Fireproof composite aluminum plate strip and preparation method thereof

Abstract

This invention belongs to the technical field of metal composite panels, specifically relating to a fire-resistant composite aluminum strip and its preparation method. The fire-resistant composite aluminum strip comprises an upper aluminum strip, a middle fire-resistant material, and a lower copper strip. The middle fire-resistant material comprises the following components by weight: 30-40 parts ethylene-vinyl acetate copolymer; 20-25 parts epoxy resin; 15-20 parts styrene-maleic anhydride copolymer; 10-15 parts linear low-density polyethylene; and 8-10 parts highly flame-retardant basalt fiber. The middle fire-resistant material provided by this invention has good mechanical properties, bonding properties, and excellent flame-retardant properties. Using it for bonding aluminum and copper strips can yield a composite aluminum strip with good bending strength and a high fire resistance rating, achieving an A1 fire rating, making it particularly suitable for fields with high flame-retardant requirements.

Description

Technical Field

[0001] This invention belongs to the field of metal composite plate technology, specifically relating to a fireproof composite aluminum plate and strip and its preparation method. Background Technology

[0002] Composite aluminum sheets and strips are sheets made by combining aluminum and aluminum alloys as the base material with another metal (such as copper) or non-metallic materials (such as mineral-filled core materials or polymer materials) through specific processes. Based on their core structure, they can be divided into two categories: The first category is metal-metal composite structures, such as copper-aluminum composite sheets and strips. These are produced by continuously casting and semi-molten rolling composite methods, where copper and copper alloy sheets and strips are laminated onto one or both sides of the aluminum and aluminum alloy base material. This composite structure achieves a metallurgical bond that complements the electrical conductivity of copper and the thermal conductivity and lightweight properties of aluminum, making it suitable for applications such as power transmission and heat exchange. The second category is metal-non-metal composite structures, such as aluminum... Composite panels (ACP) are made by hot extrusion of two layers of aluminum sheets with decorative coatings and a mineral-filled core material (such as flame-retardant mineral polymers). The outer aluminum sheet provides corrosion resistance and decoration, while the core material gives the composite panel sound insulation, heat insulation, and fire resistance. They are widely used in building curtain walls, interior decoration, and other applications. Currently, single metals / alloys are difficult to meet the comprehensive performance requirements of materials in multiple fields. Metal composite decorative materials are increasingly used and applied in more and more fields due to their advantages such as light weight, high specific strength, and rich decorative effects. At the same time, the requirements for the fire resistance of metal composite decorative materials are also becoming more and more stringent.

[0003] Chinese patent application number CN202211503908.5 discloses a magnesium-aluminum bimetallic multilayer fireproof board. This is achieved by coating an aluminum plate with a fire-retardant coating, drying it, covering the coated aluminum plate with a magnesium plate, and then covering the other side of the magnesium plate with another aluminum plate also coated with a fire-retardant coating. The aluminum and magnesium plates are bonded together with an epoxy resin adhesive. The fire-retardant coating includes epoxy resin, diaminodiphenylmethane, and ammonium polyphosphate-metal-organic framework composite. Chinese patent application number CN202411738794.1 discloses a fireproof bimetallic composite board, using an aluminum plate as the base layer. A polymer film is applied to the upper surface of the aluminum plate to form an adhesive layer. A copper plate is coated onto the upper surface of the composite material to form a fire-resistant bimetallic composite panel. The polymer film includes ethylene-vinyl acetate copolymer, epoxy resin, polymethyl methacrylate, modified polyglycidyl methacrylate, composite filler, and polyamide. The composite filler is made by chemically grafting synthesized flame retardants with silica and carbon nanotubes. The modified polyglycidyl methacrylate is made by chemically coating graphene oxide onto the surface of polyglycidyl methacrylate. Although the above patents have improved the flame retardancy of the composite panel to a certain extent by adding modified flame retardants, the flame retardant performance still cannot reach the strong flame retardant standard. Therefore, a metal composite panel material with strong fire-resistant and flame-retardant properties is needed. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a fire-resistant composite aluminum strip, comprising an upper aluminum strip, a middle fire-resistant material, and a lower copper strip. The middle fire-resistant material possesses excellent mechanical and adhesive properties, as well as superior flame-retardant properties. When used for bonding the aluminum and copper strips, a composite aluminum strip with good bending strength and a high fire resistance rating can be obtained, achieving a fire resistance rating of A1, making it particularly suitable for applications requiring high flame retardancy.

