Flame-retardant heat-insulating composite board and preparation method thereof

Abstract

The invention discloses a flame-retardant heat-insulating composite board and a preparation method thereof, the flame-retardant heat-insulating composite board comprises a base material layer, a graphene heat-insulating layer and a microporous silicon-magnesium-aluminum heat-insulating layer, the graphene heat-insulating layer is attached to the surface of one side of the base material layer, and the microporous silicon-magnesium-aluminum heat-insulating layer is attached to the surface of the side, away from the base material layer, of the graphene heat-insulating layer; the graphene flame-retardant layer is made of a graphene material and has excellent flame-retardant performance; the microporous silicon-magnesium-aluminum heat insulation layer is of a porous structure and has good heat insulation performance, a flame retardant is added into the graphene heat insulation layer, during combustion, midbody 2 macromolecules exert the excellent flame retardant performance, meanwhile, gas is generated due to thermal decomposition, a carrageenan wall layer rapidly forms carbon and expands, the transfer path of an external heat base material is blocked, and the heat insulation performance of the heat insulation layer is improved. Furthermore, raw materials such as vanillin and carrageenan are adopted, so that the environment-friendly requirement is better met.

Description

Technical Field

[0001] The present invention relates to the technical field of home furnishing board materials, and in particular to a flame retardant and heat insulating composite board material and a preparation method thereof. Background Art

[0002] With the advancement of science and technology, various high-performance materials have been widely used in various fields. Especially in the fields of aerospace, shipbuilding, automotive, home furnishing, etc., higher and higher requirements are put forward for the flame retardant and heat insulation properties of materials. However, existing flame retardant and heat insulation materials often have problems such as low flame retardancy, poor heat insulation effect, and short service life, which cannot meet the growing demand. Summary of the invention

[0003] In order to solve the above technical problems, the present invention provides a flame retardant and heat insulating composite board and a preparation method thereof.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A flame retardant heat-insulating composite board, comprising a substrate layer, a graphene heat-insulating layer and a microporous silicon-magnesium-aluminum heat-insulating layer, wherein the graphene heat-insulating layer is attached to one side of the substrate layer, and the microporous silicon-magnesium-aluminum heat-insulating layer is attached to the side of the graphene heat-insulating layer away from the substrate layer;

[0006] The graphene heat insulation layer is formed by mixing hot melt adhesive, flame retardant, graphene, short fibers and water in a weight ratio of 10:5-8:3-5:1-2:20.

[0007] The flame retardant is prepared by the following steps:

[0008] Step S1, after mixing phenylphosphoryl dichloride and 1,10-decanediamine, the mixture is heated to 55-65°C, nitrogen is introduced, and the mixture is kept warm for 6 hours. After the reaction is completed, the by-products are removed by washing with water to obtain an intermediate 1;

[0009] In step S1, phenylphosphoryl dichloride and 1,10-decanediamine react to prepare intermediate 1.

[0010] Step S2, mixing the prepared intermediate 1 and vanillin, heating to 40-45°C, and keeping the temperature for reaction for 6 hours. After the reaction is completed, washing with water to remove unreacted raw materials, to prepare intermediate 2;

[0011] The terminal amino group on the intermediate 1 prepared in step S2 reacts with vanillin to prepare an intermediate 2, which is a phosphoramide polymer flame retardant.

[0012] Step S3, adding carrageenan to deionized water, heating to 90-95° C., stirring at a uniform speed and dropping a 10% by mass sodium hydroxide aqueous solution, adding intermediate 2, stirring evenly, and making a water phase; adding Span 80 to the mixed solvent, stirring evenly, and making an oil phase; adding the water phase to the oil phase, shearing and emulsifying for 10 minutes, adding epichlorohydrin, reacting at room temperature for 4 hours, and removing the solvent by rotary evaporation to obtain a flame retardant.

[0013] In step S3, carrageenan is used as a carbon source, and the intermediate 2 is wrapped by inverse emulsion polymerization to form a core-shell structure flame retardant with carrageenan as the core and the intermediate 2 as the core. When burning, the macromolecules of the intermediate 2 not only exert excellent flame retardant properties, but also produce gas due to thermal decomposition, so that the carrageenan wall layer quickly chars and expands, blocking the transmission path of external heat to the matrix material, and further improving the flame retardant and heat insulating properties.

