A non-combustible composite fireproof board and its preparation method

Abstract

This invention discloses a non-combustible composite fireproof board and its preparation method, relating to the field of fireproof composite material technology. The non-combustible composite fireproof board comprises the following components by mass parts: 40 parts binder, which is unsaturated polyester resin; 80-100 parts composite flame retardant, which is a composition of aluminum hydroxide and dimethyl methylphosphonate; 80-100 parts high-temperature reinforcing agent, which is silicon dioxide; 20-40 parts high-temperature synergist, which is a composition of calcium carbonate, kaolin, and montmorillonite; 10-30 parts fiber reinforcing material; 100-130 parts inorganic fiber cloth; 2-3 parts curing agent; and 0.5-1.5 parts accelerator. This invention improves the flame retardant efficiency of the flame retardant, the high-temperature thermal stability and mechanical properties of the composite board, achieving a Class A non-combustible rating, thus realizing a comprehensive balance between the fire-retardant and mechanical properties of the non-combustible composite fireproof board.

Description

Technical Field

[0001] This invention relates to the field of fire-resistant composite material technology, and more specifically, to a non-combustible composite fire-resistant board and its preparation method. Background Technology

[0002] Fiber-reinforced unsaturated polyester resins are a commonly used type of composite material, possessing advantages such as ease of processing, high strength, and corrosion resistance. However, their flammability significantly limits their application in fields such as power, transportation, communications, and construction. Common techniques for improving the flame-retardant properties of fiber-reinforced unsaturated polyester resin composites include adding aluminum hydroxide flame retardants or organophosphorus flame retardants.

[0003] Aluminum hydroxide decomposes upon heating, releasing water of crystallization. This water absorbs heat and forms a protective metal oxide layer, thus providing flame retardancy. However, aluminum hydroxide has low flame retardant efficiency, requiring a large dosage when used alone as a flame retardant, which significantly reduces the processing and mechanical properties of composite fireproof boards. Organophosphorus flame retardants are substances that achieve flame retardancy through the chemical reaction of phosphorus. However, their use affects the curing performance of unsaturated polyester resin, thereby drastically reducing the processing and mechanical properties of composite fireproof boards. For these reasons, current methods for improving the flame retardant properties of fiber-reinforced unsaturated polyester resin composites suffer from technical defects such as low flame retardant efficiency. This results in large amounts of flame retardant added with poor flame retardant effects, poor high-temperature thermal stability, and failure to meet the requirements for non-combustible materials. Furthermore, these methods significantly reduce the curing and mechanical properties of the composite materials. Summary of the Invention

[0004] In view of the problem of low flame retardant performance of existing fiber-reinforced unsaturated polyester resin composite boards, the primary objective of this invention is to solve the technical problem of flame retardant and fireproof technology of fiber-reinforced unsaturated polyester resin composite materials and provide a non-combustible composite fireproof board.

[0005] The technical solution adopted in this invention is as follows:

[0006] A non-combustible composite fireproof board is composed of the following components measured in parts by mass:

[0007] 40 parts of adhesive, which is unsaturated polyester resin;

[0008] 80-100 parts of a composite flame retardant, which is a composition of aluminum hydroxide and dimethyl methylphosphonate;

[0009] 80-100 parts of high-temperature resistant reinforcing agent, which is silicon dioxide;

[0010] The high-temperature resistant synergist, in the form of 20-40 parts, is a composition of calcium carbonate, kaolin, and montmorillonite;

[0011] 10-30 parts of fiber-reinforced material;

[0012] 100-130 parts of inorganic fiber cloth;

[0013] 2-3 parts curing agent;

[0014] Accelerator 0.5-1.5 parts.

[0015] In a preferred embodiment of the present invention, the ratio of aluminum hydroxide to dimethyl methylphosphonate in the composite flame retardant is 5:1.

[0016] In a preferred embodiment of the present invention, the silica particle size range is 50-75 μm.

[0017] In a preferred embodiment of the present invention, the ratio of calcium carbonate, kaolin and montmorillonite in the high-temperature resistant synergist is 12:2:1, and the particle size is ≤5μm.

[0018] In a preferred embodiment of the present invention, the fiber reinforcing material is at least one of glass fiber, basalt fiber and carbon fiber, and has a diameter ≤10μm and a length range of 3-6mm.