[0005] The technical solution adopted by the present invention to solve the above problems is as follows:

[0006] A fireproof composite aluminum strip, comprising an upper aluminum strip, a middle fireproof material layer, and a lower copper strip.

[0007] Furthermore, the intermediate fireproof layer material comprises the following components by weight: 30-40 parts of ethylene-vinyl acetate copolymer; 20-25 parts of epoxy resin; 15-20 parts of styrene-maleic anhydride copolymer; 10-15 parts of linear low-density polyethylene; and 8-10 parts of highly flame-retardant basalt fiber.

[0008] Furthermore, the preparation method of the highly flame-retardant basalt fiber is as follows:

[0009] (1) Add ethanol aqueous solution and basalt fiber to the reaction vessel, stir evenly, add 3-chloropropyltrimethoxysilane, adjust the pH of the solution to 5-6, place at 50-60℃, react for 4-5h to obtain surface chlorinated basalt fiber.

[0010] (2) Add ethanol and surface chlorinated basalt fiber to the reaction vessel, stir evenly, add melamine polyphosphate and triethylamine, place at 70-80℃ for 5-6 hours to obtain strong flame retardant basalt fiber.

[0011] Further, in step (1), the mass ratio of basalt fiber to 3-chloropropyltrimethoxysilane is 1:0.2-0.3; and the mass ratio of water to ethanol in the ethanol aqueous solution is 1:1.5-2.

[0012] Further, in step (2), the mass ratio of surface chlorinated basalt fiber, melamine polyphosphate, and triethylamine is 1:0.2-0.3:0.05-0.06.

[0013] Furthermore, the preparation method of the polyphosphate melamine mentioned in step (2) is as follows:

[0014] S1. Add ethanol and melamine to the reaction vessel, stir until homogeneous, add 1-bromo-3-buten-2-ol and triethylamine, place at 60-70℃ and stir for 4-5 hours to obtain enol melamine.

[0015] S2. Add anhydrous diethyl ether, enol melamine and triethylamine to the reaction vessel, stir well, add diethylphosphite chloride slowly dropwise under ice bath conditions, and continue to keep the reaction at the temperature for 3-4 hours to obtain enol melamine.

[0016] S3. Add N,N-dimethylformamide and alkenyl melamine to the reaction vessel, stir until homogeneous, add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, place at 95-100℃ and stir for 9-10 hours to obtain polyphosphate melamine.

[0017] Furthermore, the molar ratio of melamine, 1-bromo-3-buten-2-ol, and triethylamine in step S1 is 1:3.1-3.2:1.5-1.6.

[0018] Furthermore, in step S2, the molar ratio of enol melamine, diethylphosphoryl chloride, and triethylamine is 1:3.2-3.3:1.7-1.8.

[0019] Further, in step S3, the molar ratio of alkenyl melamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:3.1-3.2.

[0020] The present invention also provides a method for preparing fireproof composite aluminum strip, comprising the following steps: subjecting one side surface of the upper aluminum strip and the lower copper strip to discharge corona treatment to form a corona surface; covering the corona surface of the lower copper strip with an intermediate fireproof material, and then combining it with the corona surface of the upper aluminum strip, and hot-pressing to obtain the fireproof composite aluminum strip.

[0021] Furthermore, the conditions for hot pressing are: temperature of 170-180℃, pressure of 4-5KPa, and time of 12-15s.

[0022] The present invention has the following beneficial effects:

[0023] 1. In this invention, melamine is reacted sequentially with 1-bromo-3-buten-2-ol, diethylphosphite chloride, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to obtain polyphosphate melamine. The polyphosphate melamine prepared by this invention contains melamine groups, phosphate groups, and DOPO groups. These groups can exert a PN synergistic flame retardant effect, producing a synergistic effect during the combustion process of the material, generating a dense PNO carbon layer, which has good heat insulation, oxygen barrier, flame retardant, and smoke suppression effects, thus having strong flame retardant properties.

