0018] As an optimization, the mass ratio of the silica, anhydrous ethanol, pure water, and 3-(4-formylphenoxy)propyltrimethoxysilane is 1:(10-15):(5-10):(1-2); the mass ratio of the pretreated silica, 4-propylenethiosemicarbazide, and methanol is 1:(2-3):(20-30).
[0019] As an optimization, the preparation method of the modified silica in step (4) is as follows: pre-modified silica, diphenyl ammonium phosphate, and methanol are ultrasonically mixed, which is recorded as solution A, and the mass of methanol in solution A is 15-20 times that of pre-modified silica; zinc chloride and methanol are ultrasonically mixed, which is recorded as solution B, and the mass of methanol in solution B is 5-6 times that of zinc chloride; solution B is poured into solution A, stirred for 1-2 hours, and allowed to stand for 2-3 hours to obtain modified silica; the mass ratio of pre-modified silica, diphenyl ammonium phosphate, and zinc chloride is 1:(2-3):(1.5-2.0).
[0020] As an optimization, the preparation method of the high-temperature resistant composite material for automotive wires in step (5) is as follows: take the following components: 100 parts of modified nitrile rubber, 40-50 parts of modified white carbon black, 15-20 parts of hydrogenated silicone oil, 1-2 parts of chloroplatinic acid, and 3-5 parts of vinyltrimethoxysilane, calculated by mass; plasticize the modified nitrile rubber on a double-roll mill for 3-5 minutes, add hydrogenated silicone oil, vinyltrimethoxysilane, and 1 / 2 of the modified white carbon black in turn and mix for 2-3 minutes, then add the remaining modified white carbon black and chloroplatinic acid and mix for 8-10 minutes, thinly pass 20 times to produce a sheet, let it stand for 12 hours, and then hot-press mold it on a flat vulcanizer under the conditions of 170°C, 10 minutes, and 10 MPa to obtain a high-temperature resistant composite material for automotive wires.
[0021] The present invention also provides a high-temperature resistant composite material for automobile wires prepared according to any of the above methods for preparing the high-temperature resistant composite material for automobile wires.
[0022] Compared with the prior art, the present invention has the following beneficial effects:
[0023] The high-temperature resistant composite material for automotive wires prepared by the present invention comprises modified nitrile rubber, modified silica, and hydrogen-containing silicone oil. The modified nitrile rubber is obtained by reacting epoxidized nitrile rubber with a functional monomer; the modified silica is obtained by reacting pretreated silica with 4-propylenethiosemicarbazide, and then with diphenyl ammonium phosphate and zinc chloride.
[0024] First, 2-allyl-1,3,5-triazine-2,4,6-triamine and cyanoacetyl urea are condensed and cyclized in the presence of triethyl orthoformate to form a triazine-uracil structure with antioxidant properties. The tertiary nitrogen atom and conjugated double bond system in this structure can provide lone pairs of electrons or hydrogen atoms, effectively capturing alkyl radicals and peroxyl radicals generated during rubber oxidation, thereby delaying rubber aging. The amino groups on the epoxidized nitrile rubber and functional monomer are ring-opened to graft the functional monomer and introduce vinyl groups.
[0025] The schematic diagram of the preparation process of the triazine-uracil structure is as follows:
[0026]
[0027] Secondly, the high specific surface area and porosity of silica can form a strong interaction with the rubber molecular chain, enhancing the mechanical properties of the rubber; using 3-(4-formylphenoxy)propyltrimethoxysilane to treat silica makes the silica surface contain aldehyde groups, which react with 4-propylenethiosemicarbazide to form thiosemicarbazide with antibacterial properties. Thiosemicarbazide can also complex zinc ions with diphenyl ammonium phosphate as a ligand for zinc ions, thereby simultaneously fixing diphenyl ammonium phosphate with flame retardant properties and zinc ions with antibacterial properties on the silica surface, thus giving the material good antibacterial and flame retardant properties;
[0028] Finally, vinyltrimethoxysilane was used as a solubilizer to enhance the compatibility of hydrogenated silicone oil and nitrile rubber. The modified nitrile rubber, modified silica, and hydrogenated silicone oil were cross-linked in the presence of chloroplatinic acid. The hydrogenated silicone oil underwent efficient cross-linking reaction with the ethylene functional groups in the material system through the active Si-H bonds in its molecular structure, forming a highly stable three-dimensional network structure, which significantly improved the heat resistance of the material. DETAILED DESCRIPTION
[0029] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.