[0019] In a preferred embodiment of the present invention, the inorganic fiber cloth is one or more of glass fiber cloth, basalt fiber cloth and carbon fiber cloth, and the total number of layers is 3-5.

[0020] In this invention, the combustion performance of the composite fireproof board depends on the mass ratio of each component. Under the condition of meeting the mass ratio requirements, the number of inorganic fiber cloth layers is determined according to the layer thickness or density of each type of fiber cloth.

[0021] In a preferred embodiment of the present invention, the curing agent and the accelerator are respectively a methyl ethyl ketone peroxide curing agent and a cobalt isooctanoate accelerator.

[0022] The preparation method of the above-mentioned non-combustible composite fireproof board includes:

[0023] Weigh out the binder, composite flame retardant, high-temperature reinforcing agent, high-temperature synergist, fiber reinforcing material, curing agent and accelerator according to the mass ratio, and mix them with a disperser for 3 minutes to obtain the mixed raw materials;

[0024] Based on the number of layers and density of the inorganic fiber cloth, calculate the coating amount of the mixed raw material on the inorganic fiber cloth, and then coat the mixed raw material layer by layer onto the surface of each layer of inorganic fiber cloth according to the coating amount.

[0025] Compared with the prior art, the beneficial effects of the present invention are:

[0026] (1) The present invention uses aluminum hydroxide and dimethyl methyl phosphonate to form a composite flame retardant for flame retardant treatment. Through experimental verification, the ratio of aluminum hydroxide and dimethyl methyl phosphonate in the composite flame retardant was optimized, which improved the flame retardant efficiency of the composite flame retardant and significantly improved the flame retardant properties such as oxygen index and vertical burning performance of non-combustible composite fireproof boards.

[0027] (2) This invention uses silica as a high-temperature resistant reinforcing agent, which improves the high-temperature resistance of fiber-reinforced unsaturated polyester resin composite boards, reduces their decomposition rate at high temperatures, and enhances the curing rate (in the board processing of the following examples, the curing time is 10-15 min, while the curing time of the board in the comparative example is 45 min; therefore, the curing rate of the board in this invention is significantly better than that of the board in the comparative example, and the curing performance is significantly improved compared to the prior art) and mechanical properties. Simultaneously, calcium carbonate, kaolin, and montmorillonite are used in an optimized material ratio to form a high-temperature resistant synergist, which works synergistically with the high-temperature resistant reinforcing agent to further improve the high-temperature resistance of the fiber-reinforced unsaturated polyester resin composite boards and enhance their thermal stability under high fire temperatures. Through the combined action of the high-temperature resistant reinforcing agent and the high-temperature resistant synergist, the flame retardant performance and high-temperature thermal stability of the non-combustible composite fireproof board are further improved, enabling it to reach the Class A non-combustible rating.

[0028] (3) The present invention uses fiber-reinforced materials and inorganic fiber cloth as reinforcement materials for composite materials, which can more effectively improve the mechanical properties of non-combustible composite fireproof boards. Furthermore, by optimizing the mass ratio of fiber-reinforced materials and inorganic fiber cloth, a comprehensive balance of fire-retardant and mechanical properties of non-combustible composite fireproof boards is achieved.

[0029] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, embodiments of the present invention are described in detail below. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0031] Example 1

[0032] I. Preparing raw materials

[0033] Prepare by weight parts:

[0034] 40 parts of unsaturated polyester resin were used as a binder;

[0035] A composition of 66.7 parts aluminum hydroxide and 13.3 parts dimethyl methylphosphonate was used as a composite flame retardant.

[0036] 100 parts of silica are used as a high-temperature resistant reinforcing agent, with a maximum particle size of not more than 75 μm and a minimum particle size of not less than 50 μm;

[0037] A composition of 16 parts calcium carbonate, 2.7 parts kaolin and 1.3 parts montmorillonite was used as a high-temperature resistant synergist, and the particle size of all of them was no greater than 5 μm.

[0038] A composition of 5 parts glass fiber and 15 parts basalt fiber is used as a fiber reinforcement material, wherein the fiber diameter is not greater than 10 μm, the maximum fiber length is not more than 6 mm, and the minimum fiber length is not less than 3 mm.