[0024] 2. This invention uses basalt fiber with strong flame retardancy as raw material. First, it reacts with 3-chloropropyltrimethoxysilane to obtain surface-chlorinated basalt fiber, solving the problem of poor interfacial bonding caused by its smooth surface and strong chemical inertness. This improves its compatibility with the intermediate layer fire-retardant material components and provides reaction sites for further modification. Then, the Cl- in the surface-chlorinated basalt fiber reacts with the three NH- in the melamine polyphosphate to obtain highly flame-retardant basalt fiber. The highly flame-retardant basalt fiber obtained by this invention is made with melamine... With the basalt group as the core, the three basalt fibers, phosphate ester group and DOPO group are chemically bonded together. This stable structure helps to improve the mechanical strength of the material. The basalt fiber has a melting point of about 1500℃ and has good high-temperature stability. It can maintain its structural integrity in high temperature or flame environment and will not produce molten droplets or toxic gases due to combustion. It has a strong flame retardant effect and can work synergistically with the PN flame retardant system formed by melamine group, phosphate ester group and DOPO group, thereby greatly enhancing the fire resistance and flame retardant performance of the material.

[0025] 3. The intermediate fireproof material provided by this invention has good mechanical properties, bonding properties and excellent flame retardant properties. When used for bonding aluminum strip and copper strip, it can produce composite aluminum strip with good bending strength and high fire resistance, with a fire resistance rating of A1. It is especially suitable for fields with high flame retardant requirements. Detailed Implementation

[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] All raw materials used in the following examples are commercially available products. The thickness of the upper aluminum strip and the lower copper strip is 0.5 mm; melamine CAS number 108-78-1; 1-bromo-3-buten-2-ol CAS number 64341-49-7; triethylamine CAS number 121-44-8; diethylphosphonochloride CAS number 589-57-1; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide CAS number 35948-25-5; 3-chloropropyltrimethoxysilane CAS number 2530-87-2; ethanol CAS number 64-17-5; diethyl ether CAS number 60-29-7; N,N-dimethylformamide CAS number 68-12-2; ethyl acetate CAS number 141-78-6; dichloromethane CAS number 75-09-2.

[0028] In the technical solution of this invention, the preparation method of the intermediate fireproof material is as follows: according to the weight ratio, ethylene-vinyl acetate copolymer, epoxy resin, styrene-maleic anhydride copolymer, linear low-density polyethylene and strong flame-retardant basalt fiber are mixed, melt-extruded and granulated by a twin-screw extruder, and then calendered by a calender to obtain the intermediate fireproof material; wherein the melt extrusion granulation temperature is 180℃, and the thickness of the intermediate fireproof material is 0.2mm.

[0029] Example 1

[0030] A fireproof composite aluminum strip includes an upper aluminum strip, a middle fireproof material layer, and a lower copper strip; wherein the middle fireproof material comprises the following components by weight: 40 parts of ethylene-vinyl acetate copolymer; 25 parts of epoxy resin; 18 parts of styrene-maleic anhydride copolymer; 15 parts of linear low-density polyethylene; and 10 parts of highly flame-retardant basalt fiber.

[0031] The preparation method of the highly flame-retardant basalt fiber is as follows:

[0032] (1) Add ethanol aqueous solution and basalt fiber to the reaction vessel, stir evenly, add 3-chloropropyltrimethoxysilane, adjust the pH of the solution to 6, place at 60℃ and react for 4h. After the reaction is completed, filter, wash the product with water and ethanol, and dry to obtain surface chlorinated basalt fiber; wherein the mass ratio of basalt fiber to 3-chloropropyltrimethoxysilane is 1:0.3; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:2; the mass ratio of basalt fiber to ethanol aqueous solution is 1:10.

[0033] (2) Add ethanol and surface chlorinated basalt fiber to the reaction vessel, stir evenly, add melamine polyphosphate and triethylamine, place at 70°C and react for 6 hours. After the reaction is completed, filter, wash the product with water and ethanol, and dry to obtain strong flame retardant basalt fiber; wherein the mass ratio of surface chlorinated basalt fiber, melamine polyphosphate and triethylamine is 1:0.3:0.06.

[0034] The preparation method of melamine polyphosphate is as follows:

[0035] ;

[0036] S1. Add 500mL of ethanol and 12.6g of melamine to the reaction vessel, stir well, and then add 46.8g of... 1-Bromo-3-buten-2-ol and 16.2 g of triethylamine were reacted at 65 °C for 4 h with stirring. After the reaction was complete, ethanol was removed, and the mixture was extracted with water and ethyl acetate. The organic phase was concentrated and dried to obtain 27.5 g of enol melamine. The molar ratio of melamine, 1-bromo-3-buten-2-ol, and triethylamine was 1:3.1:1.6. ESI (m / z): 337.4 [M+H]+, 1H-NMR (600 MHz, DMSO-d6, δppm): 9.21 (s, 3H), 6.18 (s, 3H), 5.89-5.94 (m, 3H), 5.26-5.32 (m, 6H), 4.25-4.30 (m, 3H), 3.23-3.30 (m, 6H).

