High-solid-content fireproof glue and preparation method thereof

Abstract

The invention provides a high-solid-content fireproof adhesive and a preparation method thereof. The fireproof adhesive comprises the following raw materials: aggregate, an anti-freezing agent, a dispersing agent, a curing agent and a defoaming agent, the aggregate comprises an inorganic material and a metal oxide, the inorganic material is silica sol and / or water glass, and the metal oxide is zirconium oxide and / or magnesium oxide; the mass of the dispersing agent is 1-5 wt% of the mass of the fireproof glue, and the dispersing agent comprises vitamin E succinic acid polyethylene glycol ester; the mass of the anti-freezing agent is 0.5 wt%-5 wt% of the mass of the fireproof glue; the volume mass ratio of the curing agent to the inorganic material is (0.5-2) mL: 10g. According to the invention, vitamin E succinic acid polyethylene glycol ester (TPGS) is used as a dispersing agent, so that zirconium oxide, magnesium oxide and other metal oxide solid particles with stable chemical properties can be effectively added in the preparation process of the fireproof glue solution, and the problem that zirconium and magnesium-containing salts or organic raw materials are usually easy to react or decompose in an alkaline environment is solved; the fire resistance and the heat insulation effect of the fireproof glue are obviously improved.

Description

Technical Field

[0001] The invention relates to the technical field of fireproof materials, and in particular to a fireproof adhesive with high solid content and a preparation method thereof. Background Art

[0002] With the increasing requirements for fire safety in the fields of construction, transportation, aviation, etc., the development of efficient fireproof materials has become a trend. Traditional fireproof adhesives mainly rely on physical insulation and flame retardant ingredients, and further improving the thermal insulation performance and stability of the materials on this basis, especially the performance in high temperature environments, is the focus of technical research and development. Zirconium and magnesium-containing materials are considered to be an effective way to improve the overall performance of fireproof adhesives due to their superior thermal insulation and high temperature resistance. Zirconium and magnesium-based materials have good thermal stability and low thermal conductivity at high temperatures, which can significantly enhance the thermal insulation effect of fireproof adhesives. Although there are many patents for fireproof glue formulas, the aggregates in the formulas are mainly silicon, and also contain a small amount of inorganic substances such as aluminum, magnesium, titanium, zirconium, zinc, etc., but the content is small, such as the Chinese patents with publication (announcement) numbers CN112358818A, CN111362662A, CN105131761B, CN105295741B, CN107263963A, CN107267103A and CN105131761A, and the total solid content in the fireproof glue is difficult to reach more than 50%.

[0003] Adding raw materials with better thermal insulation properties such as zirconium and magnesium to the fireproof adhesive can indeed improve its thermal insulation performance, but there are certain difficulties. The main reasons include the following: (1) Chemical stability: The fireproof adhesive is alkaline, and raw materials containing zirconium and magnesium are usually easy to react or decompose in an alkaline environment. 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 fireproof adhesive. (2) Dispersion and uniformity: Raw materials containing zirconium and magnesium often have high density and hardness, and may be difficult to disperse evenly in the adhesive. This unevenness will lead to inconsistent material properties and affect the overall thermal insulation effect of the fireproof adhesive. In addition, if the dispersion is poor, it may also lead to a decrease in the construction performance of the fireproof adhesive, such as poor fluidity and easy agglomeration. (3) Compatibility issues: Silica-based aggregates and raw materials containing zirconium and magnesium may be incompatible in chemical properties. Differences in thermal expansion coefficients, chemical reactivity, etc. of different materials may cause the fireproof adhesive to shrink or expand asynchronously in a high temperature environment, thereby affecting the overall structural stability and thermal insulation effect of the material. (4) Cost and process difficulty: Raw materials containing zirconium and magnesium are usually expensive and have higher processing requirements. In actual production, it is a challenge to effectively and economically add these raw materials to fireproof adhesives while ensuring their performance. In addition, this may require the development of new formulas and processes, increasing the complexity of R&D and production. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a fireproof adhesive to which zirconium and magnesium can be added and which has a high solid content, and a preparation method thereof, so as to solve the above-mentioned problems.

