A multifunctional fireproof adhesive and its preparation method and application

Abstract

The present invention discloses a multifunctional fireproof adhesive and a preparation method and application thereof, and belongs to the technical field of fireproof adhesives. The present invention successfully prepares a multifunctional fireproof adhesive by combining siloxane, phosphate, amino and borate structures. The prepared multifunctional fireproof adhesive does not add inorganic fillers and other additives, has intrinsic fireproof characteristics, is simple in composition and does not have migration and precipitation problems; the prepared multifunctional fireproof adhesive has the advantages of high-temperature dense carbonization, has a carbonization heat insulation effect at high temperature, and can achieve efficient fireproof and heat insulation; it still has good and reliable adhesion in high-temperature combustion, and can effectively avoid the safety hazards caused by the fall of the bonded object in the fire; it can also be used as a flame retardant coating for wood, and through the combustion carbonization barrier effect, the heat release and smoke release behavior of the wood are suppressed, and it has a wide range of application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of fireproof adhesives, in particular to a multifunctional fireproof adhesive and a preparation method and application thereof. Background Art

[0002] With the improvement of building safety awareness, the demand for fireproof materials is also increasing. As an important component to prevent the spread of fire, fireproof adhesives have excellent fire resistance and good adhesion. They are widely used in fireproof sealing, heat insulation and sound insulation of buildings, and protection of cable lines. In addition, fireproof adhesives also play an important role in home decoration, automobile manufacturing, and aerospace. For example, fireproof adhesives are used in laminated composite fireproof glass, and the fireproof layer directly determines the performance of fireproof glass. It has strong adhesion and can expand and foam after a fire to form a sufficient thickness, which plays a role in carbonization fireproofing and heat insulation.

[0003] However, traditional fire-retardant adhesives still have some problems. First, traditional fire-retardant adhesives are mainly composed of binders, curing agents, solvents and other additives, with variable components, and contain inorganic fillers such as borates, phosphates, and hydrated alkali metal silicates. They are prone to migration and precipitation, which will reduce their bonding and fire-resistant durability during long-term service. Secondly, traditional fire-retardant adhesives have poor high-temperature bonding after combustion and carbonization, and cannot guarantee the safe and stable operation of the bonded objects in fire scenarios. Summary of the invention

[0004] The purpose of the present invention is to provide a multifunctional fireproof adhesive and a preparation method and application thereof, so as to solve the problems that the current fireproof adhesive has many types of components, is easy to migrate and precipitate, has a short service life, and has poor high-temperature adhesion after combustion and carbonization.

[0005] To achieve the above object, the present invention provides a multifunctional fireproof adhesive, which is composed of a colorless solid compound A2, boric acid, and isopropanol, wherein the mass volume ratio of boric acid: isopropanol is 1 g: 25 mL, and the molar ratio of boric acid: colorless solid compound A2 is 1: 1.5. The structural formula of the colorless solid compound A2 is:

[0006] , where n is an integer from 1 to 10.

[0007] A method for preparing the multifunctional fireproof adhesive as described above comprises the following steps:

[0008] S1, 3-aminopropyldiethoxymethylsilane and ultrapure water were refluxed for a certain period of time, and then vacuum distilled to obtain a colorless viscous liquid product A1, the reaction formula is: , where n is an integer from 1 to 10;

[0009] S2, dissolving the colorless viscous liquid product A1 obtained in step S1 in anhydrous ethanol, slowly adding dropwise to the ethanol solution of diphenylphosphoric acid, continuing the reaction for a certain period of time after the addition, and then removing the ethanol to obtain a colorless solid product A2, the reaction formula is:

[0010] , where n is an integer from 1 to 10;

[0011] S3, dissolving boric acid in isopropanol, and then ultrasonically treating the solution at room temperature for a certain period of time, mixing the obtained solution with the colorless solid product A2 obtained in step S2, stirring and reacting for a certain period of time, and then removing part of the isopropanol to obtain a multifunctional fireproof adhesive.

[0012] Preferably, the mass ratio of 3-aminopropyldiethoxymethylsilane to ultrapure water in S1 is 3-4:1, the reflux reaction conditions are: 70-100°C reflux reaction for 4-8 hours, and the reduced pressure distillation conditions are: first 120°C, 3 hours, then 150°C, 3 hours.

[0013] Preferably, the liquid product A1 obtained in S1 in S2 is dissolved in anhydrous ethanol, the mass volume ratio of the liquid product A1:anhydrous ethanol is 1 g:10 mL, and the mass volume ratio of diphenylphosphoric acid:anhydrous ethanol in the ethanol solution of diphenylphosphoric acid is 1.0-1.1 g:5 mL.