[0037] S2. Add 400 mL of anhydrous diethyl ether, 27.5 g of enol melamine, and 14.1 g of triethylamine to the reaction vessel, stir well, and slowly add 41.0 g of diethylphosphoryl chloride dropwise while the vessel is in an ice bath. After the addition is complete, continue to keep the reaction at this temperature for 4 hours. After the reaction is complete, remove the anhydrous diethyl ether, extract with water and ethyl acetate, concentrate and dry the organic phase to obtain 48.5 g of enol melamine; the molar ratio of enol melamine, diethylphosphoryl chloride, and triethylamine is 1: 3.2:1.7; ESI(m / z): 697.7[M+H]+, 1H-NMR (600MHz, DMSO-d6, δppm): 9.23 (s, 3H), 5.90-5.94 (m, 3H) , 5.28-5.33 (m, 6H), 4.23-4.29 (m, 3H), 3.85-3.90 (m, 12H); 3.28-3.34 (m, 6H); 1.25-1.29 (m, 18H);

[0038] S3. Add 500 mL of N,N-dimethylformamide and 45.0 g of alkenyl melamine to the reaction vessel, stir well, add 43.3 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), place at 95 °C, and stir for 10 h. After the reaction is complete, extract with water and dichloromethane. The organic phase is concentrated and dried to obtain 68.7 g of polyphosphate melamine; the molar ratio of alkenyl melamine to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:3.1; ESI (m / z): 673.6 [M / 2+H]+, 1H-NMR (600 MHz, DMSO-d6, δppm): 9.20 (s, 3H), 7.75-8.00 (m, 6H), 7.41-7.50 (m, 12H), 7.31-7.36 (m, 6H), 3.86-3.92 ( m, 12H); 3.36-3.42 (m, 6H), 3.06-3.10 (m, 3H), 2.54-2.61 (m, 6H), 1.96-2.05 (m, 6H), 1.26-1.31 (m, 18H).

[0039] A method for preparing a fireproof composite aluminum strip includes the following steps: subjecting one side surface of the upper aluminum strip and the lower copper strip to discharge corona treatment to form a corona surface; covering the corona surface of the lower copper strip with an intermediate fireproof material, and then combining it with the corona surface of the upper aluminum strip, followed by hot pressing to obtain the fireproof composite aluminum strip; wherein the hot pressing conditions are: temperature 180℃, pressure 4KPa, and time 15s.

[0040] Example 2

[0041] A fireproof composite aluminum strip includes an upper aluminum strip, a middle fireproof material, and a lower copper strip; wherein the middle fireproof material includes the following components by weight: 35 parts ethylene-vinyl acetate copolymer; 23 parts epoxy resin; 15 parts styrene-maleic anhydride copolymer; 10 parts linear low-density polyethylene; and 9 parts highly flame-retardant basalt fiber.

[0042] The preparation method of the highly flame-retardant basalt fiber is as follows:

[0043] (1) Add ethanol aqueous solution and basalt fiber to the reaction vessel, stir evenly, add 3-chloropropyltrimethoxysilane, adjust the pH of the solution to 5.5, place at 50℃ and react for 4.5h. After the reaction is completed, filter, wash the product with water and ethanol, and dry to obtain surface chlorinated basalt fiber; wherein the mass ratio of basalt fiber to 3-chloropropyltrimethoxysilane is 1:0.25; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:1.5; and the mass ratio of basalt fiber to ethanol aqueous solution is 1:10.

[0044] (2) Add ethanol and surface chlorinated basalt fiber to the reaction vessel, stir evenly, add melamine polyphosphate and triethylamine, place at 75°C for 5.5 h, filter, wash the product with water and ethanol, and dry to obtain strong flame retardant basalt fiber; wherein the mass ratio of surface chlorinated basalt fiber, melamine polyphosphate and triethylamine is 1:0.25:0.055.

