Fireproof adhesive with high solid content and preparation method thereof

Abstract

The application provides a high-solid-content fireproof glue and a preparation method thereof. The raw materials of the fireproof glue include aggregates, an anti-freezing agent, a dispersing agent, a curing agent and a defoaming agent. The aggregates include inorganic materials and metal oxides. The inorganic materials are silica sol and / or water glass, and the metal oxides are zirconium oxide and / or magnesium oxide. The mass of the dispersing agent is 1 wt% to 5 wt% of the mass of the fireproof glue, and the dispersing agent includes vitamin E succinate polyethylene glycol ester. The mass of the anti-freezing agent is 0.5 wt% to 5 wt% of the mass of the fireproof glue. The volume-mass ratio of the curing agent to the inorganic materials is 0.5 to 2 mL:10 g. The application uses vitamin E succinate polyethylene glycol ester (TPGS) as the dispersing agent, so that the solid particles of metal oxides with stable chemical properties, such as zirconium oxide and magnesium oxide, can be effectively added in the preparation process of the fireproof glue liquid. The problems that the salts containing zirconium and magnesium or the organic raw materials are prone to react or decompose in an alkaline environment are overcome, and the fire resistance and the heat insulation effect of the fireproof glue are significantly improved.

Description

Technical Field

[0001] This invention relates to the field of fire-retardant materials technology, and in particular to a high-solids-content fire-retardant adhesive and its preparation method. Background Technology

[0002] With increasing demands for fire safety in fields such as construction, transportation, and aviation, the development of highly efficient fire-retardant materials has become a trend. Traditional fire-retardant adhesives mainly rely on physical insulation and flame-retardant components. Further improving the insulation performance and stability of these materials, especially their performance under high-temperature environments, is a key focus of technological research and development. Zirconium and magnesium-containing materials are considered effective ways to improve the overall performance of fire-retardant adhesives due to their superior insulation and high-temperature resistance. Zirconium and magnesium-based materials exhibit good thermal stability and low thermal conductivity at high temperatures, which can significantly enhance the insulation effect of fire-retardant adhesives. Although there are already many patents for fire-retardant adhesive formulations, the aggregates in these formulations are mainly silicon, with small amounts of inorganic substances such as aluminum, magnesium, titanium, zirconium, and zinc, but in small quantities, as seen in Chinese patents with publication (announcement) numbers CN112358818A, CN111362662A, CN105131761B, CN105295741B, CN107263963A, CN107267103A, and CN105131761A. Furthermore, the total solid content in fire-retardant adhesives is rarely more than 50%.

[0003] Adding materials with better heat insulation properties, such as zirconium and magnesium, to fire-retardant adhesives can indeed improve their heat insulation performance, but there are certain difficulties. The main reasons include the following: (1) Chemical stability: Fire-retardant adhesives are alkaline, while raw materials containing zirconium and magnesium are usually prone to reaction or decomposition in alkaline environments. For example, magnesium and its compounds may generate magnesium hydroxide under alkaline conditions, which will affect its physical properties and stability, thereby reducing the overall performance of the fire-retardant adhesive. (2) Dispersion and uniformity: Raw materials containing zirconium and magnesium often have high density and hardness, which may be difficult to disperse uniformly in the adhesive. This non-uniformity will lead to inconsistent material properties and affect the overall heat insulation effect of the fire-retardant adhesive. In addition, if the dispersion is poor, it may also lead to a decrease in the construction performance of the fire-retardant adhesive, such as poor fluidity and easy clumping. (3) Compatibility issues: Silica-based aggregates and raw materials containing zirconium and magnesium may be chemically incompatible. Differences in the coefficient of thermal expansion and chemical reactivity of different materials may cause the fire-retardant adhesive to exhibit asynchronous shrinkage or expansion in high-temperature environments, thereby affecting the overall structural stability and heat insulation effect of the material. (4) Cost and Processing Difficulty: Raw materials containing zirconium and magnesium are generally expensive and require more sophisticated processing techniques. In actual production, effectively and economically adding these raw materials to fire-retardant adhesives while ensuring their performance is a challenge. Furthermore, this may require the development of new formulations and processes, increasing the complexity of research and development and production. Summary of the Invention

[0004] Therefore, the purpose of this invention is to provide a fire-retardant adhesive that can be added with zirconium and magnesium and has a high solid content, and a method for preparing the same, thereby solving the above-mentioned problems.

[0005] The technical solution of this invention is implemented as follows:

[0006] A high-solids-content fire-retardant adhesive, wherein the raw materials of the fire-retardant adhesive include aggregates, antifreeze agents, dispersants, curing agents, and defoamers;

[0007] The aggregate comprises inorganic materials and metal oxides, wherein the inorganic materials are silica sol and / or water glass, and the metal oxides are zirconium oxide and / or magnesium oxide.