[0030] In the following examples and comparative examples, the nitrile rubber is Nandi NBR2865; the hydrogenated silicone oil is purchased from Jinan Yingyu Chemical Co., Ltd.; and the white carbon black is A200 white carbon black from Degussa, Germany.
[0031] Example 1:
[0032] A method for preparing a high-temperature resistant composite material for automotive wires, comprising the following steps:
[0033] (1) 2-allyl-1,3,5-triazine-2,4,6-triamine, cyanoacetyl urea, triethyl orthoformate, and dioxane were mixed and heated to 105°C for reflux reaction for 7 hours. After the reaction, the mixture was filtered while hot and the precipitate was retained. The precipitate was dried and recrystallized from N,N-dimethylformamide / pure water to obtain a functional monomer;
[0034] The volume ratio of N,N-dimethylformamide to pure water is 1:1; the molar ratio of 2-allyl-1,3,5-triazine-2,4,6-triamine, cyanoacetyl urea, and triethyl orthoformate is 1:1.2:3.0; the mass of dioxane is 10 times that of cyanoacetyl urea;
[0035] (2) tert-butyl hydroperoxide and molybdenum trioxide were mixed and activated at 75°C for 3 hours. After the activation, the mixture was reacted with nitrile rubber in a Rheocord 9000 torque rheometer for 40 minutes at a speed of 40 r / min. After the reaction, the mixture was dissolved in chloroform, precipitated with methanol, filtered, washed with methanol, and dried to obtain epoxidized nitrile rubber; the mass ratio of nitrile rubber, tert-butyl hydroperoxide, and molybdenum trioxide was 1:0.4:0.003;
[0036] The epoxidized nitrile rubber, functional monomer, N,N-dimethylformamide, and triethylamine were mixed, heated to 110°C for reaction for 8 hours, and after the reaction, precipitated with ethanol, washed, and dried to obtain a modified nitrile rubber; the mass ratio of the epoxidized nitrile rubber, functional monomer, N,N-dimethylformamide, and triethylamine was 1:0.1:10:0.3;
[0037] (3) Under nitrogen protection, white carbon black, anhydrous ethanol and pure water were ultrasonically dispersed for 40 minutes, and then the pH was adjusted to 4 with hydrochloric acid. 3-(4-formylphenoxy)propyltrimethoxysilane was added and reacted at 80°C for 10 hours. The pretreated white carbon black was obtained by centrifugal filtration, washing and drying. The mass ratio of white carbon black, anhydrous ethanol, pure water and 3-(4-formylphenoxy)propyltrimethoxysilane was 1:10:5:1. Under nitrogen protection, the pretreated white carbon black, 4-propylenethiocarbazide and methanol were ultrasonically mixed in a mass ratio of 1:2:20, heated to 65°C, refluxed for 2 hours, and centrifuged, washed and dried to obtain pre-modified white carbon black.
[0038] (4) Pre-modified silica, diphenyl ammonium phosphate, and methanol were ultrasonically mixed and recorded as solution A, where the mass of methanol in solution A was 15 times that of pre-modified silica; zinc chloride and methanol were ultrasonically mixed and recorded as solution B, where the mass of methanol in solution B was 5 times that of zinc chloride; solution B was poured into solution A and stirred for 2 h, allowed to stand for 3 h, filtered, washed, and dried to obtain modified silica; the mass ratio of pre-modified silica, diphenyl ammonium phosphate, and zinc chloride was 1:2:1.5;
[0039] (5) Weigh the following components: 100 parts by mass of modified nitrile rubber, 40 parts by mass of modified silica, 15 parts by mass of hydrogenated silicone oil, 1 part by mass of chloroplatinic acid, and 3 parts by mass of vinyl trimethoxysilane; plasticize the modified nitrile rubber on a two-roll mill for 5 minutes, add hydrogenated silicone oil, vinyl trimethoxysilane, and 1 / 2 of the modified silica in turn and mix for 3 minutes, then add the remaining modified silica and chloroplatinic acid and mix for 10 minutes, pass the mixture through the mill 20 times to produce a sheet, let it stand for 12 hours, and then hot-press it on a flat vulcanizer to obtain a high-temperature resistant composite material for automotive wires, under the conditions of 170°C, 10 minutes, and 10 MPa.
