Preparation method of graphene-doped thermal insulation and fireproof material for fire doors

Abstract

The invention discloses a preparation method of a graphene-doped thermal insulation and fireproof material for fireproof doors. The method comprises the following steps: an addition reaction is performed between the thiol group (-SH) of thiolated graphene and the olefin portion of dibutyltin maleate; the reaction forms a more stable sulfide bond through direct addition of the thiol group to a carbon-carbon double bond; such a structural change enhances the interaction between the graphene and other components, thereby improving the thermal stability and flame retardancy of the fireproof material; an addition reaction is performed between the silicon-hydrogen bond (Si-H) in 1,1-bis(dimethylsilyl)ferrous acid and the olefin portion of dibutyltin maleate; the reaction forms a silicon-carbon bond (Si-C) of ferrocene through the addition of a silicon atom to the carbon-carbon double bond, thereby further enhancing the structural stability and high-temperature resistance of the material; the graphene-doped thermal insulation and fireproof material for fireproof doors prepared by the invention meets the A1-class fireproof building material standard.

Description

Technical Field

[0001] The present invention relates to the technical field of fireproof material preparation, in particular to a method for preparing a graphene-doped heat-insulating fireproof material for fireproof doors. Background Art

[0002] Fire doors prevent the spread of smoke and flames in the event of a fire. They are primarily installed at entrances and exits to important rooms, fire partitions, evacuation routes, and duct shafts. The fireproofing materials used in fire doors are crucial to maintaining their fire resistance, integrity, and thermal insulation.

[0003] Chinese patent CN109796843A: discloses a method for preparing a fireproof material, which is made from epoxy resin, iron oxide, ethyl acetate, propylene glycol butyl ether, graphene, titanium dioxide, aluminate, strontium chromate, ammonium metaborate, carbon fiber, dibutyl phthalate, propylene glycol methyl ether, aluminum powder, ceramic powder, polypropylene and asbestos.

[0004] Chinese patent CN113930080A: belongs to the field of fireproof material preparation technology, and discloses a fireproof material based on corn straw and its preparation method. The preparation method of the fireproof material based on corn straw includes: preparation of modified diatomaceous earth; preparation of raw materials for fireproof material preparation; pretreatment of raw materials for fireproof material preparation; preparation of fermentation bacteria liquid; preparation of fireproof material.

[0005] Chinese patent CN111499315A belongs to the field of fireproof material preparation technology, specifically relating to a high-temperature resistant fireproof material, its preparation method, and application. This high-temperature resistant fireproof material comprises a gel material and a skeleton material. The mass fraction of aluminum oxide in the gel material is 33-50%, and the skeleton material has a hollow structure. By controlling the mass fraction of aluminum oxide in the gel material to 33-50%, the gel material can be fully hydrated, providing early strength and improving the fireproof material's resistance to breakdown. When the mass fraction of aluminum oxide in the gel material is less than 33%, the fireproof material's high-temperature resistance is poor.

[0006] The fireproof materials prepared by the above patents and existing technologies have disadvantages such as the production process is not environmentally friendly, too heavy, severe corrosion, short life, and poor fire resistance. Summary of the Invention

[0007] The purpose of the present invention is to provide a method for preparing a graphene-doped thermal insulation and fireproof material for fire doors, so as to effectively solve the problems existing in the prior art.

[0008] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0009] A method for preparing a graphene-doped thermal insulation and fireproof material for fireproof doors, the operating steps of which are as follows:

[0010] S1: Add 100-200 parts of fly ash / gangue fiber to 800-1000 parts of water, then add 2-5 parts of graphene flame retardant synergist and 4-6 parts of polyvinyl alcohol. Stir quickly until evenly mixed, pour into a mold, and filter out excess water.

[0011] S2: removing excess graphene / polyvinyl alcohol solution from the mold, taking it out and drying it, thereby obtaining a graphene-doped thermal insulation and fireproof material for the fireproof door.

[0012] In an exemplary embodiment of the present invention, the drying temperature is 60-80° C. and the drying time is 18-24 hours.

