Anti-electromagnetic shielding conductive flame-retardant silane elastomer as well as preparation and application thereof
By synthesizing P-PAN in conductive elastomers and using it in composite silane-based elastomers, the problem of traditional flame retardants affecting the conductivity is solved, and the coordinated improvement of high flame retardant and high conductivity is achieved, meeting the high-performance needs in special fields such as armored vehicle components.
Patent Information
- Application Number
- CN202510394184.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-31
- Publication Date
- 2025-06-06
AI Technical Summary
The addition of traditional flame retardants affects the conductivity and electromagnetic shielding resistance, making it difficult to meet the requirements of high flame retardant and high conductivity in special fields.
By synthesizing the modifier P-PAN with flame retardant components and conductive group, it is used in γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane and nanosilica composite silane-based elastomers, the flame retardant and conductive properties are improved through reaction polymerization and synergistic flame retardant effects.
The flame retardant performance and conductivity are improved, the impact of flame retardant addition on conductivity and electromagnetic shielding performance is reduced, and the high-performance needs in special fields such as armored vehicle components are met.
Smart Images
Figure CN120098449A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to conductive elastomer technology, and in particular to an anti-electromagnetic shielding conductive flame-retardant silane elastomer and a preparation method thereof, as well as application of the elastomer in the preparation of armored vehicle parts. Background Art
[0002] Conductive elastomer is a fully cured silicone containing a variety of highly conductive particles. It can provide good shielding performance and environmental sealing. It is often used in special fields such as armored vehicle parts to protect electronic components in the cabin through anti-electromagnetic shielding performance. However, in special fields, it requires higher flame retardant performance to meet the application requirements in special fields. The addition of traditional flame retardants affects the conductivity and anti-electromagnetic shielding performance. Summary of the invention
[0003] The present invention is developed in view of the above problems, and its purpose is to provide an anti-electromagnetic shielding conductive flame-retardant silane elastomer and a preparation method thereof, so as to solve the problem that the addition of traditional flame retardants affects the conductive performance and anti-electromagnetic shielding.
[0004] The present invention firstly provides a method for preparing an anti-electromagnetic shielding conductive flame-retardant silane elastomer, wherein nano silicon dioxide is added into water and stirred, and after being evenly dispersed, a silane mixture of γ-aminopropyl triethoxysilane and γ-methacryloxypropyl trimethoxysilane is added, heated to 95°C-98°C and reacted for 2h-3h, then P-PAN is added and stirred for 1h-2h, then stirring is stopped, the temperature is raised to 110°C-115°C and the reaction is continued for 4h-5h, and the silane elastomer is obtained by cooling to room temperature, wherein the mass ratio of nano silicon dioxide, water, γ-aminopropyl triethoxysilane, γ-methacryloxypropyl trimethoxysilane and P-PAN is (10-12):100:(20-22):(15-20):(20-22), and the structural formula of P-PAN is as follows.
[0005]
[0006] Furthermore, the mass ratio of nano-silica, water, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and P-PAN is 10:100:20:15:20.
[0007] Wherein P-PAN is prepared by the following method: Phytic acid and polyaniline are added to a mixture of N,N-dimethylformamide and distilled water, and reacted at a temperature of 95°C to 98°C for 4h to 5h, wherein the solid-liquid ratio is (5~6) g:100 mL, the mass ratio of phytic acid to polyaniline is 1:(4~5), and the volume ratio of N,N-dimethylformamide to distilled water is (1.2~1.5):1; then a certain amount of phytic acid is continuously dripped at a rate of 30 drops / min, the temperature is raised to 105°C to 108°C and the reaction is continued for 4h to 5h, wherein the solid-liquid ratio of the dripped phytic acid to the mixture is (5~6) g:500 mL; after cooling to room temperature, the reactant is transferred to a rotary evaporator to remove the solvent, and then washed and filtered with excess distilled water to obtain P-PAN; Its synthetic chemical formula is as follows.
[0008]
[0009] Specifically, the solvent was removed by rotary evaporation at a temperature of 80°C to 85°C; Specifically, the volume ratio of the mixed solution to the excess distilled water is 1:(5-6).
[0010] Specifically, the stirring rate may be 500-600 rpm.
[0011] The present invention also provides an anti-electromagnetic shielding conductive flame-retardant silane elastomer prepared by the above preparation method and application of the anti-electromagnetic shielding conductive flame-retardant silane elastomer in the preparation of armored vehicle parts.
[0012] According to the present invention, a flame retardant component and a conductive group modifier P-PAN are synthesized and used in a γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and nano-silica composite silane-based elastomer, so that the flame retardant performance and the conductive performance are improved through reaction polymerization and synergistic flame retardant effect.
[0013] According to the inventor's research: 1. The ionic bond formed by the reaction of phytic acid and PAN provides an electronic environment and reduces the impact on conductivity.
[0014] 2. At the same time, polyhydroxyl and silane hydroxyl systems have good compatibility, which reduces the impact of flame retardant addition on conductivity and electromagnetic shielding performance.