[0040] Example 2:
[0041] A method for preparing a high-temperature resistant composite material for automotive wires, comprising the following steps:
[0042] (1) 2-allyl-1,3,5-triazine-2,4,6-triamine, cyanoacetyl urea, triethyl orthoformate, and dioxane were mixed and heated to 100°C for reflux reaction for 8 hours. After the reaction was completed, the hot filter was retained and the precipitate was dried and recrystallized from N,N-dimethylformamide / pure water to obtain a functional monomer;
[0043] The volume ratio of N,N-dimethylformamide to pure water is 1:1; the molar ratio of 2-allyl-1,3,5-triazine-2,4,6-triamine, cyanoacetyl urea, and triethyl orthoformate is 1:1.3:3.2; the mass of dioxane is 11 times that of cyanoacetyl urea;
[0044] (2) tert-butyl hydroperoxide and molybdenum trioxide were mixed and activated at 70°C for 2.5 hours. After the activation, the mixture was reacted with nitrile rubber in a Rheocord 9000 torque rheometer for 35 minutes at a speed of 35 r / min. After the reaction, the mixture was dissolved in chloroform, precipitated with methanol, filtered, washed with methanol, and dried to obtain epoxidized nitrile rubber; the mass ratio of nitrile rubber, tert-butyl hydroperoxide, and molybdenum trioxide was 1:0.5:0.003;
[0045] The epoxidized nitrile rubber, functional monomer, N,N-dimethylformamide, and triethylamine were mixed, heated to 105°C for 7 hours, and precipitated with ethanol after the reaction, washed, and dried to obtain a modified nitrile rubber; the mass ratio of the epoxidized nitrile rubber, functional monomer, N,N-dimethylformamide, and triethylamine was 1:0.15:12:0.4;
[0046] (3) Under nitrogen protection, white carbon black, anhydrous ethanol and pure water were ultrasonically dispersed for 35 minutes, and then the pH was adjusted to 3.5 with hydrochloric acid. 3-(4-formylphenoxy)propyltrimethoxysilane was added and reacted at 75°C for 9 hours. The pretreated white carbon black was obtained by centrifugal filtration, washing and drying. The mass ratio of white carbon black, anhydrous ethanol, pure water and 3-(4-formylphenoxy)propyltrimethoxysilane was 1:13:7:1.5. Under nitrogen protection, the pretreated white carbon black, 4-propylenethiocarbazide and methanol were ultrasonically mixed in a mass ratio of 1:2.5:25, heated to 63°C, refluxed for 1.5 hours, and centrifuged, washed and dried to obtain pre-modified white carbon black.
[0047] (4) Pre-modified silica, diphenyl ammonium phosphate, and methanol were ultrasonically mixed and recorded as solution A. The mass of methanol in solution A was 17 times that of pre-modified silica. Zinc chloride and methanol were ultrasonically mixed and recorded as solution B. The mass of methanol in solution B was 5.5 times that of zinc chloride. Solution B was poured into solution A and stirred for 1.2 hours. After standing for 2.5 hours, the solution was filtered, washed, and dried to obtain modified silica. The mass ratio of pre-modified silica, diphenyl ammonium phosphate, and zinc chloride was 1:2.5:1.7.
[0048] (5) Weigh the following components: 100 parts by mass of modified nitrile rubber, 45 parts by mass of modified silica, 17 parts by mass of hydrogenated silicone oil, 1.5 parts by mass of chloroplatinic acid, and 4 parts by mass of vinyl trimethoxysilane; plasticize the modified nitrile rubber on a two-roll mill for 4 minutes, add hydrogenated silicone oil, vinyl trimethoxysilane, and 1 / 2 of the modified silica in turn and mix for 2.5 minutes, then add the remaining modified silica and chloroplatinic acid and mix for 9 minutes, pass the mixture through thinner 20 times to produce a sheet, let it stand for 12 hours, and then hot-press it on a flat vulcanizer to obtain a high-temperature resistant composite material for automotive wires, under the conditions of 170°C, 10 minutes, and 10 MPa.