[0014] Preferably, after the addition of S2 is completed, the reaction is continued at 60-90° C. for 9-12 hours, and the anhydrous ethanol is removed by rotary evaporation.

[0015] Preferably, the mass volume ratio of boric acid to isopropanol in S3 is 1 g:25 mL, and after the boric acid is dissolved in isopropanol, ultrasonic treatment is performed at room temperature for 30 minutes.

[0016] Preferably, the isopropanol solution of boric acid in S3 and the colorless solid product A2 obtained in S2 are mixed at a molar ratio of 1:1.5, and the stirring reaction conditions are 70-100° C. and the stirring reaction is carried out for 30 minutes.

[0017] Preferably, the partial removal of isopropanol in S3 is carried out by heating the mixture to 105° C. to remove 1 / 5-1 / 2 of the total amount of isopropanol.

[0018] The multifunctional fireproof adhesive as described above is used in the fields of building fireproof sealing, heat and sound insulation, cable line protection, home decoration, automobile manufacturing, and aerospace. When used, the multifunctional fireproof adhesive is evenly coated on the surface of the target object and cured at 110° C. for 3-20 hours.

[0019] The above problems can be effectively avoided by designing an intrinsic fireproof adhesive with a simple composition and combining different fireproof structures in one. For example, the present invention introduces phosphate esters, amino structures, etc. into the multi-in-one fireproof adhesive to generate an expanding heat-insulating carbon layer at high temperature; introduces structures such as siloxanes and borates to improve its water resistance; at the same time, siloxanes and borates can improve the high-temperature thermal stability of the fireproof adhesive, and obtain a more stable and dense heat-insulating carbon layer after combustion; in addition, the combustion products of the fireproof adhesive are similar in composition to the bonded objects such as glass, which helps to maintain the adhesion of the adhesive during high-temperature combustion and prevent the objects from falling off during high-temperature combustion.

[0020] Therefore, the present invention provides a multifunctional fireproof adhesive and a preparation method and application thereof, and its specific technical effects are as follows:

[0021] (1) The present invention successfully prepares a multifunctional fireproof adhesive by combining siloxane, phosphate, amino and borate structures. The prepared multifunctional fireproof adhesive does not add inorganic fillers and other additives, has intrinsic fireproof characteristics, is simple in composition and does not have migration and precipitation problems;

[0022] (2) The multifunctional fireproof adhesive prepared by the present invention has the advantages of high-temperature dense carbonization, has a carbonization and heat insulation effect at high temperature, and can achieve efficient fireproof and heat insulation; it still has good and reliable adhesion during high-temperature combustion, and can effectively avoid the safety hazards caused by the adhesion falling off in the fire;

[0023] (3) The multifunctional fire-retardant adhesive prepared by the present invention can also be used as a flame-retardant coating for wood. Through the barrier effect of burning into carbon, the heat release and smoke release behavior of the wood are suppressed, and it has a wide application prospect.

[0024] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for use in the description of the embodiments of the present invention will be briefly introduced below. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative labor.

[0026] Figure 1 is the colorless viscous liquid product A1 in Example 1 of the present invention 1 H-NMR spectrum;

[0027] Figure 2 is the colorless solid product A2 in Example 1 of the present invention 1 H-NMR spectrum;

[0028] Figure 3 is the colorless solid product A2 in Example 1 of the present invention 31 P-NMR spectrum;

[0029] Figure 4 is the high temperature charring test result of the multifunctional fireproof adhesive prepared in Example 1 in Example 2 of the present invention;

[0030] Figure 5 is the thermal insulation test result of the double-layer glass without any coating in the fourth embodiment of the present invention;

[0031] Figure 6 is the thermal insulation test result of the double-layer glass coated with the multifunctional fireproof adhesive prepared in Example 1 in Example 4 of the present invention;

[0032] Figure 7 This is the test result of the combustion heat release inhibition capability of the multifunctional fireproof adhesive prepared in Example 1 in Example 5 of the present invention. DETAILED DESCRIPTION

[0033] The technical solution of the present invention is further described below through the accompanying drawings and embodiments.

[0034] In order to make the purpose, technical scheme and advantages of the present application clearer, more thorough and more complete, the technical scheme of the present invention is clearly and completely described below through the accompanying drawings and examples. The following detailed descriptions are all descriptions of the embodiments, and are intended to provide further detailed descriptions of the present invention. Unless otherwise specified, all technical terms used in the present invention have the same meaning as those generally understood by those skilled in the art to which the present application belongs.

[0035] The instruments, equipment, reagents and materials used in the examples were all obtained through commercial channels.