[0014] Furthermore, the hot melt adhesive is ethylene-vinyl acetate copolymer, the length of the short fibers is 60 μm, and the short fibers are glass fibers.

[0015] Furthermore, in step S1, the molar ratio of phenylphosphoryl dichloride to 1,10-decanediamine is controlled to be 1:2.

[0016] Furthermore, in step S2, the molar ratio of intermediate 1 to vanillin is controlled to be 1:2.

[0017] Furthermore, in step S3, the weight ratio of carrageenan, intermediate 2, sodium hydroxide aqueous solution and deionized water is controlled to be 2:1:0.02:10, the volume ratio of the mixed solvent and Span 80 is 100:2, the volume ratio of the aqueous phase and the oil phase is 1:2, and the mixed solvent is a mixture of cyclohexane and chloroform in a volume ratio of 4-5:1.

[0018] Furthermore, the substrate layer is a log artificial composite board.

[0019] A method for preparing a flame retardant and heat insulating composite board comprises the following steps:

[0020] A graphene heat insulation layer is attached to one surface of the substrate layer, and a microporous silicon-magnesium-aluminum heat insulation layer is attached to the surface of the graphene heat insulation layer away from the substrate layer to obtain a flame retardant heat insulation composite board.

[0021] Beneficial effects of the present invention:

[0022] The present invention prepares a flame retardant and heat-insulating composite board material. The graphene flame retardant layer adopts graphene material and has excellent flame retardant performance. The microporous silicon magnesium aluminum heat insulation layer adopts a porous structure and has good heat insulation performance. A flame retardant is added to the graphene heat insulation layer. During the preparation process of the flame retardant, a phosphoramide polymer flame retardant intermediate 2 is first prepared. Then carrageenan is used as a carbon source. The prepared intermediate 2 is wrapped by inverse emulsion polymerization to form a core-shell structure flame retardant with carrageenan as the core and the intermediate 2 as the core. When burned, the macromolecules of the intermediate 2 produce gas due to thermal decomposition while exerting excellent flame retardant performance, so that the carrageenan wall layer quickly chars and expands, thereby blocking the transmission path of the external heat matrix material, further improving the flame retardant and heat-insulating performance. Moreover, the use of raw materials such as vanillin and carrageenan is more in line with environmental protection requirements. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] Example 1

[0025] A flame retardant heat-insulating composite board, comprising a substrate layer, a graphene heat-insulating layer and a microporous silicon-magnesium-aluminum heat-insulating layer, wherein the graphene heat-insulating layer is attached to one side of the substrate layer, and the microporous silicon-magnesium-aluminum heat-insulating layer is attached to the side of the graphene heat-insulating layer away from the substrate layer;

[0026] The flame retardant heat insulating composite board is manufactured by the following steps:

[0027] A graphene heat insulation layer is attached to one surface of the substrate layer, and a microporous silicon-magnesium-aluminum heat insulation layer is attached to the surface of the graphene heat insulation layer away from the substrate layer to obtain a flame retardant heat insulation composite board.

[0028] The graphene heat insulation layer is formed by mixing hot melt adhesive, flame retardant, graphene, short fibers and water in a weight ratio of 10:5:3-5:1:20.

[0029] The flame retardant is prepared by the following steps:

[0030] Step S1, after mixing phenylphosphoryl dichloride and 1,10-decanediamine, the temperature was raised to 55°C, nitrogen was introduced, and the temperature was kept for reaction for 6 hours. After the reaction was completed, the by-products were washed with water to obtain intermediate 1, and the molar ratio of phenylphosphoryl dichloride to 1,10-decanediamine was controlled to be 1:2;

[0031] Step S2, mixing the prepared intermediate 1 and vanillin, heating to 40°C, and keeping the temperature for reaction for 6 hours. After the reaction is completed, washing with water to remove unreacted raw materials to obtain intermediate 2, and controlling the molar ratio of intermediate 1 to vanillin to be 1:2;