[0005] The technical solution of the present invention is achieved in this way:

[0006] A fireproof adhesive with a high solid content, the raw materials of which include aggregate, antifreeze agent, dispersant, curing agent and defoaming agent;

[0007] The aggregate comprises an inorganic material and a metal oxide, wherein the inorganic material is silica sol and / or water glass, and the metal oxide is zirconium oxide and / or magnesium oxide;

[0008] The mass of the dispersant is 1%wt to 5%wt of the mass of the fireproof glue, and the dispersant includes vitamin E succinate polyethylene glycol ester;

[0009] The mass of the antifreeze agent is 0.5%wt to 5%wt of the mass of the fireproof glue;

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

[0011] Calculated by solid content, the mass ratio of the defoamer to the aggregate is 0.1-2:100.

[0012] A further solution is that the mass of the dispersant is 3%wt~5%wt of the mass of the fireproof glue; the mass of the antifreeze agent is 0.5%wt~4%wt of the mass of the fireproof glue; and the volume mass ratio of the curing agent and the inorganic material is 0.8~1.2mL:10g.

[0013] In a further embodiment, the antifreeze agent comprises a polyol, and the polyol comprises at least one of glycerol, ethylene glycol or propylene glycol.

[0014] In a further embodiment, the curing agent comprises an epoxy compound, and the epoxy compound comprises at least one of ethylene oxide, propylene oxide, epoxy resin or epichlorohydrin.

[0015] In a further embodiment, the defoaming agent comprises organic silicon and / or polyether-modified silicone oil.

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

[0017] A further solution is that the particle size of the zirconium oxide is 2 to 20 nm, and the pore size is 0.5 to 20 nm; the particle size of the magnesium oxide is 2 to 20 nm, and the pore size is 0.5 to 20 nm.

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

[0019] According to the formula, aggregates are weighed, antifreeze agent, defoamer and dispersant are added, and stirred at 70-90° C. to obtain a sol; after the sol is cooled to 20-28° C., a curing agent is added and stirred continuously to obtain the fireproof adhesive.

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

[0021] On the other hand, the present invention also provides the use of the fireproof adhesive in preparing fireproof glass.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The invention selects aggregate, antifreeze agent, dispersant, curing agent and defoaming agent in scientific proportions, and the infusion type composite fireproof glass prepared by the fireproof glue provided has a fireproof and heat-insulating time of more than 50 minutes, an average visible light transmittance of 85-87%, and good fireproof performance of the glass.

[0024] The present invention uses vitamin E succinate polyethylene glycol ester (TPGS) as a dispersant, which can effectively add solid particles of metal oxides such as zirconium oxide and magnesium oxide in the preparation process of the fireproof glue, overcoming the problem that raw materials containing zirconium and magnesium are usually prone to reaction or decomposition in an alkaline environment. In addition, vitamin E succinate polyethylene glycol ester also improves the compatibility of metal oxide solid particles with other compounds in the fireproof glue, and the addition amount of metal oxide solid particles can account for 25% of the total solid content, and the solid content of the fireproof glue can reach up to 58%, which does not affect its fluidity and operability during use. This fireproof glue containing zirconium, magnesium and high solid content can significantly improve the fire resistance and heat insulation effect of the material. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. 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.

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

[0027] Unless otherwise specified, the materials, reagents, etc. used in the embodiments of the present invention can be obtained from commercial sources.

[0028] The silica sol and sodium silicate used in the examples of the present invention were purchased from Foshan Ke Ning New Material Technology Co., Ltd.

[0029] In the embodiment, the national standard GB / T 9978.1-2008 is used to test the fire resistance. The fireproof board sample is placed at the fire source, the test temperature is 1000°C, and the temperature of the glass back-fire surface and the fire resistance time are recorded and observed. During the test, when cracks appear on the composite fireproof board and the flame penetrates, it can be considered that its integrity is destroyed, thus reaching the fire resistance limit; as for its thermal insulation, it is judged according to the temperature of the back-fire surface of the fireproof board. During the test, when the temperature of the back-fire surface of the composite fireproof board reaches 140°C, it can be judged that the fireproof board loses its thermal insulation effect and reaches the fire resistance limit.