[0036] Embodiment 1

[0037] A multifunctional fireproof adhesive is prepared, and the specific steps are as follows:

[0038] S1. Add 20.3 g of 3-aminopropyldiethoxymethylsilane and 5.4 g of ultrapure water into a three-necked round-bottom flask and reflux at 90°C for 6 hours. Then perform vacuum distillation at 120°C for 3 hours and 150°C for 3 hours to obtain a colorless viscous liquid product A1. The reaction formula is as follows:

[0039] .

[0040] The colorless viscous liquid product A1 obtained by nuclear magnetic resonance detection 1 H-NMR spectrum, the results are as follows Figure 1shown.

[0041] S2, take 5 g of the colorless viscous liquid product A1 prepared in step S1 and 10.4 g of diphenylphosphoric acid, respectively, and dissolve them in 50 mL of anhydrous ethanol. Then add the obtained ethanol solution of diphenylphosphoric acid to a condensation reflux device, and then slowly drop the prepared colorless viscous liquid product A1 in anhydrous ethanol to the ethanol solution of diphenylphosphoric acid, and continue to react at 70 ° C for 12 hours after the dropwise addition. Remove ethanol by rotary evaporation to obtain a colorless solid product A2, the reaction formula is as follows:

[0042] .

[0043] The colorless solid product A2 obtained by nuclear magnetic resonance detection 1 H-NMR spectrum, the results are as follows Figure 2 The colorless solid product A2 obtained by nuclear magnetic resonance detection 31 P-NMR spectrum, the results are as follows Figure 3 shown.

[0044] S3, dissolve 0.1 g of boric acid in 2.5 mL of isopropanol, and then ultrasonicate at room temperature for 30 minutes. Take 25 mL of the resulting solution, mix it with 9 g of the colorless solid product A2 obtained in step S2, and then heat and stir at 75 ° C for 30 minutes, then heat the system to 105 ° C to remove 1 / 2 of the isopropanol, and the resulting viscous solution is the multifunctional fireproof adhesive.

[0045] Embodiment 2

[0046] The high-temperature charring property of the multifunctional fire-retardant adhesive prepared in Example 1 was investigated.

[0047] The multifunctional fireproof adhesive prepared in Example 1 was poured into a polytetrafluoroethylene mold, and taken out after curing at 110° C. for 5 hours. The structural formula of the cured multifunctional fireproof adhesive was determined to be:

[0048] .

[0049] Thermogravimetric analysis was performed using a thermogravimetric analyzer. The results are shown in Figure 4 As shown, the carbon residue rate of the multifunctional fireproof adhesive prepared in Example 1 at 800°C is 37.8%, and the carbon residue rate refers to the residual mass percentage of the sample at 800°C in thermogravimetric analysis.

[0050] Embodiment 3

[0051] The adhesion of the multifunctional fireproof adhesive prepared in Example 1 was investigated.

[0052] The multifunctional fireproof adhesive prepared in Example 1 is coated on the surface of the glass, and then another piece of glass is covered on the coated multifunctional fireproof adhesive. At room temperature, a shear strength test is performed on the double-layer glass with the multifunctional fireproof adhesive prepared in Example 1 coated in the middle using a universal testing machine. The measured shear strength is shown in Table 1.

[0053] Then the double-layer glass coated with the multifunctional fireproof adhesive prepared in Example 1 was carbonized at 600° C. for 1 hour, cooled to room temperature and then subjected to a shear strength test again. The measured shear strengths are shown in Table 1.

[0054] Table 1

[0055] .

[0056] Embodiment 4

[0057] The thermal insulation properties of the multifunctional fireproof adhesive prepared in Example 1 were examined.

[0058] Put two clean glasses together tightly, light a butane torch to heat one glass for 1800 s, then stop heating and use an infrared thermal imager to monitor the temperature change of the other glass. The results are as follows: Figure 5 As shown in Figure 2, within 240 s of heating, the glass temperature on the other side quickly rises to 675 °C.

[0059] The method of Example 3 was used to prepare double-layer glass with the multifunctional fireproof adhesive prepared in Example 1 in the middle. One side of the glass was heated for 1800 s by a butane spray gun, and then the heating was stopped. The temperature change of the other side of the glass was monitored by an infrared thermal imager. The results are as follows: Figure 6 As shown in Figure 3, within 400 s of heating, the glass temperature on the other side only rises to 550 °C.

[0060] Embodiment 5

[0061] The multifunctional fireproof adhesive prepared in Example 1 was investigated for its ability to inhibit the heat release from the combustion of flame-retardant wood.