[0045] A method for preparing a fireproof composite aluminum strip includes the following steps: subjecting one side surface of the upper aluminum strip and the lower copper strip to discharge corona treatment to form a corona surface; covering the corona surface of the lower copper strip with an intermediate fireproof material, and then combining it with the corona surface of the upper aluminum strip, followed by hot pressing to obtain the fireproof composite aluminum strip; wherein the hot pressing conditions are: temperature 175℃, pressure 4.5KPa, and time 14s.

[0046] Example 3

[0047] A fireproof composite aluminum strip includes an upper aluminum strip, a middle fireproof material, and a lower copper strip; wherein the middle fireproof material includes the following components by weight: 30 parts ethylene-vinyl acetate copolymer; 20 parts epoxy resin; 20 parts styrene-maleic anhydride copolymer; 12 parts linear low-density polyethylene; and 8 parts highly flame-retardant basalt fiber.

[0048] The preparation method of the highly flame-retardant basalt fiber is as follows:

[0049] (1) Add ethanol aqueous solution and basalt fiber to the reaction vessel, stir evenly, add 3-chloropropyltrimethoxysilane, adjust the pH of the solution to 5, place at 55℃ and react for 5h. After the reaction is completed, filter, wash the product with water and ethanol, and dry to obtain surface chlorinated basalt fiber; wherein the mass ratio of basalt fiber to 3-chloropropyltrimethoxysilane is 1:0.2; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:1.8; and the mass ratio of basalt fiber to ethanol aqueous solution is 1:10.

[0050] (2) Add ethanol and surface chlorinated basalt fiber to the reaction vessel, stir evenly, add melamine polyphosphate and triethylamine, place at 80°C and react for 5 hours. After the reaction is completed, filter, wash the product with water and ethanol, and dry to obtain strong flame retardant basalt fiber; wherein the mass ratio of surface chlorinated basalt fiber, melamine polyphosphate and triethylamine is 1:0.2:0.05.

[0051] A method for preparing a fireproof composite aluminum strip includes the following steps: subjecting one side surface of the upper aluminum strip and the lower copper strip to discharge corona treatment to form a corona surface; covering the corona surface of the lower copper strip with an intermediate fireproof material, and then combining it with the corona surface of the upper aluminum strip, followed by hot pressing to obtain the fireproof composite aluminum strip; wherein the hot pressing conditions are: temperature 170℃, pressure 5KPa, and time 12s.

[0052] Example 4

[0053] A fireproof composite aluminum strip includes an upper aluminum strip, a middle fireproof material layer, and a lower copper strip; wherein the middle fireproof material comprises the following components by weight: 40 parts of ethylene-vinyl acetate copolymer; 20 parts of epoxy resin; 16 parts of styrene-maleic anhydride copolymer; 14 parts of linear low-density polyethylene; and 9 parts of highly flame-retardant basalt fiber.

[0054] The preparation method of the highly flame-retardant basalt fiber is as follows:

[0055] (1) Add ethanol aqueous solution and basalt fiber to the reaction vessel, stir evenly, add 3-chloropropyltrimethoxysilane, adjust the pH of the solution to 5.5, place at 60℃ and react for 5h. After the reaction is completed, filter, wash the product with water and ethanol, and dry to obtain surface chlorinated basalt fiber; wherein the mass ratio of basalt fiber to 3-chloropropyltrimethoxysilane is 1:0.25; the mass ratio of water to ethanol in the ethanol aqueous solution is 1:2; the mass ratio of basalt fiber to ethanol aqueous solution is 1:10.

[0056] (2) Add ethanol and surface chlorinated basalt fiber to the reaction vessel, stir evenly, add melamine polyphosphate and triethylamine, place at 80°C for 6 hours, filter after the reaction is completed, wash the product with water and ethanol, and dry to obtain strong flame retardant basalt fiber; wherein the mass ratio of surface chlorinated basalt fiber, melamine polyphosphate and triethylamine is 1:0.25:0.05.

[0057] A method for preparing a fireproof composite aluminum strip includes the following steps: subjecting one side surface of the upper aluminum strip and the lower copper strip to discharge corona treatment to form a corona surface; covering the corona surface of the lower copper strip with an intermediate fireproof material, and then combining it with the corona surface of the upper aluminum strip, followed by hot pressing to obtain the fireproof composite aluminum strip; wherein the hot pressing conditions are: temperature of 180℃, pressure of 5KPa, and time of 13s.

[0058] Comparative Example 1

[0059] The fireproof material in the intermediate layer is different from that in Example 1.

