Amine-modified adenosine triphosphate flame retardant, preparation method thereof, and application thereof in fire retardant coating

Abstract

The present invention discloses an amine-modified adenosine triphosphate flame retardant. The preparation method comprises: dropwise adding an adenosine triphosphate solution to an amine solution, carrying out a reaction under stirring and heat preservation; and cooling, centrifuging, and drying the resulting reaction product to obtain the amine-modified adenosine triphosphate flame retardant. The amine-modified adenosine triphosphate flame retardant of the present invention has excellent environmental and flame retardant properties. When used in the preparation of fire-retardant coatings, it can achieve advantages such as good storage performance, long fire protection time, long service life, good weather resistance, good decorative properties, and water-based environmental protection. Furthermore, the preparation method is simple, the raw materials are widely available, and the product is environmentally friendly, making it suitable for widespread application.

Description

Technical Field

[0001] The invention belongs to the technical field of fireproof materials, and particularly relates to an amine-modified adenosine triphosphate flame retardant, a preparation method thereof, and application thereof in fireproof coatings. Background Art

[0002] Intumescent fire-retardant coatings are usually composed of adhesives, intumescent flame retardant systems and filler additives. When a fire occurs, the adhesive melts and the acid source in the intumescent flame retardant system decomposes to release acidic substances. The acidic substances promote the dehydration and carbonization of the adhesive and carbon source, causing the gas source to decompose, release non-combustible gases and generate viscous fluid coke. The two combine to form a honeycomb carbon layer, thereby isolating air and heat transfer to achieve excellent fireproofing and heat insulation effects.

[0003] ATP is a common biological product and a major source of energy for animals, with a wide range of sources. ATP's molecular structure contains an acid source (three phosphate groups), a carbon source (ribose), and a gas source (adenine), making it a high-quality bio-based flame retardant. However, ATP is easily hydrolyzed and has a low thermal decomposition temperature (5% mass loss in air is only 60 degrees), making it difficult to apply and preserve in practice. In addition, when applying it to fire-retardant coatings, it is usually necessary to control the corresponding reaction conditions and reaction temperature, and it is also necessary to overcome issues such as compatibility with other components.

[0004] At present, the society advocates concepts such as environmental protection and greenness, and the environmental performance of coatings has received a lot of attention; further exploration of efficient and environmentally friendly flame retardants and their preparation methods has important research and application significance. Summary of the Invention

[0005] The main purpose of the present invention is to address the deficiencies in the prior art and provide an amine-modified adenosine triphosphate flame retardant with good environmental protection and flame retardant effects. The amine-modified adenosine triphosphate flame retardant is used to prepare fire-retardant coatings, which have the advantages of good storage performance, long fire protection time, long service life, good weather resistance, good decorativeness, rust prevention function, water-based and environmentally friendly, and raw materials derived from bio-based materials. The preparation method involved is simple, the fire protection effect is excellent, and the amine-modified adenosine triphosphate flame retardant is suitable for promotion and application.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] A method for preparing an amine-modified adenosine triphosphate flame retardant comprises the following steps:

[0008] 1) dissolving an amine substance in water, heating and stirring uniformly to obtain an amine salt solution; then adding adenosine triphosphate solution dropwise thereto, and carrying out a reaction under stirring and heat preservation;

[0009] 2) Cooling the obtained reaction product to room temperature and centrifuging to obtain a solid precipitate; then drying the solid precipitate to obtain the amine-modified ATP flame retardant.

[0010] In the above scheme, the amine substance can be selected from furfural amine or dopamine.

[0011] In the above scheme, the molar ratio of the amine substance to adenosine triphosphate is 1:(1.3-2).

[0012] In the above scheme, the heating and stirring temperature in step 1) is 25-40° C. and the time is 20-30 min.

[0013] In the above scheme, the insulation reaction temperature is 25-40°C and the time is 40 minutes to 1 hour.