[0062] The heat release behavior of flame-retardant wood was analyzed using a cone calorimeter. The size of the wood sample was 10×10×2 cm. 3 The adhesive prepared in Example 1 was applied to the upper surface of the wood at a coating amount of 0.05 g / cm 2 In the cone calorimeter test, the wood was ignited by electric spark ignition, and the wood sample of the same volume without any coating was used as a control. The thermal radiation power of the cone calorimeter was adjusted to 35 kW / m 2 , the temperature was adjusted to 700 °C for measurement.

[0063] The results are as follows Figure 7As shown, the total heat release of wood without any fireproofing material is 60 MJ / m 2 The total heat release of the wood coated with the multifunctional fireproof adhesive prepared in Example 1 was reduced to 38 MJ / m 2 . It shows that the multifunctional fireproof adhesive prepared in Example 1 can significantly inhibit the release of combustion heat.

[0064] Therefore, the present invention successfully prepares a multifunctional fireproof adhesive by combining siloxane, phosphate, amino and borate structures into one. The prepared multifunctional fireproof adhesive does not add inorganic fillers and other additives, has intrinsic fireproof characteristics, is simple in composition and does not have migration and precipitation problems; the prepared multifunctional fireproof adhesive has the advantages of high-temperature dense carbonization, has a carbonization and heat insulation effect at high temperatures, and can achieve efficient fireproofing and heat insulation; it still has good and reliable adhesion during high-temperature combustion, and can effectively avoid safety hazards caused by the detachment of the adherends in a fire; it can also be used as a flame-retardant coating for wood, and the heat release and smoke release behavior of the wood are suppressed through the combustion and carbonization barrier effect, and has broad application prospects.

[0065] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A multifunctional fireproof adhesive, characterized in that: It is composed of a colorless solid compound A2, boric acid, and isopropanol. The mass volume ratio of boric acid: isopropanol is 1 g: 25 mL, and the molar ratio of boric acid: colorless solid compound A2 is 1: 1.

5. The structural formula of the colorless solid compound A2 is: , where n is an integer from 1 to 10; The preparation method of the multifunctional fireproof adhesive comprises the following steps: S1, 3-aminopropyldiethoxymethylsilane and ultrapure water were refluxed for a certain period of time, and then reduced pressure distillation was performed to obtain a colorless viscous liquid product A1, and the reaction formula is: , where n is an integer from 1 to 10; S2, dissolving the colorless viscous liquid product A1 obtained in S1 in anhydrous ethanol, slowly adding it dropwise to the ethanol solution of diphenylphosphoric acid, continuing the reaction for a certain period of time after the addition, and then removing the ethanol to obtain a colorless solid product A2, the reaction formula is: , where n is an integer from 1 to 10; S3, dissolving boric acid in isopropanol, and then ultrasonically treating the solution at room temperature for a certain period of time, mixing the resulting solution with the colorless solid product A2 obtained in step S2, stirring and reacting for a certain period of time, and then removing part of the isopropanol to obtain a multifunctional fireproof adhesive; The mass ratio of 3-aminopropyldiethoxymethylsilane to ultrapure water in S1 is 3-4:1, the reflux reaction conditions are: 70-100 ° C reflux reaction for 4-8 hours, and the reduced pressure distillation conditions are: first 120 ° C, 3 hours, then 150 ° C, 3 hours; In said S2, the liquid product A1 obtained in S1 is dissolved in anhydrous ethanol, the mass volume ratio of the liquid product A1:anhydrous ethanol is 1 g:10 mL, and the mass volume ratio of diphenylphosphoric acid:anhydrous ethanol in the ethanol solution of diphenylphosphoric acid is 1.0-1.1 g:5 mL; After the addition of S2 is completed, the reaction is continued at 60-90°C for 9-12 hours, and the anhydrous ethanol is removed by rotary evaporation; In S3, after the boric acid is dissolved in isopropanol, ultrasonic treatment is performed at room temperature for 30 minutes; The isopropanol solution of boric acid in step S3 is mixed with the colorless solid product A2 obtained in step S2 at a molar ratio of 1:1.5, and the stirring reaction condition is 70-100° C. for 30 minutes.

2. A multifunctional fireproof adhesive according to claim 1, characterized in that: The isopropanol is partially removed in S3 by heating to 105° C., and 1 / 5-1 / 2 of the total amount of isopropanol is removed.

3. An application of the multifunctional fireproof adhesive as claimed in claim 1 in the fields of building fireproof sealing, heat insulation and sound insulation, cable line protection, home decoration, automobile manufacturing, and aerospace, characterized in that: During application, the multifunctional fireproof adhesive is evenly coated on the surface of the target object.

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