[0049] Example 3:
[0050] A method for preparing a high-temperature resistant composite material for automotive wires, comprising the following steps:
[0051] (1) 2-allyl-1,3,5-triazine-2,4,6-triamine, cyanoacetyl urea, triethyl orthoformate, and dioxane were mixed and heated to 95°C for 7 hours under reflux. After the reaction, the mixture was filtered while hot and the precipitate was retained. The precipitate was dried and recrystallized from N,N-dimethylformamide / pure water to obtain a functional monomer.
[0052] The volume ratio of N,N-dimethylformamide to pure water is 1:1; the molar ratio of 2-allyl-1,3,5-triazine-2,4,6-triamine, cyanoacetyl urea, and triethyl orthoformate is 1:1.4:3.4; the mass of dioxane is 11 times that of cyanoacetyl urea;
[0053] (2) tert-butyl hydroperoxide and molybdenum trioxide were mixed and activated at 65°C for 2 hours. After the activation, the mixture was reacted with nitrile rubber in a Rheocord 9000 torque rheometer for 30 minutes at a speed of 30 r / min. After the reaction, the mixture was dissolved in chloroform, precipitated with methanol, filtered, washed with methanol, and dried to obtain epoxidized nitrile rubber. The mass ratio of nitrile rubber, tert-butyl hydroperoxide, and molybdenum trioxide was 1:0.6:0.004.
[0054] The epoxidized nitrile rubber, functional monomer, N,N-dimethylformamide, and triethylamine were mixed, heated to 100°C and reacted for 7 hours. After the reaction, the modified nitrile rubber was obtained by ethanol precipitation, washing, and drying. The mass ratio of the epoxidized nitrile rubber, functional monomer, N,N-dimethylformamide, and triethylamine was 1:0.2:15:0.5.
[0055] (3) Under nitrogen protection, white carbon black, anhydrous ethanol and pure water were ultrasonically dispersed for 30 minutes, and then the pH was adjusted to 3 with hydrochloric acid. 3-(4-formylphenoxy)propyltrimethoxysilane was added and reacted at 75°C for 8 hours. The pretreated white carbon black was obtained by centrifugal filtration, washing and drying. The mass ratio of white carbon black, anhydrous ethanol, pure water and 3-(4-formylphenoxy)propyltrimethoxysilane was 1:15:10:2. Under nitrogen protection, the pretreated white carbon black, 4-propylenethiocarbazide and methanol were ultrasonically mixed in a mass ratio of 1:3:30, heated to 60°C, refluxed for 1 hour, and centrifuged, washed and dried to obtain pre-modified white carbon black.
[0056] (4) Pre-modified silica, diphenyl ammonium phosphate, and methanol were ultrasonically mixed and recorded as solution A, where the mass of methanol in solution A was 20 times that of pre-modified silica; zinc chloride and methanol were ultrasonically mixed and recorded as solution B, where the mass of methanol in solution B was 6 times that of zinc chloride; solution B was poured into solution A and stirred for 1 hour, allowed to stand for 2 hours, filtered, washed, and dried to obtain modified silica; the mass ratio of pre-modified silica, diphenyl ammonium phosphate, and zinc chloride was 1:3:2.0;
[0057] (5) Weigh the following components: 100 parts by mass of modified nitrile rubber, 50 parts by mass of modified silica, 20 parts by mass of hydrogenated silicone oil, 2 parts by mass of chloroplatinic acid, and 5 parts by mass of vinyl trimethoxysilane; plasticize the modified nitrile rubber on a double-roll mill for 3 minutes, add hydrogenated silicone oil, vinyl trimethoxysilane, and 1 / 2 of the modified silica in turn and mix for 2 minutes, then add the remaining modified silica and chloroplatinic acid and mix for 8 minutes, pass the mixture through thinner 20 times to form a sheet, let it stand for 12 hours, and then hot-press it on a flat vulcanizer to obtain a high-temperature resistant composite material for automotive wires, under the conditions of 170°C, 10 minutes, and 10 MPa.