[0008] The mass of the dispersant is 1% wt to 5% wt of the fire retardant adhesive, and the dispersant includes polyethylene glycol succinate containing vitamin E.

[0009] The antifreeze agent is 0.5% wt to 5% wt of the fire retardant adhesive.

[0010] The volume-to-mass ratio of the curing agent to the inorganic material is 0.5–2 mL: 10 g;

[0011] Based on solid content, the mass ratio of the defoamer to the aggregate is 0.1 to 2:100.

[0012] A further embodiment is that the mass of the dispersant is 3% wt to 5% wt of the fire retardant adhesive; the mass of the antifreeze agent is 0.5% wt to 4% wt of the fire retardant adhesive; and the volume-to-mass ratio of the curing agent to the inorganic material is 0.8 to 1.2 mL: 10 g.

[0013] A further embodiment is that the antifreeze agent comprises a polyol, wherein the polyol comprises at least one of glycerol, ethylene glycol, or propylene glycol.

[0014] A further embodiment is that the curing agent comprises an epoxy compound, which includes at least one of ethylene oxide, propylene oxide, epoxy resin, or epichlorohydrin.

[0015] A further option is that the defoamer includes organosilicon and / or polyether-modified silicone oil.

[0016] A further embodiment is that the mass ratio of the inorganic material to the metal oxide is 10:0.8 to 1.5, and the solid content of the silica sol and / or water glass is 50% to 60%.

[0017] A further embodiment is that the zirconium oxide particles have a particle size of 2–20 nm and a pore size of 0.5–20 nm; the magnesium oxide particles have a particle size of 2–20 nm and a pore size of 0.5–20 nm.

[0018] On one hand, the present invention provides a method for preparing the above-mentioned fire-retardant adhesive, comprising the following steps:

[0019] According to the formula, weigh the aggregate, add antifreeze, defoamer and dispersant, stir at 70-90℃ to obtain sol; after the sol cools to 20-28℃, add curing agent and continue stirring to obtain the fireproof adhesive.

[0020] A further approach is to stir at 70–90°C for 2–4 hours.

[0021] On the other hand, the present invention also provides the application of the above-mentioned fire-retardant adhesive in the preparation of fire-retardant glass.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] The present invention uses a scientifically proportioned mixture of aggregates, antifreeze, dispersant, curing agent and defoamer to prepare a fireproof composite fireproof glass with a fire resistance and heat insulation time of more than 50 minutes and an average visible light transmittance of 85-87%, exhibiting good fire resistance performance.

[0024] This invention utilizes polyethylene glycol emulsion succinate (TPGS) as a dispersant, effectively adding solid particles of metal oxides such as zirconium oxide and magnesium oxide during the preparation of fire-retardant adhesives. This overcomes the problem that zirconium and magnesium-containing raw materials are prone to reaction or decomposition in alkaline environments. Furthermore, TPGS also improves the compatibility of the metal oxide solid particles with other compounds in the fire-retardant adhesive. The addition amount of metal oxide solid particles can reach 25% of the total solid content, and the solid content of the fire-retardant adhesive can reach up to 58%, without affecting its flowability and workability during use. This fire-retardant adhesive, containing zirconium and magnesium and with a high solid content, can significantly improve the fire resistance and heat insulation effect of materials. Detailed Implementation

[0025] 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.

[0026] Unless otherwise specified, the experimental methods used in the embodiments of this invention are all conventional methods.

[0027] Unless otherwise specified, all materials and reagents used in the embodiments of this invention are commercially available.

[0028] The silica sol and sodium silicate used in the embodiments of the present invention were purchased from Foshan Kening New Materials Technology Co., Ltd.

[0029] In this embodiment, the fire resistance performance was tested according to the national standard GB / T 9978.1-2008. The fireproof board sample was placed at a fire source, and the test temperature was 1000℃. The temperature of the unexposed surface of the glass and the fire resistance time were recorded and observed. During the test, when the composite fireproof board developed cracks that allowed flame penetration, its integrity was considered compromised, thus reaching its fire resistance limit. Its thermal insulation performance was determined based on the temperature of the unexposed surface of the fireproof board. During the test, when the temperature of the unexposed surface of the composite fireproof board reached 140℃, it was determined that the fireproof board had lost its thermal insulation effect and reached its fire resistance limit.

[0030] In this embodiment, a Lambda 950 spectrophotometer was used to measure visible light transmittance.

[0031] Example 1

[0032] Weigh 1000g of silica sol (50% solids content after calcination at 500℃), add 5g of polyether-modified silicone oil, 40g of glycerin, and 50g of vitamin E succinate polyethylene glycol ester. Stir at 80℃ for 180min to obtain a sol. Cool the sol to room temperature, add 80mL of propylene oxide curing agent, and stir for 0.5h to obtain a fire-retardant adhesive.