[0039] The inorganic fiber cloth consists of 50 parts by mass of basalt fiber cloth and 50 parts by mass of carbon fiber cloth, with one layer of basalt fiber cloth and two layers of carbon fiber cloth, for a total of three layers of inorganic fiber cloth. The thickness and density of the basalt fiber cloth are greater than those of each layer of carbon fiber cloth.

[0040] Two parts of methyl ethyl ketone peroxide curing agent;

[0041] 0.5 parts of cobalt isooctanoate accelerator.

[0042] II. Preparation of Non-combustible Composite Fireproof Boards

[0043] The binder, composite flame retardant, high-temperature reinforcing agent, high-temperature synergist, fiber reinforcing material, methyl ethyl ketone peroxide curing agent and cobalt isooctanoate accelerator are mixed in a disperser for 3 minutes to obtain a mixed raw material;

[0044] The mixed raw materials are evenly coated onto each layer of inorganic fiber cloth, and the layers of inorganic fiber cloth are bonded together to obtain a non-combustible composite fireproof board product. After standing for 72 hours, the product is tested.

[0045] III. Product Technical Performance Testing

[0046] The limiting oxygen index, vertical burning rating, flammability rating and tensile strength of the non-combustible composite fireproof board were tested and the test data were recorded.

[0047] Example 2

[0048] I. Preparing raw materials

[0049] Prepare by weight parts:

[0050] 40 parts of unsaturated polyester resin were used as a binder;

[0051] A composition of 80 parts aluminum hydroxide and 16 parts dimethyl methylphosphonate is used as a composite flame retardant;

[0052] 95 parts of silica are used as a high-temperature resistant reinforcing agent, with a maximum particle size of not more than 75 μm and a minimum particle size of not less than 50 μm;

[0053] A composition of 32 parts calcium carbonate, 5.3 parts kaolin and 2.7 parts montmorillonite was used as a high-temperature synergist, and the particle size of all of them was no greater than 5 μm.

[0054] Ten parts of carbon fiber are used as fiber reinforcement material, with a fiber diameter not greater than 10 μm, a maximum fiber length not exceeding 6 mm, and a minimum fiber length not less than 3 mm.

[0055] The inorganic fiber cloth is 120 parts glass fiber cloth, with a total of 4 layers;

[0056] Two parts of methyl ethyl ketone peroxide curing agent;

[0057] 1.0 part of cobalt isooctanoate accelerator.

[0058] II. Preparation of Non-combustible Composite Fireproof Boards

[0059] The binder, composite flame retardant, high-temperature reinforcing agent, high-temperature synergist, fiber reinforcing material, methyl ethyl ketone peroxide curing agent and cobalt isooctanoate accelerator are mixed in a disperser for 3 minutes to obtain a mixed raw material;

[0060] The mixed raw materials are evenly coated onto each layer of inorganic fiber cloth, and the layers of inorganic fiber cloth are bonded together to obtain a non-combustible composite fireproof board product. After standing for 72 hours, the product is tested.

[0061] III. Product Technical Performance Testing

[0062] The limiting oxygen index, vertical burning rating, flammability rating and tensile strength of the non-combustible composite fireproof board were tested and the test data were recorded.

[0063] Example 3

[0064] I. Preparing raw materials

[0065] Prepare by weight parts:

[0066] 40 parts of unsaturated polyester resin were used as a binder;

[0067] A composition of 75 parts aluminum hydroxide and 15 parts dimethyl methylphosphonate is used as a composite flame retardant;

[0068] 90 parts of silica are used as a high-temperature resistant reinforcing agent, with a maximum particle size of not more than 75 μm and a minimum particle size of not less than 50 μm;

[0069] A composition of 24 parts calcium carbonate, 4 parts kaolin and 2 parts montmorillonite was used as a high-temperature resistant synergist, and the particle size of each of them was no greater than 5 μm.

[0070] A composition of 10 parts glass fiber and 10 parts carbon fiber is used as a fiber reinforcement material, wherein the fiber diameter is not greater than 10 μm, the maximum fiber length is not more than 6 mm, and the minimum fiber length is not less than 3 mm.

[0071] The inorganic fiber cloth comprises 50 parts by weight of basalt fiber cloth and 60 parts by weight of glass fiber cloth, wherein both the basalt fiber cloth and the glass fiber cloth are two layers, for a total of four layers of inorganic fiber cloth.