[0013] In an exemplary embodiment of the present invention, the preparation method of the graphene flame retardant synergist is:

[0014] H1: Add 2-4 parts of 1,1'-bis(dimethylsilyl)iron, 3.5-7 parts of dibutyltin maleate, 0.002-0.02 parts of platinum chloride, and 200-300 parts of N,N-dimethylformamide to an autoclave and disperse by ultrasonication under nitrogen protection;

[0015] H2: Add 30-50 parts of thiol-modified graphene and 3-6 parts of agmatine, perform ultrasonic dispersion, filter, and dry to obtain a graphene flame retardant synergist.

[0016] In an exemplary embodiment of the present invention, the ultrasonic dispersion temperature of H1 is 60-80° C. and the time is 1-3 h.

[0017] In an exemplary embodiment of the present invention, the ultrasonic dispersion temperature of H2 is 60-80°C and the time is 18-24 hours.

[0018] In an exemplary embodiment of the present invention, the thiol-modified graphene is a commercially available product with a size of 1-4.2 μm and an S content of 2.0-8.6 wt %, such as the product produced by Shandong Jincheng Graphene Technology Co., Ltd.

[0019] Reaction mechanism

[0020] Mercapto-olefin addition reaction: The mercapto group (-SH) of thiolated graphene reacts with the olefin portion of dibutyltin maleate. This reaction is achieved by direct addition of the mercapto group to the carbon-carbon double bond to form a more stable sulfide bond. This structural change enhances the interaction between graphene and other components, improving the thermal stability and flame retardant properties of the fireproof material.

[0021] Silicon-hydrogen addition reaction: The silicon-hydrogen bond (Si-H) in 1,1'-bis(dimethylsilyl)iron undergoes an addition reaction with the olefin portion of dibutyltin maleate; this reaction forms the silicon-carbon bond (Si-C) of ferrocene through the addition of silicon atoms to the carbon-carbon double bond, further enhancing the structural stability and high-temperature resistance of the material.

[0022] Technical Effects

[0023] The present invention provides a method for preparing a graphene-doped thermal insulation and fireproof material for fireproof doors. Compared with the prior art, the present invention has the following significant effects:

[0024] 1. The graphene-doped thermal insulation and fireproof material for fire doors prepared by the present invention has a low bulk density, indicating high porosity and good thermal insulation performance;

[0025] 2. The graphene-doped thermal insulation and fireproof material for fire doors prepared by the present invention has a layered structure, the fibers in the material are interwoven, and there are a large number of pores, light texture, and good thermal insulation performance;

[0026] 3. The graphene-doped thermal insulation and fireproof material for fireproof doors prepared by the present invention meets the Class A fireproof building material standard;

[0027] 4. The graphene flame retardant synergist prepared by the present invention can effectively improve the thermal stability and flame retardant properties of fireproof materials, and at the same time, further enhance the structural stability and high temperature resistance of fireproof materials. DETAILED DESCRIPTION

[0028] The technical solutions of the present invention are described in detail below in conjunction with specific embodiments so that those skilled in the art can better understand and implement the technical solutions of the present invention. The specific functional details disclosed herein should not be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching those skilled in the art to employ the present invention in various ways in virtually any appropriate detailed embodiment.

[0029] 1. Fire protection level: Tested in accordance with GB8624-2012;

[0030] 2. Bulk density test: Bulk density = mass of fireproof material / volume of fireproof material.

[0031] Example 1

[0032] A method for preparing a graphene-doped thermal insulation and fireproof material for fireproof doors, the operating steps of which are as follows:

[0033] S1: Add 100g fly ash / gangue fiber to 800g water, then add 2g graphene flame retardant synergist and 4g polyvinyl alcohol, stir quickly and evenly, pour into a mold, and filter out excess water;

[0034] S2: removing excess graphene / polyvinyl alcohol solution from the mold, taking it out and drying it, thereby obtaining a graphene-doped thermal insulation and fireproof material for the fireproof door.

[0035] The drying temperature is 60° C. and the drying time is 18 hours.