[0060] A fireproof composite aluminum strip includes an upper aluminum strip, a middle fireproof material layer, and a lower copper strip; wherein the middle fireproof material comprises the following components by weight: 40 parts of ethylene-vinyl acetate copolymer; 25 parts of epoxy resin; 18 parts of styrene-maleic anhydride copolymer; 15 parts of linear low-density polyethylene; and 10 parts of highly flame-retardant basalt fiber.

[0061] The preparation method of the highly flame-retardant basalt fiber is as follows:

[0062] (1) Same as step (1) in Example 1;

[0063] (2) Add ethanol and surface chlorinated basalt fiber to the reaction vessel, stir evenly, add alkenyl melamine and triethylamine, place at 70°C for 6 hours, filter after the reaction is complete, wash the product with water and ethanol, and dry to obtain strong flame retardant basalt fiber; wherein the mass ratio of surface chlorinated basalt fiber, alkenyl melamine and triethylamine is 1:0.3:0.06.

[0064] The preparation method of a fireproof composite aluminum plate and strip is the same as that in Example 1.

[0065] Comparative Example 2

[0066] The fireproof material in the intermediate layer is different from that in Example 1.

[0067] A fireproof composite aluminum strip includes an upper aluminum strip, a middle fireproof material layer, and a lower copper strip; wherein the middle fireproof material comprises the following components by weight: 40 parts of ethylene-vinyl acetate copolymer; 25 parts of epoxy resin; 18 parts of styrene-maleic anhydride copolymer; 15 parts of linear low-density polyethylene; and 10 parts of highly flame-retardant basalt fiber.

[0068] The preparation method of the highly flame-retardant basalt fiber is as follows:

[0069] (1) Same as step (1) in Example 1;

[0070] (2) Add ethanol and surface chlorinated basalt fiber to the reaction vessel, stir evenly, add enol melamine and triethylamine, place at 70°C and react for 6 hours. After the reaction is completed, filter, wash the product with water and ethanol, and dry to obtain strong flame retardant basalt fiber; wherein the mass ratio of surface chlorinated basalt fiber, enol melamine and triethylamine is 1:0.3:0.06.

[0071] The preparation method of a fireproof composite aluminum plate and strip is the same as that in Example 1.

[0072] Comparative Example 3

[0073] The fireproof material in the intermediate layer is different from that in Example 1.

[0074] A fireproof composite aluminum strip includes an upper aluminum strip, a middle fireproof material, and a lower copper strip; wherein the middle fireproof material includes the following components by weight: 40 parts of ethylene-vinyl acetate copolymer; 25 parts of epoxy resin; 18 parts of styrene-maleic anhydride copolymer; 15 parts of linear low-density polyethylene; and 10 parts of basalt fiber.

[0075] The preparation method of a fireproof composite aluminum plate and strip is the same as that in Example 1.

[0076] Comparative Example 4

[0077] The fireproof material in the intermediate layer is different from that in Example 1.

[0078] A fireproof composite aluminum strip includes an upper aluminum strip, a middle fireproof material layer, and a lower copper strip; wherein the middle fireproof material comprises the following components by weight: 40 parts of ethylene-vinyl acetate copolymer; 25 parts of epoxy resin; 18 parts of styrene-maleic anhydride copolymer; and 15 parts of linear low-density polyethylene.

[0079] The preparation method of a fireproof composite aluminum plate and strip is the same as that in Example 1.

[0080] Test case

[0081] Performance tests were conducted on the intermediate fireproof materials and fireproof composite aluminum strips provided in Examples 1 to 4 and Comparative Examples 1 to 4. The intermediate fireproof materials were tested as follows: tensile shear strength according to GB / T 7124-2008 standard; peel strength according to GB / T 7122-1996 standard; limiting oxygen index according to GB / T 2406.2-2009 standard. The fireproof composite aluminum strips were tested as follows: flexural strength according to JCT 2561-2020 standard; flammability rating according to GB 8624-2012 standard. The test results are shown in Table 1.