[0033] The fire-retardant adhesive obtained in Example 1 was injected into the cavity of laminated glass (ordinary soda-lime silicate glass, 2 mm thick), with an adhesive layer thickness of 3 mm. After curing at 80°C for 2 hours, a potted composite fire-retardant glass was obtained. After fire resistance testing, the fire resistance and heat insulation time was 30 minutes, and the average visible light transmittance was 87.0%.

[0034] Examples 2-5

[0035] The formulations of the fire-retardant adhesives in Examples 2-5 are as follows:

[0036] Table 1. Types and contents of each component in the fire-retardant adhesives of Examples 2-5

[0037]

[0038] Note: The particle size of zirconium oxide and magnesium oxide solid particles is 2-20 nm, and the pore size is 0.5-20 nm.

[0039] According to the above formula, weigh the aggregate, add antifreeze, defoamer and dispersant, and stir at 80℃ for 180 min to obtain a sol. Then cool the above sol to room temperature, add curing agent, and stir for 0.5 h to obtain the fire retardant adhesives of Examples 2-5 respectively.

[0040] The fireproof adhesives obtained in Examples 2-5 were injected into the cavities of laminated glass (the glass was ordinary soda-lime-silicon glass with a thickness of 2 mm). The adhesive layer was 3 mm thick and cured at 80°C for 2 hours to obtain the injected composite fireproof glass. The results of its performance testing are shown in Table 2.

[0041] Table 2. Performance Test Results of Composite Fireproof Glass

[0042] project Example 2 Example 3 Example 4 Example 5 Fire resistance and heat insulation time (min) 57 52 67 63 Average transmittance of visible light (%) 86.4 86.4 85.5 85.6

[0043] As shown in Table 2 above, the fire-resistant composite fireproof glass made using the fire-retardant adhesive of Examples 2-5 has a fire resistance and heat insulation time of 52-67 minutes and an average visible light transmittance of 85.5%-86.4%.

[0044] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications are also considered to be within the scope of protection of the present invention.

Claims

1. A high-solids-content fire-retardant adhesive, characterized in that, The raw materials of the fire-retardant adhesive include aggregates, antifreeze agents, dispersants, curing agents, and defoamers; the antifreeze agent includes polyols, and the polyols include at least one of glycerol, ethylene glycol, or propylene glycol; The aggregate comprises inorganic materials and metal oxides in a mass ratio of 10:0.8~1.5, wherein the inorganic materials are silica sol and / or water glass, and the metal oxides are zirconium oxide and / or magnesium oxide; the solid content of the silica sol and / or water glass is 50%~60%; the particle size of the zirconium oxide is 2~20 nm, and the pore size is 0.5~20 nm; the particle size of the magnesium oxide is 2~20 nm, and the pore size is 0.5~20 nm. The mass of the dispersant is 1%wt to 5%wt of the fire retardant adhesive, and the dispersant includes polyethylene glycol vitamin E succinate. The antifreeze agent is 0.5%wt to 5%wt of the fire retardant adhesive. The volume-to-mass ratio of the curing agent to the inorganic material is 0.5~2 mL:10 g; Based on solid content, the mass ratio of the defoamer to the aggregate is 0.1~2:

100.

2. The high-solids-content fire-retardant adhesive according to claim 1, characterized in that, The mass of the dispersant is 3%wt to 5%wt of the fire retardant adhesive; the mass of the antifreeze agent is 0.5%wt to 4%wt of the fire retardant adhesive; and the volume-to-mass ratio of the curing agent to the inorganic material is 0.8 to 1.2 mL: 10 g.

3. A high-solids-content fire-retardant adhesive according to claim 1 or 2, characterized in that, The curing agent includes an epoxy compound, which includes at least one of ethylene oxide, propylene oxide, epoxy resin, or epichlorohydrin.

4. The high solids content fire-retardant adhesive according to claim 1, characterized in that, The defoamer includes organosilicon and / or polyether-modified silicone oil.

5. The method for preparing the fire-retardant adhesive according to any one of claims 1 to 4, characterized in that, Includes the following steps: According to the formula, weigh the aggregate, add antifreeze, defoamer and dispersant, stir at 70~90℃ to obtain sol; after the sol cools to 20~28℃, add curing agent and continue stirring to obtain the fireproof adhesive.

6. The method for preparing the fire-retardant adhesive according to claim 5, characterized in that, Stir at 70~90℃ for 2~4 hours.

7. The application of the fire-retardant adhesive according to any one of claims 1 to 4 or the fire-retardant adhesive prepared by the preparation method according to claim 5, characterized in that, The fire-retardant adhesive is used in the preparation of fire-resistant glass.

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