[0072] 2.5 parts of methyl ethyl ketone peroxide curing agent;

[0073] 1.0 part of cobalt isooctanoate accelerator.

[0074] II. Preparation of Non-combustible Composite Fireproof Boards

[0075] The binder, composite flame retardant, high-temperature reinforcing agent, high-temperature synergist, fiber reinforcing material, methyl ethyl ketone peroxide curing agent and cobalt isooctanoate accelerator are mixed in a disperser for 3 minutes to obtain a mixed raw material;

[0076] The mixed raw materials are evenly coated onto each layer of inorganic fiber cloth, and the layers of inorganic fiber cloth are bonded together to obtain a non-combustible composite fireproof board product. After standing for 72 hours, the product is tested.

[0077] III. Product Technical Performance Testing

[0078] The limiting oxygen index, vertical burning rating, flammability rating and tensile strength of the non-combustible composite fireproof board were tested and the test data were recorded.

[0079] Example 4

[0080] I. Preparing raw materials

[0081] Prepare by weight parts:

[0082] 40 parts of unsaturated polyester resin were used as a binder;

[0083] A composition of 83.3 parts aluminum hydroxide and 16.7 parts dimethyl methylphosphonate was used as a composite flame retardant.

[0084] 80 parts of silica are used as a high-temperature resistant reinforcing agent, with a maximum particle size of not more than 75 μm and a minimum particle size of not less than 50 μm;

[0085] A composition of 30 parts calcium carbonate, 5 parts kaolin and 2.5 parts montmorillonite was used as a high-temperature resistant synergist, and the particle size of all of them was no greater than 5 μm.

[0086] A composition of 10 parts glass fiber, 10 parts basalt fiber and 10 parts carbon fiber is used as a fiber reinforcement material, wherein the fiber diameter is not greater than 10 μm, the maximum fiber length is not more than 6 mm and the minimum fiber length is not less than 3 mm.

[0087] The inorganic fiber cloth comprises 30 parts by mass of glass fiber cloth, 50 parts by mass of basalt fiber cloth and 50 parts by mass of carbon fiber cloth, wherein there is 1 layer of glass fiber cloth, 2 layers of basalt fiber cloth and 2 layers of carbon fiber cloth, for a total of 5 layers of inorganic fiber cloth.

[0088] 3 parts of methyl ethyl ketone peroxide curing agent;

[0089] 1.5 parts of cobalt isooctanoate accelerator.

[0090] II. Preparation of Non-combustible Composite Fireproof Boards

[0091] The binder, composite flame retardant, high-temperature reinforcing agent, high-temperature synergist, fiber reinforcing material, methyl ethyl ketone peroxide curing agent and cobalt isooctanoate accelerator are mixed in a disperser for 3 minutes to obtain a mixed raw material;

[0092] The mixed raw materials are evenly coated onto each layer of inorganic fiber cloth, and the layers of inorganic fiber cloth are bonded together to obtain a non-combustible composite fireproof board product. After standing for 72 hours, the product is tested.

[0093] III. Product Technical Performance Testing

[0094] The limiting oxygen index, vertical burning rating, flammability rating and tensile strength of the non-combustible composite fireproof board were tested and the test data were recorded.

[0095] Comparative Example 1

[0096] I. Preparing raw materials

[0097] Prepare by weight parts:

[0098] 40 parts of unsaturated polyester resin were used as a binder;

[0099] 100 parts aluminum hydroxide as a flame retardant;

[0100] 30 parts of glass fiber are used as fiber reinforcement material, with a fiber diameter not greater than 10μm, a maximum fiber length not exceeding 6mm, and a minimum fiber length not less than 3mm;

[0101] The inorganic fiber cloth is carbon fiber cloth, with a mass fraction of 130 parts, consisting of 4 layers of inorganic fiber cloth.

[0102] Two parts of methyl ethyl ketone peroxide curing agent;

[0103] 1.0 part of cobalt isooctanoate accelerator.

[0104] II. Preparation of Composite Fireproof Boards

[0105] The binder, flame retardant, fiber reinforcement material, methyl ethyl ketone peroxide curing agent and cobalt isooctanoate accelerator are mixed in a disperser for 3 minutes to obtain a mixed raw material;

[0106] The mixed raw materials were evenly coated onto each layer of inorganic fiber cloth, and the layers of inorganic fiber cloth were bonded together to obtain a composite fireproof board product. After standing for 72 hours, the product was tested.