[0082] Table 1 Test Results

[0083]

[0084] As shown in Table 1, the intermediate fireproof materials provided in Examples 1 to 4 of this invention have high shear strength and peel strength, and the limiting oxygen index can reach over 40%, indicating that they have good mechanical properties, bonding properties, and excellent flame retardant properties. When used for bonding aluminum and copper strips, composite aluminum strips with good bending strength and high fire resistance can be obtained. Compared with Comparative Examples 1 to 4, the intermediate fireproof material in Example 1 of this invention includes highly flame-retardant basalt fiber. The highly flame-retardant basalt fiber is based on melamine groups, which are chemically bonded to three basalt fibers, phosphate groups, and DOPO groups. This stable structure helps to improve the mechanical strength of the material. The basalt fiber has a melting point of up to about 1500℃, which has good high-temperature stability. It can maintain structural integrity in high-temperature or flame environments and will not produce molten droplets or toxic gases due to combustion. It has a strong flame-retardant effect and can work synergistically with the PN flame-retardant system formed by melamine groups, phosphate groups, and DOPO groups, thereby greatly enhancing the fire-retardant performance of the material.

[0085] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A fireproof composite aluminum plate strip, characterized by, The fireproof composite aluminum strip comprises an upper aluminum strip, a middle fireproof material layer, and a lower copper strip; the middle fireproof material comprises the following components by weight: 30-40 parts ethylene-vinyl acetate copolymer; 20-25 parts epoxy resin; 15-20 parts styrene-maleic anhydride copolymer; 10-15 parts linear low-density polyethylene; and 8-10 parts highly flame-retardant basalt fiber. The preparation method of the highly flame-retardant basalt fiber is as follows: (1) Add ethanol aqueous solution and basalt fiber to the reaction vessel, stir evenly, add 3-chloropropyltrimethoxysilane, adjust the pH of the solution to 5-6, place at 50-60℃, react for 4-5h to obtain surface chlorinated basalt fiber. (2) Add ethanol and surface chlorinated basalt fiber to the reaction vessel, stir evenly, add melamine polyphosphate and triethylamine, place at 70-80℃ for 5-6 hours to obtain strong flame retardant basalt fiber. The preparation method of the polyphosphate melamine mentioned in step (2) is as follows: S1. Add ethanol and melamine to the reaction vessel, stir until homogeneous, add 1-bromo-3-buten-2-ol and triethylamine, place at 60-70℃ and stir for 4-5 hours to obtain enol melamine. S2. Add anhydrous diethyl ether, enol melamine and triethylamine to the reaction vessel, stir well, add diethylphosphite chloride slowly dropwise under ice bath conditions, and continue to keep the reaction at the temperature for 3-4 hours to obtain enol melamine. S3. Add N,N-dimethylformamide and alkenyl melamine to the reaction vessel, stir until homogeneous, add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, place at 95-100℃ and stir for 9-10 hours to obtain polyphosphate melamine.

2. The fireproof composite aluminum sheet and strip according to claim 1, characterized in that, The mass ratio of basalt fiber and 3-chloropropyltrimethoxysilane in step (1) is 1:0.2-0.

3.

3. The fireproof composite aluminum sheet and strip according to claim 1, characterized in that, The mass ratio of water to ethanol in the ethanol-water solution described in step (1) is 1:1.5-2.

4. The fireproof composite aluminum sheet and strip according to claim 1, characterized in that, The mass ratio of surface chlorinated basalt fiber, polyphosphate melamine, and triethylamine in step (2) is 1:0.2-0.3:0.05-0.

06.

5. The fireproof composite aluminum sheet and strip according to claim 1, characterized in that, The molar ratio of melamine, 1-bromo-3-buten-2-ol, and triethylamine in step S1 is 1:3.1-3.2:1.5-1.

6.

6. The fireproof composite aluminum sheet and strip according to claim 1, characterized in that, The molar ratio of enol melamine, diethylphosphoryl chloride, and triethylamine in step S2 is 1:3.2-3.3:1.7-1.

8.

7. The fireproof composite aluminum sheet and strip according to claim 1, characterized in that, The molar ratio of alkenyl melamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in step S3 is 1:3.1-3.

2.

8. A method for preparing a fire-resistant composite aluminum sheet / strip as described in any one of claims 1-7, characterized in that, The process includes the following steps: applying a corona discharge treatment to one side of the upper aluminum strip and the lower copper strip to form a corona surface; covering the corona surface of the lower copper strip with an intermediate fireproof material, and then combining it with the corona surface of the upper aluminum strip, followed by hot pressing to obtain a fireproof composite aluminum strip.

9. The method for preparing a fireproof composite aluminum plate and strip according to claim 8, characterized in that, The conditions for hot pressing are: temperature 170-180℃, pressure 4-5kPa, and time 12-15s.

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