[0036] The preparation method of the graphene flame retardant synergist is:

[0037] H1: Add 2 g of 1,1'-bis(dimethylsilyl)iron, 3.5 g of dibutyltin maleate, 0.002 g of platinum chloride, and 200 g of N,N-dimethylformamide to an autoclave and disperse by ultrasonication under nitrogen protection;

[0038] H2: 30 g of thiol-modified graphene and 3 g of agmatine were added, ultrasonically dispersed, filtered, and dried to obtain a graphene flame retardant synergist.

[0039] The ultrasonic dispersion temperature of H1 is 60°C and the time is 1 hour.

[0040] The ultrasonic dispersion temperature of H2 is 60°C and the time is 18 hours.

[0041] The thiol-modified graphene is a commercially available product with a size of 1 μm and an S content of 2.0 wt %, such as the product produced by Shandong Jincheng Graphene Technology Co., Ltd.

[0042] Example 2

[0043] A method for preparing a graphene-doped thermal insulation and fireproof material for fireproof doors, the operating steps of which are as follows:

[0044] S1: Add 140g of fly ash / gangue fiber to 850g of water, then add 3g of graphene flame retardant synergist and 5g of polyvinyl alcohol. Stir quickly until evenly mixed, then pour into a mold and filter out excess water.

[0045] S2: removing excess graphene / polyvinyl alcohol solution from the mold, taking it out and drying it, thereby obtaining a graphene-doped thermal insulation and fireproof material for the fireproof door.

[0046] The drying temperature is 65° C. and the drying time is 20 hours.

[0047] The preparation method of the graphene flame retardant synergist is as follows:

[0048] H1: Add 3 g of 1,1'-bis(dimethylsilyl)iron, 5 g of dibutyltin maleate, 0.01 g of platinum chloride, and 240 g of N,N-dimethylformamide to an autoclave and disperse by ultrasonication under nitrogen protection;

[0049] H2: 35 g of thiol-modified graphene and 4 g of agmatine were added, ultrasonically dispersed, filtered, and dried to obtain a graphene flame retardant synergist.

[0050] The ultrasonic dispersion temperature of H1 is 65° C. and the time is 2 h.

[0051] The ultrasonic dispersion temperature of H2 is 65°C and the time is 20 hours.

[0052] The thiol-modified graphene is a commercially available product with a size of 2 μm and an S content of 4 wt %, such as the product produced by Shandong Jincheng Graphene Technology Co., Ltd.

[0053] Example 3

[0054] A method for preparing a graphene-doped thermal insulation and fireproof material for fireproof doors, the operating steps of which are as follows:

[0055] S1: Add 180g of fly ash / gangue fiber to 950g of water, then add 4g of graphene flame retardant synergist and 5g of polyvinyl alcohol. Stir quickly until evenly mixed, then pour into a mold and filter out excess water.

[0056] S2: removing excess graphene / polyvinyl alcohol solution from the mold, taking it out and drying it, thereby obtaining a graphene-doped thermal insulation and fireproof material for the fireproof door.

[0057] The drying temperature is 75° C. and the drying time is 22 hours.

[0058] The preparation method of the graphene flame retardant synergist is as follows:

[0059] H1: Add 3 g of 1,1'-bis(dimethylsilyl)iron, 6 g of dibutyltin maleate, 0.015 g of platinum chloride, and 280 g of N,N-dimethylformamide to an autoclave and disperse by ultrasonication under nitrogen protection;

[0060] H2: 45 g of thiol-modified graphene and 5 g of agmatine were added, ultrasonically dispersed, filtered, and dried to obtain a graphene flame retardant synergist.

[0061] The ultrasonic dispersion temperature of H1 is 75° C. and the time is 2 h.

[0062] The ultrasonic dispersion temperature of H2 is 75°C and the time is 22 hours.

[0063] The thiol-modified graphene is a commercially available product with a size of 3 μm and an S content of 6 wt %, such as the product produced by Shandong Jincheng Graphene Technology Co., Ltd.