[0032] Step S3, adding carrageenan to deionized water, heating to 90° C., stirring at a uniform speed and dropping a 10% by mass sodium hydroxide aqueous solution, adding intermediate 2, stirring evenly, and making a water phase; adding Span 80 to the mixed solvent, stirring evenly, and making an oil phase; adding the water phase to the oil phase, shearing and emulsifying for 10 minutes, adding epichlorohydrin, reacting at room temperature for 4 hours, and removing the solvent by rotary evaporation to obtain a flame retardant, controlling the weight ratio of carrageenan, intermediate 2, sodium hydroxide aqueous solution and deionized water to be 2:1:0.02:10, the volume ratio of the mixed solvent and Span 80 to be 100:2, the volume ratio of the water phase to the oil phase to be 1:2, and the mixed solvent is a mixture of cyclohexane and chloroform in a volume ratio of 4:1.

[0033] The hot melt adhesive is ethylene-vinyl acetate copolymer, the length of the short fibers is 60 μm, and the short fibers are glass fibers.

[0034] The substrate layer is a log artificial composite board.

[0035] Example 2

[0036] A flame retardant heat-insulating composite board, comprising a substrate layer, a graphene heat-insulating layer and a microporous silicon-magnesium-aluminum heat-insulating layer, wherein the graphene heat-insulating layer is attached to one side of the substrate layer, and the microporous silicon-magnesium-aluminum heat-insulating layer is attached to the side of the graphene heat-insulating layer away from the substrate layer;

[0037] The flame retardant heat insulating composite board is manufactured by the following steps:

[0038] A graphene heat insulation layer is attached to one surface of the substrate layer, and a microporous silicon-magnesium-aluminum heat insulation layer is attached to the surface of the graphene heat insulation layer away from the substrate layer to obtain a flame retardant heat insulation composite board.

[0039] The graphene heat insulation layer is formed by mixing hot melt adhesive, flame retardant, graphene, short fibers and water in a weight ratio of 10:6:4:1.2:20.

[0040] The flame retardant is prepared by the following steps:

[0041] Step S1, after mixing phenylphosphoryl dichloride and 1,10-decanediamine, the temperature was raised to 55°C, nitrogen was introduced, and the temperature was kept for reaction for 6 hours. After the reaction was completed, the by-products were washed with water to obtain intermediate 1, and the molar ratio of phenylphosphoryl dichloride to 1,10-decanediamine was controlled to be 1:2;

[0042] Step S2, mixing the prepared intermediate 1 and vanillin, heating to 40°C, and keeping the temperature for reaction for 6 hours. After the reaction is completed, washing with water to remove unreacted raw materials to obtain intermediate 2, and controlling the molar ratio of intermediate 1 to vanillin to be 1:2;

[0043] Step S3, adding carrageenan to deionized water, heating to 90° C., stirring at a uniform speed and dropping a 10% by mass sodium hydroxide aqueous solution, adding intermediate 2, stirring evenly, and making a water phase; adding Span 80 to the mixed solvent, stirring evenly, and making an oil phase; adding the water phase to the oil phase, shearing and emulsifying for 10 minutes, adding epichlorohydrin, reacting at room temperature for 4 hours, and removing the solvent by rotary evaporation to obtain a flame retardant, controlling the weight ratio of carrageenan, intermediate 2, sodium hydroxide aqueous solution and deionized water to be 2:1:0.02:10, the volume ratio of the mixed solvent and Span 80 to be 100:2, the volume ratio of the water phase to the oil phase to be 1:2, and the mixed solvent is a mixture of cyclohexane and chloroform in a volume ratio of 4:1.

[0044] The hot melt adhesive is ethylene-vinyl acetate copolymer, the length of the short fibers is 60 μm, and the short fibers are glass fibers.

[0045] The substrate layer is a log artificial composite board.

[0046] Example 3

[0047] A flame retardant heat-insulating composite board, comprising a substrate layer, a graphene heat-insulating layer and a microporous silicon-magnesium-aluminum heat-insulating layer, wherein the graphene heat-insulating layer is attached to one side of the substrate layer, and the microporous silicon-magnesium-aluminum heat-insulating layer is attached to the side of the graphene heat-insulating layer away from the substrate layer;

[0048] The flame retardant heat insulating composite board is manufactured by the following steps:

[0049] A graphene heat insulation layer is attached to one surface of the substrate layer, and a microporous silicon-magnesium-aluminum heat insulation layer is attached to the surface of the graphene heat insulation layer away from the substrate layer to obtain a flame retardant heat insulation composite board.