[0107] III. Product Technical Performance Testing

[0108] The limiting oxygen index, vertical burning rating, flammability rating and tensile strength of the composite fireproof board were tested and the test data were recorded.

[0109] The technical performance of the raw materials, formulations (content by mass parts) and the obtained non-combustible composite fireproof board products of the above embodiments, as well as the raw materials, formulations (content by mass parts) and the obtained composite fireproof board products of the comparative embodiments, are compared. The specific data are shown in Table 1.

[0110] Table 1

[0111]

[0112] Table 1 shows that comparing the examples with Comparative Example 1, the use of composite flame retardants, high-temperature reinforcing agents, and high-temperature synergists in non-combustible composite fireproof boards can significantly improve the oxygen index and combustion performance rating of the boards. The examples used aluminum hydroxide and dimethyl methylphosphonate in a mass ratio of 5:1 to form a composite flame retardant. When the mass fraction of the composite flame retardant was 80-100 parts, the oxygen index of the non-combustible composite fireproof board could be increased to over 50%. The comparative example used aluminum hydroxide as a flame retardant; when its mass fraction was 100 parts, the oxygen index of the composite board was 30%. In this embodiment, silica was used as a high-temperature resistant reinforcing agent, and calcium carbonate, kaolin, and montmorillonite in a mass ratio of 12:2:1 were used as a high-temperature resistant synergist. The two work synergistically to improve the high-temperature resistance of the non-combustible composite fireproof board, reduce its decomposition rate at high temperatures, and enhance its flame retardant properties and high-temperature thermal stability under fire conditions. When the high-temperature resistant reinforcing agent was 80-100 parts and the high-temperature resistant synergist was 20-40 parts, the fire performance rating of the non-combustible composite fireproof board reached Class A non-combustible level as specified in the national standard "Classification of Burning Performance of Building Materials and Products" (GB 8624-2012). In the comparative embodiment, no high-temperature resistant reinforcing agent or high-temperature resistant synergist was used, and the fire performance rating of the composite fireproof board was Class B2.

[0113] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. 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 non-combustible composite fireproof board, characterized in that, It consists of the following components measured in parts by mass: 40 parts of adhesive, which is unsaturated polyester resin; The composite flame retardant, consisting of 80-100 parts, is a composition of aluminum hydroxide and dimethyl methylphosphonate, with the ratio of aluminum hydroxide to dimethyl methylphosphonate being 5:

1. 80-100 parts of high-temperature resistant reinforcing agent, which is silicon dioxide; The high-temperature resistant synergist is 20-40 parts, which is a composition of calcium carbonate, kaolin and montmorillonite, and the ratio of calcium carbonate, kaolin and montmorillonite is 12:2:1, and the particle size is ≤5μm. 10-30 parts of fiber-reinforced material, wherein the fiber-reinforced material is at least one of glass fiber, basalt fiber and carbon fiber, and the diameter is ≤10μm and the length ranges from 3-6mm; 100-130 parts of inorganic fiber cloth; 2-3 parts curing agent; Accelerator 0.5-1.5 parts.

2. The non-combustible composite fireproof board according to claim 1, characterized in that, The particle size range of silica is 50-75 μm.

3. The non-combustible composite fireproof board according to claim 1, characterized in that, The inorganic fiber cloth is one or more of glass fiber cloth, basalt fiber cloth and carbon fiber cloth, and the total number of layers is 3-5.

4. The non-combustible composite fireproof board according to claim 1, characterized in that, The curing agent and accelerator are respectively methyl ethyl ketone peroxide curing agent and cobalt isooctanoate accelerator.

5. A method for preparing the non-combustible composite fireproof board according to any one of claims 1-4, characterized in that, include: Weigh out the binder, composite flame retardant, high-temperature reinforcing agent, high-temperature synergist, fiber reinforcing material, curing agent and accelerator according to the mass ratio, and mix them with a disperser for 3 minutes to obtain the mixed raw materials; Based on the number of layers and density of the inorganic fiber cloth, calculate the coating amount of the mixed raw material on the inorganic fiber cloth, and then coat the mixed raw material layer by layer onto the surface of each layer of inorganic fiber cloth according to the coating amount.

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