[0058] Comparative Example 1:
[0059] The preparation method of the high-temperature resistant composite material for automotive wires in Comparative Example 1 differs from that in Example 2 in that the nitrile rubber is not modified, specifically, steps (1) to (2) are not included, and step (5) is modified as follows: the following components are weighed: 100 parts of nitrile rubber, 45 parts of modified silica, 17 parts of hydrogenated silicone oil, 1.5 parts of chloroplatinic acid, and 4 parts of vinyltrimethoxysilane, by mass; the modified nitrile rubber is plasticized on a two-roll mill for 4 minutes, hydrogenated silicone oil, vinyltrimethoxysilane, and 1 / 2 of the modified silica are added in sequence and kneaded for 2.5 minutes, and then the remaining modified silica and chloroplatinic acid are added and kneaded for 9 minutes. The sheet is thinned 20 times and allowed to stand for 12 hours, and then hot-pressed on a flat vulcanizer to obtain a high-temperature resistant composite material for automotive wires. The conditions are 170°C, 10 minutes, and 10 MPa. The remaining steps are the same as in Example 2.
[0060] Comparative Example 2:
[0061] The preparation method of the high-temperature resistant composite material for automotive wires in Comparative Example 2 differs from that in Example 2 in that the silica is not modified, specifically, steps (3) to (4) are not included, and step (5) is modified as follows: the following components are weighed: 100 parts of modified nitrile rubber, 45 parts of silica, 17 parts of hydrogenated silicone oil, 1.5 parts of chloroplatinic acid, and 4 parts of vinyltrimethoxysilane, by mass; the modified nitrile rubber is plasticized on a two-roll mill for 4 minutes, hydrogenated silicone oil, vinyltrimethoxysilane, and 1 / 2 of the modified silica are added in sequence and kneaded for 2.5 minutes, and then the remaining modified silica and chloroplatinic acid are added and kneaded for 9 minutes. The sheet is thinned 20 times and allowed to stand for 12 hours, and then hot-pressed on a flat vulcanizer to obtain the high-temperature resistant composite material for automotive wires. The conditions are 170°C, 10 minutes, and 10 MPa. The remaining steps are the same as in Example 2.
[0062] Comparative Example 3:
[0063] The preparation method of the high-temperature resistant composite material for automotive wires in Comparative Example 3 differs from that in Example 2 in that hydrogen-containing silicone oil is not included. Specifically, step (5) is modified as follows: the following components are weighed: 100 parts by mass of modified nitrile rubber and 45 parts by mass of modified silica; the modified nitrile rubber is plasticized on a two-roll mill for 4 minutes, 1 / 2 of the modified silica is added and mixed for 2.5 minutes, and then the remaining modified silica is added and mixed for 9 minutes. The sheet is thinned 20 times and allowed to stand for 12 hours before being hot-pressed on a flat vulcanizer to obtain the high-temperature resistant composite material for automotive wires. The conditions are 170°C, 10 minutes, and 10 MPa. The remaining steps are the same as in Example 2.
[0064] Test Example 1, heat resistance test:
[0065] Test method: A TGA / DSC1 thermogravimetric analyzer (Mettler Toledo, Switzerland) was used for the determination of the initial thermal decomposition temperature under the following conditions: nitrogen atmosphere, initial temperature of 30°C, and heating rate of 10°C / min. The results are shown in Table 1.
[0066] Initial thermal decomposition temperature (℃) Example 1 429.7 Example 2 431.3 Example 3 431.9 Comparative Example 1 418.1 Comparative Example 2 421.3 Comparative Example 3 413.6
[0067] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the material prepared by the present invention has good heat resistance.
[0068] The heat resistance of Examples 1 to 3 is better than that of the comparative example, indicating that vinyltrimethoxysilane is used as a solubilizer to enhance the compatibility of hydrogenated silicone oil and nitrile rubber. The modified nitrile rubber, modified silica, and hydrogenated silicone oil are cross-linked in the presence of chloroplatinic acid. The hydrogenated silicone oil undergoes an efficient cross-linking reaction with the ethylene functional groups in the material system through the active Si-H bonds in its molecular structure, forming a highly stable three-dimensional network structure, which significantly improves the heat resistance of the material.
[0069] Test Example 2, anti-aging performance test:
[0070] Test method: The material anti-aging performance was determined in an aging test chamber with reference to standard GB / T3512-2001. The test conditions were 125°C and 168 hours. The tensile strength before and after aging was tested and the tensile strength retention before and after aging was calculated. The results are shown in Table 2.
[0071] Tensile Strength Test Method: The material was cut into I-type dumbbell-shaped specimens with a thickness of 2 mm and a working width of 4 mm. The tensile strength of the specimens was measured using a GT-AI-7000M tensile testing machine in accordance with GB / T 528-2009. The results are shown in Table 2.