[0064] Example 4

[0065] A method for preparing a graphene-doped thermal insulation and fireproof material for fireproof doors, the operating steps of which are as follows:

[0066] S1: Add 200g fly ash / gangue fiber to 1000g water, then add 5g graphene flame retardant synergist and 6g polyvinyl alcohol, stir quickly and evenly, pour into a mold, and filter out excess water;

[0067] S2: removing excess graphene / polyvinyl alcohol solution from the mold, taking it out and drying it, thereby obtaining a graphene-doped thermal insulation and fireproof material for the fireproof door.

[0068] The drying temperature is 80° C. and the drying time is 24 hours.

[0069] The preparation method of the graphene flame retardant synergist is as follows:

[0070] H1: Add 4 g of 1,1'-bis(dimethylsilyl)iron, 7 g of dibutyltin maleate, 0.02 g of platinum chloride, and 300 g of N,N-dimethylformamide to an autoclave and disperse by ultrasonication under nitrogen protection;

[0071] H2: 50 g of thiol-modified graphene and 6 g of agmatine were added, ultrasonically dispersed, filtered, and dried to obtain a graphene flame retardant synergist.

[0072] The ultrasonic dispersion temperature of H1 is 80°C and the time is 3 hours.

[0073] The ultrasonic dispersion temperature of H2 is 80°C and the time is 24 hours.

[0074] The thiol-modified graphene is a commercially available product with a size of 4.2 μm and an S content of 8.6 wt %, such as the product produced by Shandong Jincheng Graphene Technology Co., Ltd.

[0075] Comparative Example 1

[0076] No graphene flame retardant synergist was added, and other procedures were the same as in Example 1.

[0077] Comparative Example 2

[0078] Without adding 1'-bis(dimethylsilyl)iron, the other steps were the same as in Example 1.

[0079] Comparative Example 3

[0080] The other steps were the same as in Example 1 except that dibutyltin maleate was not added.

[0081] Test results:

[0082]

[0083]

[0084] Through the data analysis of the above examples and comparative examples, the graphene flame retardant synergist of the present invention can effectively improve the flame retardant properties of fireproof materials; the graphene-doped thermal insulation fireproof material for fireproof doors prepared by the present invention has a low bulk density and good thermal insulation performance.

[0085] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as above in terms of a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can, without departing from the scope of the technical solution of the present invention, make some changes or modifications to equivalent embodiments using the technical contents disclosed above. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a graphene-doped thermal insulation and fireproof material for fire doors, the operating steps of which are as follows: S1: Add 100-200 parts of fly ash / gangue fiber to 800-1000 parts of water, then add 2-5 parts of graphene flame retardant synergist and 4-6 parts of polyvinyl alcohol. Stir quickly until evenly mixed, pour into a mold, and filter out excess water. S2: removing excess graphene / polyvinyl alcohol solution from the mold, taking it out and drying it, thereby obtaining a graphene-doped thermal insulation and fireproof material for the fire door; The preparation method of the graphene flame retardant synergist is: H1: Add 2-4 parts of 1,1'-bis(dimethylsilyl)iron, 3.5-7 parts of dibutyltin maleate, 0.002-0.02 parts of platinum chloride, and 200-300 parts of N,N-dimethylformamide to an autoclave and disperse by ultrasonication under nitrogen protection; H2: Add 30-50 parts of thiol-modified graphene and 3-6 parts of agmatine, perform ultrasonic dispersion, filter, and dry to obtain a graphene flame retardant synergist.

2. The method for preparing a graphene-doped thermal insulation and fireproof material for fire doors according to claim 1, characterized in that: The drying temperature in step S2 is 60-80° C. and the drying time is 18-24 hours.

3. The method for preparing a graphene-doped thermal insulation and fireproof material for fire doors according to claim 1, characterized in that: The ultrasonic dispersion temperature in step H1 is 60-80° C. and the time is 1-3 h.

4. The method for preparing a graphene-doped thermal insulation and fireproof material for fire doors according to claim 1, characterized in that: The ultrasonic dispersion temperature in step H2 is 60-80° C. and the time is 18-24 h.

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