[0014] The invention discloses a fire-retardant coating based on an amine salt-modified adenosine triphosphate flame retardant. The components and their weight percentages include: 35-60% bisphenol A waterborne epoxy resin emulsion, 0-20% ammonium polyphosphate, 0-20% pentaerythritol, 0-15% melamine, 0.5-1% dispersant, 0.5-1% defoamer, 0.5-1% n-octanol, and 5-20% amine-modified adenosine triphosphate flame retardant.

[0015] In the above solution, the solid content of the bisphenol A type waterborne epoxy resin emulsion is 40-50%.

[0016] In the above solution, the dispersant is wetting dispersant 5040 or the like.

[0017] In the above solution, the defoaming agent is silicone defoaming agent 470 or the like.

[0018] The principle of the present invention is:

[0019] The present invention utilizes an amine-containing salt to react with adenosine triphosphate (ATP) to form a salt to prepare a composite flame retardant. The adenine group of ATP can participate in the amino group reaction of amine substances, and the resulting modified flame retardant can significantly improve the performance of fire-retardant coatings. At the same time, the ATP contained in it has a low thermal decomposition temperature and can effectively protect against fire in the early stages of the occurrence. Adenosine triphosphate is derived from biological organisms and is inherently extremely unstable. After the salt-forming reaction with the amine-containing salt, its stability can be effectively improved, thereby obtaining a wider temperature range of application.

[0020] The present invention adopts a one-step green synthesis process. Under the premise of not destroying the structure, performance and effect of ATP itself, deionized water is used as a carrier, and the product reacts with an amine substance at room temperature. After stirring, the product is centrifuged to obtain a solid product. Since ATP itself contains three high-energy phosphate bonds and has a high phosphorus content, it is easier to form carbon after dehydration. The carbon source can become a carbonizing agent, and the carbon element is the key to forming a carbon layer. In addition, the amino group and the hydroxyl group can be used as an acid source, a gas source, and a carbon source in the intumescent flame retardant system. After compounding with an amine salt, the amine salt also contains nitrogen. The gas source formed by the nitrogen element can better cooperate to form an intumescent carbon layer, and promote the generation of non-combustible gases such as N2 and CO2 in the system to effectively block combustion. Therefore, the carbon layer can be expanded after combustion, and a higher residual carbon amount and carbon layer thickness can be obtained, with a longer fire resistance time, good stability, and a long storage time.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1) The flame retardant containing ATP modified by amine salts of the present invention is used to obtain a fire retardant coating having the advantages of long fire resistance, excellent adhesion, short drying time, good crack resistance, etc., and can have good flame retardancy, mechanical properties, durability and stability, etc., and is suitable for promotion and application;

[0023] 2) The introduced ATP has a low thermal decomposition temperature and can protect the substrate in the early stages of a fire;

[0024] 3) The flame retardant of the present invention has a simple preparation method, low reaction temperature, a wide range of raw materials, is environmentally friendly, and is suitable for promotion and application. DETAILED DESCRIPTION

[0025] For a better understanding of the present invention, the following examples further describe the present invention, but the present invention is not limited to the following examples.

[0026] In the following examples, the solid content of the bisphenol A waterborne epoxy resin emulsion used is 40%; the dispersant is wetting dispersant 5040; and the defoaming agent is silicone defoamer 470.

[0027] Example 1

[0028] An amine-modified adenosine triphosphate flame retardant, the preparation method of which comprises the following steps:

[0029] 1) Weigh 3.8 g of furfural amine and dissolve it in 100 ml of deionized water. Place the mixture in a 500 ml three-necked round-bottom flask and stir at 30°C for 30 min using a heat-collecting constant-temperature magnetic stirrer and a multifunctional electric stirrer to obtain a furfural amine solution.

[0030] 2) Weigh 5.1 g of ATP and dissolve it in 100 ml of deionized water. Place the mixture in a 500 ml beaker and stir with a magnetic stirrer at room temperature for 30 min to obtain an ATP solution.