[0072] Table 2
[0073] Tensile strength retention (%) Example 1 88.76 Example 2 89.34 Example 3 89.66 Comparative Example 1 62.41 Comparative Example 2 80.37 Comparative Example 3 83.24
[0074] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 2, it can be found that the material prepared by the present invention has good anti-aging performance.
[0075] The anti-aging performance of Examples 1 to 3 is better than that of the comparative example; this indicates that 2-allyl-1,3,5-triazine-2,4,6-triamine and cyanoacetyl urea are condensed and cyclized in the presence of triethyl orthoformate to generate a triazine-uracil structure with antioxidant properties. The tertiary nitrogen atom and conjugated double bond system in this structure can provide lone pairs of electrons or hydrogen atoms, effectively capturing alkyl radicals and peroxy radicals generated during the rubber oxidation process, thereby delaying rubber aging.
[0076] Test Example 3, flame retardant performance test:
[0077] Test Method: The materials prepared in the Examples and Comparative Examples were cut to a size of 100 mm × 13 mm × 13 mm. The limiting oxygen index (LOI) was measured using a JF-3 LOI tester in accordance with GB / T 2406-2008. The results are shown in Table 3.
[0078] Table 3
[0079] Limiting oxygen index (%) Example 1 31.3 Example 2 32.6 Example 3 32.5 Comparative Example 1 28.5 Comparative Example 2 26.4 Comparative Example 3 29.1
[0080] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 3, it can be found that the material prepared by the present invention has good flame retardant properties.
[0081] The flame retardant performance of the embodiment is better than that of the comparative example; the high specific surface area and porosity of silica can form a strong interaction with the rubber molecular chain, thereby enhancing the mechanical properties of the rubber; 3-(4-formylphenoxy)propyltrimethoxysilane is used to treat silica to make the silica surface contain aldehyde groups, and the aldehyde groups react with 4-propylenethiosemicarbazone to form thiosemicarbazones, which can also complex zinc ions with diphenyl ammonium phosphate as a ligand for zinc ions, thereby fixing diphenyl ammonium phosphate with flame retardant properties on the silica surface, thereby giving the material good antibacterial and flame retardant properties.
[0082] Test Example 4, test of antibacterial performance:
[0083] Test Method: The materials prepared in the Examples and Comparative Examples were cut to a size of 50 mm × 50 mm × 2 mm. Antibacterial performance was tested in accordance with the national standard GB / T31402-2015. The strain used was Escherichia coli (ATCC 25922). The results are shown in Table 4.
[0084] Table 4
[0085] Antibacterial rate (%) Example 1 96.33 Example 2 96.41 Example 3 97.69 Comparative Example 1 92.24 Comparative Example 2 32.17 Comparative Example 3 94.37
[0086] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 4, it can be found that the material prepared by the present invention has good antibacterial properties.
[0087] The antibacterial properties of Examples 1 to 3 are better than those of the comparative example; this indicates that the use of 3-(4-formylphenoxy)propyltrimethoxysilane to treat silica makes the surface of silica contain aldehyde groups, and the aldehyde groups react with 4-propylenethiosemicarbazide to generate thiosemicarbazide with antibacterial properties. The thiosemicarbazide can also complex zinc ions with diphenylammonium phosphate as a ligand for zinc ions, thereby fixing zinc ions with antibacterial properties on the surface of silica, thereby giving the material good antibacterial properties.
[0088] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.
Claims
1. A method for preparing a high-temperature resistant composite material for automotive wires, characterized in that: The method comprises the following preparation steps: (1) reacting 2-allyl-1,3,5-triazine-2,4,6-triamine and cyanoacetyl urea to obtain a functional monomer; (2) reacting the epoxidized nitrile rubber and the functional monomer to obtain a modified nitrile rubber; (3) reacting pretreated silica and 4-propylenethiosemicarbazide to obtain pre-modified silica; (4) reacting pre-modified silica, diphenyl ammonium phosphate, and zinc chloride to obtain modified silica; (5) The following components: modified nitrile rubber, modified white carbon black, hydrogenated silicone oil, chloroplatinic acid, and vinyltrimethoxysilane are mixed and hot-pressed to obtain a high-temperature resistant composite material for automotive wires.