[0050] The graphene heat insulation layer is formed by mixing hot melt adhesive, flame retardant, graphene, short fibers and water in a weight ratio of 10:7:4:1.5:20.

[0051] The flame retardant is prepared by the following steps:

[0052] Step S1, after mixing phenylphosphoryl dichloride and 1,10-decanediamine, the temperature was raised to 65°C, nitrogen was introduced, and the temperature was kept for reaction for 6 hours. After the reaction was completed, the by-products were washed with water to obtain intermediate 1, and the molar ratio of phenylphosphoryl dichloride to 1,10-decanediamine was controlled to be 1:2;

[0053] Step S2, mixing the prepared intermediate 1 and vanillin, heating to 45°C, and keeping the temperature to react for 6 hours. After the reaction is completed, washing with water to remove unreacted raw materials to prepare intermediate 2, and controlling the molar ratio of intermediate 1 to vanillin to be 1:2;

[0054] Step S3, adding carrageenan to deionized water, heating to 95°C, stirring at a uniform speed and dropping a 10% sodium hydroxide aqueous solution, adding intermediate 2, stirring evenly, and making a water phase; adding Span 80 to the mixed solvent, stirring evenly, and making an oil phase; adding the water phase to the oil phase, shearing and emulsifying for 10 minutes, adding epichlorohydrin, reacting at room temperature for 4 hours, and removing the solvent by rotary evaporation to obtain a flame retardant, controlling the weight ratio of carrageenan, intermediate 2, sodium hydroxide aqueous solution and deionized water to be 2:1:0.02:10, the volume ratio of the mixed solvent and Span 80 to be 100:2, the volume ratio of the water phase to the oil phase to be 1:2, and the mixed solvent is a mixture of cyclohexane and chloroform in a volume ratio of 4.8:1.

[0055] The hot melt adhesive is ethylene-vinyl acetate copolymer, the length of the short fibers is 60 μm, and the short fibers are glass fibers.

[0056] The substrate layer is a log artificial composite board.

[0057] Example 4

[0058] A flame retardant heat-insulating composite board, comprising a substrate layer, a graphene heat-insulating layer and a microporous silicon-magnesium-aluminum heat-insulating layer, wherein the graphene heat-insulating layer is attached to one side of the substrate layer, and the microporous silicon-magnesium-aluminum heat-insulating layer is attached to the side of the graphene heat-insulating layer away from the substrate layer;

[0059] The flame retardant heat insulating composite board is manufactured by the following steps:

[0060] A graphene heat insulation layer is attached to one surface of the substrate layer, and a microporous silicon-magnesium-aluminum heat insulation layer is attached to the surface of the graphene heat insulation layer away from the substrate layer to obtain a flame retardant heat insulation composite board.

[0061] The graphene heat insulation layer is formed by mixing hot melt adhesive, flame retardant, graphene, short fibers and water in a weight ratio of 10:8:5:2:20.

[0062] The flame retardant is prepared by the following steps:

[0063] Step S1, after mixing phenylphosphoryl dichloride and 1,10-decanediamine, the temperature was raised to 65°C, nitrogen was introduced, and the temperature was kept for reaction for 6 hours. After the reaction was completed, the by-products were washed with water to obtain intermediate 1, and the molar ratio of phenylphosphoryl dichloride to 1,10-decanediamine was controlled to be 1:2;

[0064] Step S2, mixing the prepared intermediate 1 and vanillin, heating to 45°C, and keeping the temperature to react for 6 hours. After the reaction is completed, washing with water to remove unreacted raw materials to prepare intermediate 2, and controlling the molar ratio of intermediate 1 to vanillin to be 1:2;

[0065] Step S3, adding carrageenan to deionized water, heating to 95° C., stirring at a uniform speed and dropping a 10% by mass sodium hydroxide aqueous solution, adding intermediate 2, stirring evenly, and making a water phase; adding Span 80 to the mixed solvent, stirring evenly, and making an oil phase; adding the water phase to the oil phase, shearing and emulsifying for 10 minutes, adding epichlorohydrin, reacting at room temperature for 4 hours, and removing the solvent by rotary evaporation to obtain a flame retardant, controlling the weight ratio of carrageenan, intermediate 2, sodium hydroxide aqueous solution and deionized water to be 2:1:0.02:10, the volume ratio of the mixed solvent and Span 80 to be 100:2, the volume ratio of the water phase to the oil phase to be 1:2, and the mixed solvent is a mixture of cyclohexane and chloroform in a volume ratio of 5:1.