[0031] 3) Using a dropping funnel, add the ATP solution dropwise to the furfurylamine solution at 30°C over one hour, and continue stirring at 30°C for 1 hour to allow for full reaction.

[0032] 4) Cooling the resulting product to room temperature; centrifuging at 8000 rpm for 5 minutes using a high-speed centrifuge, repeating three times to obtain a solid precipitate; and then vacuum drying the solid precipitate in a vacuum oven at 60° C. for 24 hours to obtain a furfurylamine-modified adenosine triphosphate flame retardant.

[0033] Example 2

[0034] An amine-modified adenosine triphosphate flame retardant, the preparation method of which comprises the following steps:

[0035] 1) Weigh 2 g of dopamine and dissolve it in 100 ml of deionized water. Place the mixture in a 500 ml three-necked round-bottom flask and stir at 40°C for 30 min using a heat-collecting constant-temperature magnetic stirrer and a multifunctional electric stirrer to prepare a dopamine solution.

[0036] 2) Weigh 4 g of ATP and dissolve it in 100 ml of deionized water. Place the mixture in a 500 ml beaker and stir with a magnetic stirrer at room temperature for 30 min to obtain an ATP solution.

[0037] 3) Using a dropping funnel, add the ATP solution dropwise to the dopamine solution at 40°C over one hour, and continue stirring at 40°C for 1 hour to allow for a complete reaction.

[0038] 4) The obtained product was subjected to rotary evaporation at 50° C. in a rotary evaporator to obtain a solid product; and the solid product was naturally dried to obtain a dopamine-modified adenosine triphosphate flame retardant.

[0039] Application Example 1

[0040] The furfurylamine-modified adenosine triphosphate flame retardant obtained in Example 1 is used to prepare a fire retardant coating, and the specific steps include:

[0041] 1) Weigh the raw materials; the components and their mass percentages include: 60% bisphenol A waterborne epoxy resin emulsion, 10% deionized water, 10% polyphosphate ammonium, 5% pentaerythritol, 5% melamine, 1% dispersant, 0.5% defoamer, 0.5% n-octanol, and 8% furfurylamine-modified adenosine triphosphate flame retardant;

[0042] 2) Grinding the weighed ammonium polyphosphate, pentaerythritol, melamine, and furfurylamine-modified adenosine triphosphate flame retardant into a powder without particles, then adding water to fully grind and mix; then adding a defoamer and a dispersant, and continuing to fully grind;

[0043] 3) Finally, add bisphenol A type waterborne epoxy resin emulsion and n-octanol and grind and mix thoroughly to obtain the fire retardant coating.

[0044] Application Example 2

[0045] The amine-modified adenosine triphosphate flame retardant obtained in Example 2 was used to prepare a fire retardant coating, and the specific steps included:

[0046] 1) Weigh the raw materials; the components and their mass percentages include: 60% bisphenol A type waterborne epoxy resin emulsion, 10% deionized water, 10% polyphosphate ammonium, 5% pentaerythritol, 5% melamine, 1% dispersant, 0.5% defoamer, 0.5% n-octanol, and 8% dopamine-modified adenosine triphosphate flame retardant.

[0047] 2) Grinding the weighed ammonium polyphosphate, pentaerythritol, melamine, and dopamine-modified adenosine triphosphate flame retardant into a powder without particles, then adding water to fully grind and mix; then adding a defoamer and a dispersant, and continuing to fully grind;

[0048] 3) Finally, add bisphenol A type waterborne epoxy resin emulsion and n-octanol and grind and mix thoroughly to obtain the fire retardant coating.