[0015] 3. The P element in phytic acid and the N element in polyaniline form a PN synergistic flame retardant system. At the same time, silane forms a Si-O-Si cross-linked structure during the pyrolysis process, which supplements the dense carbon layer. DETAILED DESCRIPTION
[0016] The specific implementation methods of the present invention are used to provide necessary disclosure for those skilled in the art to fully understand the present invention, and are intended to effectively support the claims of the present invention. At the same time, this section will involve the interpretation or definition of the features and terms of the technical solution of the present invention. Those skilled in the art should understand the scope of the claims of the present invention in conjunction with the explanation of the specific features and terms in the specification, and should not arbitrarily distort the true connotations represented by the features and terms of the present invention.
[0017] It must be understood that in any work involving the definition of the scope of the claims of the present invention, the specific embodiments provided by the present invention can be used to fully support the appropriate summaries of equivalent or superior solutions summarized therefrom, and the scope of the claims should never be understood as not exceeding the examples themselves. It must also be understood that with the development of technology and the emergence of new scenarios, the technical solutions provided by the embodiments of the present application will also be applicable to similar technical problems within the scope of those skilled in the art without any creative work, and the scope of protection of the present invention should not be limited to the examples recorded in the specific implementation methods of the present invention.
[0018] [Modifier P-PAN and its preparation] P-PAN is a synthetic flame retardant and conductive group modifier, and its structural formula is as follows.
[0019]
[0020] Preparation Example 1: 10 g of phytic acid and 40 g of polyaniline were added to a mixture of 600 mL of N,N-dimethylformamide and 400 mL of distilled water, and reacted at 95°C for 4 hours, and then 10 g of phytic acid was dripped into the reaction vessel at a rate of 30 drops per minute, and the temperature was raised to 105°C and the reaction was continued for 4 hours. After cooling to room temperature 25°C, the reactants were transferred to a rotary evaporator, and the solvent was removed by a rotary evaporator at 80°C to obtain a product, and the product was washed and filtered through 2000 mL of excess distilled water to obtain P-PAN.
[0021] Preparation Example 2: 10g of phytic acid and 50g of polyaniline were placed in 550mL of N,N-dimethylformamide and 450mL of distilled water, and reacted at 98°C for 5 hours, and then 12g of phytic acid was dripped into the reaction container at a rate of 30 drops per minute, and the temperature was raised to 108°C and the reaction was continued for 5 hours. After cooling to room temperature 25°C, the reactants were transferred to a rotary evaporator, and the solvent was removed by a rotary evaporator at 85°C to obtain the product, and the product was washed and filtered through 3000mL of excess distilled water to obtain P-PAN.
[0022] The synthetic chemical formula is as follows.
[0023]
[0024] By synthesizing P-PAN, a flame retardant component and a conductive group modifier, and using it in γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and nano-silica composite silane-based elastomer, the flame retardant and conductive properties are improved through reaction polymerization and synergistic flame retardant effect.
[0025] [Silane elastomer and its preparation] The silane elastomer proposed in the present invention has anti-electromagnetic shielding, conductive and flame retardant properties, and is specifically suitable for use in, for example, armored vehicle parts, and protects electronic components in the cabin through anti-electromagnetic shielding performance. The application is, for example, as a conductive spacer, conductive layer, conductive shell, etc. of electronic components that need to shield electromagnetics and require conductive and flame retardant properties.
[0026] The materials and equipment used in the following examples and comparative examples are described as follows.
[0027] Material: Nano-silicon dioxide: particle size 80-100nm Polyaniline: degree of polymerization 800-1000 equipment: The reaction container is provided with a 500-1200 rpm speed stirrer and a heating function. The present invention does not limit the specific equipment product.
[0028] The present invention provides the following preparation method of the silane elastomer.
[0029] Embodiment 1: Add 10g of nano-silica into a reaction container containing 100g of water and start stirring at a rate of 500 rpm. After being evenly dispersed, add into a mixture of 20g of γ-aminopropyltriethoxysilane and 15g of γ-methacryloxypropyltrimethoxysilane, heat to 95°C and react for 2h. Then add 20g of P-PAN into the reaction system and continue stirring for 1h, then stop stirring, heat to 110°C and continue reacting for 4h, and cool to room temperature 25°C to obtain a conductive flame-retardant silane elastomer.
[0030] Embodiment 2: 12g of nano-silica was added to a reaction container containing 100g of water and stirred at a rate of 600 rpm. After being evenly dispersed, it was added into a mixed solution of 22g of γ-aminopropyltriethoxysilane and 20g of γ-methacryloxypropyltrimethoxysilane, heated to 98°C and reacted for 3h. Then 22g of P-PAN was added to the reaction system and stirring was continued for 2h, then stirring was stopped, the temperature was raised to 115°C and the reaction was continued for 5h. The conductive flame-retardant silane elastomer was obtained after cooling to room temperature of 25°C.