[0066] The hot melt adhesive is ethylene-vinyl acetate copolymer, the length of the short fibers is 60 μm, and the short fibers are glass fibers.

[0067] The substrate layer is a log artificial composite board.

[0068] Comparative Example 1

[0069] Compared with Example 1, no flame retardant is added to the graphene thermal insulation layer in this comparative example.

[0070] The performance of the graphene thermal insulation layers prepared in Examples 1-4 and Comparative Example 1 was tested, and the results are shown in Table 1 below:

[0071] Table 1

[0072] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Flame retardant grade V0 V0 V0 V0 V2

[0073] It can be seen from Table 1 above that the hot melt adhesives prepared in Examples 1-4 of the present invention have excellent heat resistance.

[0074] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A flame retardant heat insulating composite board, characterized in that: It includes a substrate layer, a graphene thermal insulation layer and a microporous silicon-magnesium-aluminum thermal insulation layer, wherein the graphene thermal insulation layer is attached to one side of the substrate layer, and the microporous silicon-magnesium-aluminum thermal insulation layer is attached to the side of the graphene thermal insulation layer away from the substrate layer; The graphene heat insulation layer is formed by mixing hot melt adhesive, flame retardant, graphene, short fibers and water in a weight ratio of 10:5-8:3-5:1-2:20; The flame retardant is prepared by the following steps: Step S1, after mixing phenylphosphoryl dichloride and 1,10-decanediamine, the mixture is heated to 55-65°C, nitrogen is introduced, and the mixture is kept warm for 6 hours. After the reaction is completed, the mixture is washed with water to obtain an intermediate 1; Step S2, mixing the prepared intermediate 1 and vanillin, heating to 40-45°C, keeping the temperature for reaction for 6 hours, and washing with water after the reaction to obtain intermediate 2; Step S3, adding carrageenan to deionized water, heating to 90-95° C., stirring at a uniform speed and dropping a 10% by mass sodium hydroxide aqueous solution, adding intermediate 2, stirring evenly, and making a water phase; adding Span 80 to the mixed solvent, stirring evenly, and making an oil phase; adding the water phase to the oil phase, shearing and emulsifying for 10 minutes, adding epichlorohydrin, reacting at room temperature for 4 hours, and removing the solvent by rotary evaporation to obtain a flame retardant.

2. The flame retardant and heat insulating composite board according to claim 1, characterized in that: The hot melt adhesive is ethylene-vinyl acetate copolymer, the length of the short fibers is 60 μm, and the short fibers are glass fibers.

3. The flame retardant and heat insulating composite board according to claim 1, characterized in that: In step S1, the molar ratio of phenylphosphoryl dichloride to 1,10-decanediamine is controlled to be 1:

2.

4. The flame retardant and heat insulating composite board according to claim 1, characterized in that: In step S2, the molar ratio of intermediate 1 to vanillin is controlled to be 1:

2.

5. The flame retardant and heat insulating composite board according to claim 1, characterized in that: In step S3, the weight ratio of carrageenan, intermediate 2, sodium hydroxide aqueous solution and deionized water is controlled to be 2:1:0.02:10, the volume ratio of the mixed solvent and Span 80 is 100:2, the volume ratio of the water phase and the oil phase is 1:2, and the mixed solvent is a mixture of cyclohexane and chloroform in a volume ratio of 4-5:

1.

6. The flame retardant and heat insulating composite board according to claim 1, characterized in that: The substrate layer is a log artificial composite board.

7. The method for preparing a flame retardant and heat insulating composite board according to claim 1, characterized in that: The steps include: A graphene heat insulation layer is attached to one surface of the substrate layer, and a microporous silicon-magnesium-aluminum heat insulation layer is attached to the surface of the graphene heat insulation layer away from the substrate layer to obtain a flame retardant heat insulation composite board.