[0049] Comparative Example 1

[0050] A water-based intumescent fire-retardant coating, the preparation method of which is substantially the same as that of Application Example 1, except that an adenosine triphosphate solution is added dropwise to a furfurylamine solution at a temperature of 40°C over 30 minutes using a dropping funnel, and stirring is continued at 40°C for 1 hour to allow sufficient reaction; the resulting product is cooled to room temperature; centrifuged at 10,000 rpm for 3 minutes using a high-speed centrifuge, and repeated twice to obtain a solid precipitate; and then placed in a vacuum oven and vacuum-dried at 65°C for 24 hours to obtain the furfurylamine-modified adenosine triphosphate salt flame retardant.

[0051] Comparative Example 2

[0052] A water-based intumescent fire-retardant coating, the preparation method of which is substantially the same as that of Application Example 2, except that an adenosine triphosphate solution is added dropwise to a dopamine solution at a temperature of 45°C using a dropping funnel within 40 minutes, and stirring is continued at 45°C for 1 hour to allow sufficient reaction; the resulting product is rotary evaporated in a rotary evaporator at 65°C to obtain a solid product; and the product is naturally dried to obtain the dopamine-modified adenosine triphosphate salt flame retardant.

[0053] Comparative Example 3

[0054] A water-based intumescent fire-retardant coating, the preparation method of which is substantially the same as that of Application Example 1, except that the components and their mass percentages are as follows: 60% bisphenol A water-based epoxy resin emulsion, 10% deionized water, 10% polyphosphate ammonium, 5% pentaerythritol, 5% melamine, 1% dispersant, 0.5% defoamer, 0.5% n-octanol, and 8% adenosine triphosphate solution.

[0055] Comparative Example 4

[0056] A water-based intumescent fire-retardant coating, the preparation method of which is substantially the same as that of Application Example 2, except that the components and their mass percentages are: 60% bisphenol A water-based epoxy resin emulsion, 10% deionized water, 10% polyphosphate ammonium, 5% pentaerythritol, 5% melamine, 1% dispersant, 0.5% defoamer, 0.5% n-octanol, and 8% adenosine triphosphate solution.

[0057] The intumescent fire retardant coatings obtained in Application Example 12 and Comparative Examples 1-4 were subjected to fire resistance tests, and the results are shown in Table 1.

[0058] Table 1 Performance test results of the intumescent fire retardant coatings obtained in Application Examples 1, 2 and Comparative Examples 1 to 4

[0059]

[0060]

[0061] The above embodiments are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.

Claims

1. A method for preparing an amine-modified adenosine triphosphate flame retardant, characterized in that: The steps include: 1) dissolving an amine substance in water, heating and stirring to obtain an amine salt solution; then adding adenosine triphosphate solution dropwise thereto, and carrying out a reaction under stirring and heat preservation; 2) cooling the obtained reaction product to room temperature and centrifuging to obtain a solid precipitate; then drying the solid precipitate to obtain the amine-modified ATP flame retardant; The amine substance is furfuralamine or dopamine; The molar ratio of the amine substance to adenosine triphosphate is 1:(1.3-2); The insulation reaction temperature is 25-40° C. and the time is 40 min-1 h.

2. The preparation method according to claim 1, characterized in that Step 1) The heating and stirring temperature is 25-40° C. and the time is 20-30 min.

3. Amine-modified adenosine triphosphate flame retardant prepared by the preparation method according to any one of claims 1 to 2.

4. The fire retardant coating containing an amine salt-modified adenosine triphosphate flame retardant according to claim 3, characterized in that: The components and their mass percentages include: 35-60% of bisphenol A waterborne epoxy resin emulsion, 0-20% of polyphosphate ammonium, 0-20% of pentaerythritol, 0-15% of melamine, 0.5-1% of dispersant, 0.5-1% of defoamer, 0.5-1% of n-octanol, and 5-20% of amine-modified adenosine triphosphate flame retardant.

5. The fire retardant coating according to claim 4, characterized in that: The solid content of the bisphenol A type waterborne epoxy resin emulsion is 40-50%.

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