[0031] [Ordinary and comparative silane elastic preparation] Comparative Example 1 (ordinary silane elastomer): Add 10 g of nano-silica into a reaction container containing 100 g of water and start stirring at a rate of 500 rpm. After being evenly dispersed, add a mixture of 20 g of γ-aminopropyltriethoxysilane and 15 g of γ-methacryloxypropyltrimethoxysilane and continue stirring for 1 hour, then stop stirring, heat to 110°C and react for 4 hours, and cool to room temperature 25°C to obtain a common silane elastomer.
[0032] Comparative Example 2 (Phytic acid is directly added to PAN to synthesize P-PAN): 20 g of phytic acid and 40 g of polyaniline were added to a mixed solution of 600 mL of N,N-dimethylformamide and 400 mL of distilled water, and reacted at 105°C for 4 hours. After cooling to room temperature (25°C), the reactants were transferred to a rotary evaporator, and the solvent was removed by the rotary evaporator at 80°C to obtain a product. The product was washed and filtered with 2000 mL of excess distilled water to obtain a comparative P-PAN. 10g of nano-silica was added to a reaction container containing 100g of water and stirred at a rate of 500 rpm. After being evenly dispersed, 20g of γ-aminopropyltriethoxysilane and 15g of γ-methacryloxypropyltrimethoxysilane were added to the silane solution, heated to 95°C and reacted for 2h. Then 20g of comparison P-PAN was added to the reaction system and stirring was continued for 1h, then stirring was stopped, the temperature was raised to 110°C and the reaction was continued for 4h, and then cooled to room temperature 25°C to obtain a comparison flame retardant silane elastomer.
[0033] [test]
[0034] According to the test results, the analysis performance comparison is as follows.
[0035] Comparison of Example 1 with the Comparative Example: 1. The peak heat release rate obtained by cone calorimeter test is 65.5% lower than that of the common silane elastomer in comparative example 1 and 46.4% lower than that in comparative example 2.
[0036] 2. The test conductivity of the sample was improved by 28.6% compared with the ordinary sample in Comparative Example 1 and by 17.4% compared with Comparative Example 2 by using a dual-electrical four-probe tester.
[0037] 3. The average electromagnetic shielding effectiveness is 41.8dB, which is 90.9% higher than the ordinary sample in Comparative Example 1 and 20.46% higher than that in Comparative Example 2.
[0038] Comparison of Example 2 with the Comparative Example: 1. The peak heat release rate obtained by cone calorimeter test is 59.5% lower than that of the common silane elastomer in comparative example 1 and 38.6% lower than that in comparative example 2.
[0039] 2. The test conductivity of the sample was improved by 24.3% compared with the ordinary sample in Comparative Example 1 and 13.4% compared with Comparative Example 2 by using a dual-electrical four-probe tester.
[0040] 3. The average electromagnetic shielding effectiveness is 41.8dB, which is 81.8% higher than that of the ordinary sample in Comparative Example 1 and 14.5% higher than that of Comparative Example 2.
Claims
1. A method for preparing an electromagnetic shielding conductive flame-retardant silane elastomer, It is characterized in that Add nano-silicon dioxide into water and start stirring. After being evenly dispersed, add a silane mixture of γ-aminopropyl triethoxysilane and γ-methacryloxypropyl trimethoxysilane, heat to 95°C~98°C and react for 2h~3h, then add P-PAN and continue stirring for 1h~2h, then stop stirring, heat to 110°C~115°C and continue reacting for 4h~5h, and cool to room temperature to obtain the silane elastomer, wherein the mass ratio of nano-silicon dioxide, water, γ-aminopropyl triethoxysilane, γ-methacryloxypropyl trimethoxysilane and P-PAN is (10~12):100:(20~22):(15~20):(20~22), wherein the structural formula of P-PAN is as follows 。 2. The preparation method according to claim 1, wherein The mass ratio of nano-silica, water, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and P-PAN is 10:100:20:15:
20.
3. The preparation method according to claim 1, wherein P-PAN was prepared by the following method: Add phytic acid and polyaniline to a mixture of N,N-dimethylformamide and distilled water, and react at 95°C-98°C for 4h-5h, wherein the material-liquid ratio is (5-6) g:100 mL, the mass ratio of phytic acid and polyaniline is 1:(4-5), and the volume ratio of N,N-dimethylformamide and distilled water is (1.2-1.5):1; Then, a certain amount of phytic acid is continuously added at a rate of 30 drops / min, the temperature is raised to 105° C. to 108° C., and the reaction is continued for 4 h to 5 h, wherein the material-liquid ratio of the added phytic acid to the mixed solution is (5 to 6) g: 500 mL; After cooling to room temperature, the reactants were transferred to a rotary evaporator to remove the solvent, and then washed and filtered with distilled water to obtain P-PAN; Its synthetic chemical formula is as follows 。 4. The preparation method according to claim 3, wherein The solvent was removed by rotary evaporation at 80°C~85°C.
5. The preparation method according to claim 3, wherein: The volume ratio of the mixed solution to the excess distilled water is 1:(2-3).
6. The preparation method according to claim 3, wherein: The stirring rate is 500~600 rpm.
7. An electromagnetic shielding and flame-retardant silane elastomer prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the anti-electromagnetic shielding conductive flame-retardant silane elastomer according to claim 7 in the preparation of armored vehicle parts.