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

[0031] Example 1

[0032] Weigh 1000g of silica sol (50% residual solid content after calcination at 500°C), add 5g of polyether-modified silicone oil, 40g of glycerol and 50g of vitamin E succinate polyethylene glycol ester, stir for 180min at 80°C to obtain sol. Then cool the sol to room temperature, add 80mL of propylene oxide curing agent, stir for 0.5h to obtain fireproof adhesive.

[0033] The fireproof adhesive obtained in Example 1 was poured into the cavity of laminated glass (the glass was ordinary soda-lime-silica glass with a thickness of 2 mm), the adhesive layer was 3 mm thick, and cured at 80°C for 2 hours to obtain a poured composite fireproof glass. After the fire resistance test, the fire insulation time was 30 minutes, and the average visible light transmittance was 87.0%.

[0034] Embodiment 2-5

[0035] The formulas of the fireproof glue of Examples 2-5 are as follows:

[0036] Table 1 Types and contents of components of fireproof adhesive in Example 2-5

[0037]

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

[0039] According to the above formula, aggregates were weighed, antifreeze agent, defoamer and dispersant were added, and the mixture was stirred at 80°C for 180 minutes to obtain a sol. The sol was then cooled to room temperature, a curing agent was added, and the mixture was stirred for 0.5 hours to obtain fireproof adhesives of Examples 2-5, respectively.

[0040] The fireproof adhesive obtained in Examples 2-5 was poured into the cavity of laminated glass (the glass was ordinary soda-lime-silica glass with a thickness of 2 mm) respectively, with a thickness of 3 mm. After curing at 80°C for 2 hours, poured composite fireproof glass was obtained. The results of performance testing are shown in Table 2.

[0041] Table 2 Composite fire-resistant glass performance test results

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

[0043] It can be seen from Table 2 above that the fireproof composite fireproof glass prepared by using the fireproof adhesive of Examples 2-5 has a fire-resistant and heat-insulating time of 52 to 67 minutes and an average visible light transmittance of 85.5% to 86.4%.

[0044] The above is a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several improvements and modifications without departing from the principle of the present invention. These improvements and modifications are also considered to be within the scope of protection of the present invention.

Claims

1. A fireproof adhesive with high solid content, characterized in that: The raw materials of the fireproof glue include aggregate, antifreeze agent, dispersant, curing agent and defoaming agent; The aggregate comprises an inorganic material and a metal oxide, wherein the inorganic material is silica sol and / or water glass, and the metal oxide is zirconium oxide and / or magnesium oxide; The mass of the dispersant is 1%wt to 5%wt of the mass of the fireproof glue, and the dispersant includes vitamin E succinate polyethylene glycol ester; The mass of the antifreeze 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 material is 0.5-2 mL:10 g; Calculated by solid content, the mass ratio of the defoamer to the aggregate is 0.1-2:

100.

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

3. A high solid content fireproof adhesive according to claim 1 or 2, characterized in that: The antifreeze agent includes a polyol, and the polyol includes at least one of glycerol, ethylene glycol or propylene glycol.

4. A high solid content fireproof adhesive according to claim 1 or 2, characterized in that: The curing agent includes an epoxy compound, and the epoxy compound includes at least one of ethylene oxide, propylene oxide, epoxy resin or epichlorohydrin.

5. The high solid content fireproof adhesive according to claim 1, characterized in that: The defoaming agent includes organic silicon and / or polyether modified silicone oil.

6. The high solid content fireproof adhesive according to claim 1, characterized in that: The mass ratio of the inorganic material to the metal oxide is 10:0.8-1.5, and the solid content of the silica sol and / or water glass is 50%-60%.

7. A high solid content fireproof adhesive according to claim 6, characterized in that: 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.

8. The method for preparing the fireproof adhesive according to any one of claims 1 to 7, characterized in that: The steps include: According to the formula, aggregates are weighed, antifreeze agent, defoamer and dispersant are added, and stirred at 70-90° C. to obtain a sol; after the sol is cooled to 20-28° C., a curing agent is added and stirred continuously to obtain the fireproof adhesive.

9. The method for preparing the fireproof adhesive according to claim 8, characterized in that: Stir at 70-90°C for 2-4 hours.

10. The use of the fireproof adhesive according to any one of claims 1 to 7, characterized in that: The fireproof adhesive is used in preparing fireproof glass.

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