2. The method for preparing a high-temperature resistant composite material for automotive wires according to claim 1, characterized in that: The preparation method of the functional monomer in step (1) is as follows: 2-allyl-1,3,5-triazine-2,4,6-triamine, cyanamide, triethyl orthoformate, and dioxane are mixed, heated to 95-105° C., and refluxed for 7-9 hours to obtain the functional monomer.
3. The method for preparing a high-temperature resistant composite material for automotive wires according to claim 2, characterized in that: The molar ratio of the 2-allyl-1,3,5-triazine-2,4,6-triamine, cyanoacetyl urea and triethyl orthoformate is 1:(1.2-1.4):(3.0-3.4); the mass of the dioxane is 10-12 times that of cyanoacetyl urea.
4. The method for preparing a high-temperature resistant composite material for automotive wires according to claim 1, characterized in that: The preparation method of the modified nitrile rubber in step (2) is as follows: tert-butyl hydroperoxide and molybdenum trioxide are mixed, activated at 65-75° C. for 2-3 hours, and reacted with the nitrile rubber in a torque rheometer for 30-40 minutes after the activation to obtain epoxidized nitrile rubber; and epoxidized nitrile rubber, functional monomer, N,N-dimethylformamide, and triethylamine are mixed, heated to 100-110° C. and reacted for 6-8 hours to obtain the modified nitrile rubber.
5. The method for preparing a high-temperature resistant composite material for automotive wires according to claim 4, characterized in that: The mass ratio of the nitrile rubber, tert-butyl hydroperoxide, and molybdenum trioxide is 1:(0.4-0.6):(0.003-0.004); the mass ratio of the epoxidized nitrile rubber, functional monomer, N,N-dimethylformamide, and triethylamine is 1:(0.1-0.2):(10-15):(0.3-0.5).
6. The method for preparing a high-temperature resistant composite material for automotive wires according to claim 1, characterized in that: The preparation method of the pre-modified silica in step (3) is as follows: after ultrasonically dispersing silica, anhydrous ethanol and pure water for 30-40 minutes, using hydrochloric acid to adjust the pH to 3-4, adding 3-(4-formylphenoxy)propyltrimethoxysilane, and reacting at 70-80°C for 8-10 hours to obtain pre-treated silica; mixing the pre-treated silica, 4-propylenethiosemicarbazide and methanol, heating to 60-65°C, and reflux reaction for 1-2 hours to obtain pre-modified silica.
7. The method for preparing a high-temperature resistant composite material for automotive wires according to claim 6, characterized in that: The mass ratio of the white carbon black, anhydrous ethanol, pure water, and 3-(4-formylphenoxy)propyltrimethoxysilane is 1:(10-15):(5-10):(1-2); the mass ratio of the pretreated white carbon black, 4-propylenethiosemicarbazide, and methanol is 1:(2-3):(20-30).
8. The method for preparing a high-temperature resistant composite material for automotive wires according to claim 1, characterized in that: The preparation method of the modified silica in step (4) is as follows: pre-modified silica, diphenyl ammonium phosphate, and methanol are mixed and recorded as solution A, zinc chloride and methanol are mixed and recorded as solution B, solution B is poured into solution A and stirred for 1-2 hours, and then allowed to stand for 2-3 hours to obtain modified silica; The mass ratio of pre-modified white carbon black, diphenyl ammonium phosphate and zinc chloride is 1:(2-3):(1.5-2.0).
9. The method for preparing a high-temperature resistant composite material for automotive wires according to claim 1, characterized in that: The preparation method of the high-temperature resistant composite material for automotive wires in step (5) is as follows: weigh the following components: 100 parts of modified nitrile rubber, 40-50 parts of modified white carbon black, 15-20 parts of hydrogenated silicone oil, 1-2 parts of chloroplatinic acid, and 3-5 parts of vinyltrimethoxysilane, calculated by mass; plasticize the modified nitrile rubber for 3-5 minutes, add hydrogenated silicone oil, vinyltrimethoxysilane, and 1 / 2 of the modified white carbon black in sequence and mix for 2-3 minutes, then add the remaining modified white carbon black and chloroplatinic acid and mix for 8-10 minutes, and then stand and hot-press to obtain the high-temperature resistant composite material for automotive wires.
10. A high-temperature resistant composite material for automotive electric wires prepared according to the method according to any one of claims 1 to 9.