Red intumescent fireproof sealing material and production process thereof

Abstract

The invention belongs to the technical field of materials, and particularly relates to a red intumescent fireproof sealing material and a production process thereof.The sealing material is prepared by mixing an acrylic emulsion serving as a matrix with an aluminum hydroxide synergistic flame retardant and the like serving as additives. Wherein the aluminum hydroxide synergistic flame retardant is prepared by modifying the surface of aluminum hydroxide with a macromolecular nitrogen-phosphorus flame retardant, the macromolecular nitrogen-phosphorus flame retardant can form a transition structure at the interface of the aluminum hydroxide and acrylic resin to promote the aluminum hydroxide to be uniformly dispersed in the sealing material, and the sealing material can be enhanced by utilizing the advantages of the aluminum hydroxide; the macromolecular nitrogen-phosphorus flame retardant can quickly form an expanded carbon layer to isolate heat and oxygen when the material burns, and meanwhile, aluminum hydroxide serving as an inorganic flame retardant can cooperate with the macromolecular nitrogen-phosphorus flame retardant to effectively improve the flame retardant property of the material, so that the effect that the fireproof flame retardant property of the material can be greatly enhanced by adding a small amount of the flame retardant can be achieved.

Description

Technical Field

[0001] This invention belongs to the field of materials technology, specifically relating to a red intumescent fireproof sealing material and its production process. Background Technology

[0002] Currently, most red intumescent fire-retardant sealants use polyurethane, silicone, or neoprene rubber as the elastic matrix, employing ammonium polyphosphate-melamine-pentaerythritol as the classic intumescent flame-retardant system. Organic red pigments such as permanent red and lithol red are added to adjust the color, along with plasticizers, crosslinking agents, and reinforcing fillers. It forms an expanded char layer to block flames through the decomposition and foaming of the flame-retardant system at high temperatures. Relying on the elastic matrix to adapt to gap deformation, it is widely used in scenarios such as gaps in building firewalls and cable penetrations through floor slabs, combining fireproofing, sealing, and decorative warning functions.

[0003] To achieve high fire resistance, existing fire-retardant sealants often increase the amount of ammonium polyphosphate to over 40%, resulting in a loose and porous expanded char layer that is prone to collapse under high temperatures and airflow impact, thus compromising the fire-retardant effect. Furthermore, high filler content of flame retardant weakens the interfacial adhesion between the sealant and the substrate, requiring additional primer application and increasing construction costs. Conversely, reducing the amount of flame retardant significantly reduces the fire-retardant effect, allowing flames to easily penetrate the sealant layer.

[0004] Based on this, the present invention provides a fire-retardant sealant material that can solve the problems existing in the prior art. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a red intumescent fireproof sealing material and its production process.

[0006] A first aspect of the present invention provides a red intumescent fire-retardant sealing material, comprising the following raw materials measured in parts by weight: 45-50 parts acrylic emulsion; 1-3 parts calcium carbonate; 5-7 parts sepiolite fiber; 3-6.5 parts of aluminum hydroxide synergistic flame retardant; 2-4 parts colorant; 0.5-1 part wetting agent; Dispersant 0.5-1 part; 0.1-0.5 parts of defoamer; Thickener 0.5-1.5 parts; Preservative: 0.1-0.3 parts; The aluminum hydroxide synergistic flame retardant is aluminum hydroxide with surface-modified macromolecular nitrogen and phosphorus flame retardants.

[0007] As a preferred embodiment of the present invention, the acrylic emulsion has a solid content of 50%.

[0008] As a preferred embodiment of the present invention, the aluminum hydroxide synergistic flame retardant is prepared by the following method: Step 1: Organically modify aluminum hydroxide using a surface-modifying agent to obtain halogenated modified aluminum hydroxide; Step 2: Add halomodified aluminum hydroxide to N,N-dimethylformamide and disperse it evenly by ultrasonication. Then add piperazine to the formed dispersion, add the catalyst, turn on the heater, raise the temperature to 70-80℃, keep it warm and stir for 2-4 hours, then add the oxophosphorus hexane derivative. After the addition is complete, adjust the temperature to 85-95℃, continue stirring for 9-18 hours, then stop the heating and discharge the material.

[0009] As a preferred embodiment of the present invention, in step one, the surface modification agent is any one of 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, or 3-bromopropyltrimethoxysilane.

[0010] As a preferred embodiment of the present invention, in step two, the catalyst is triethylamine or triethylenediamine.

[0011] As a preferred embodiment of the present invention, in step two, the oxophosphorus hexane derivative is prepared by the following method: [(6-oxo-6H-dibenzo[c,e][1,2]oxophosphazenehexane-6-yl)methyl]succinate bis(2-hydroxyethyl) ester and 2-chloroethyl isocyanate were added to 1,4-dioxane. After the addition was complete, the mixture was mechanically stirred until homogeneous. Then, a tin catalyst was added. After the addition was complete, the temperature was controlled at 60-70℃ and stirred for 6-9 hours. The solvent was then evaporated to remove the solvent, and the crude product was collected and purified.

[0012] As a preferred embodiment of the present invention, the molar ratio of [(6-oxo-6H-dibenzo[c,e][1,2]oxophosphoroxane-6-yl)methyl]succinate bis(2-hydroxyethyl) ester and 2-chloroethyl isocyanate is 1:2.

[0013] As a preferred embodiment of the present invention, the tin catalyst is any one of methyl tin mercaptan, octyl tin mercaptan, dibutyltin diacetate, stannous octoate, or dibutyltin dilaurate.

[0014] Specifically, in the above technical solution, a silane coupling agent is first used as a surface modifier to modify the surface of aluminum hydroxide. Halogen substituents are then modified on the surface of the aluminum hydroxide to obtain halogenated modified aluminum hydroxide. Next, using the halogen substituents of the halogenated modified aluminum hydroxide as polymerization sites, piperazine as an intermediate linker, and oxophosphorus hexane derivatives as chain extenders, the halogen substituents and secondary amine groups undergo continuous substitution reactions under the action of a catalyst, thereby modifying the surface of aluminum hydroxide with a macromolecular nitrogen-phosphorus flame retardant having an alternating piperazine-oxophosphorus hexane structure.

[0015] The oxophosphorus hexane derivative is prepared by reacting the active hydroxyl substituents in the structure of [(6-oxo-6H-dibenzo[c,e][1,2]oxophosphorus hexane-6-yl)methyl]succinate bis(2-hydroxyethyl) ester and 2-chloroethyl isocyanate with the isocyanate group under the action of a tin catalyst.

[0016] As a preferred embodiment of the present invention, the colorant is iron oxide red; the wetting agent is alkyl polyoxyethylene ether; the dispersant is BYK-346; the defoamer is NYK-065; the thickener is sodium hydroxyethyl cellulose; and the preservative is methylisothiazolinone.

[0017] A second aspect of the present invention provides a manufacturing process for a red intumescent fire-retardant sealing material, comprising the following steps: Step 1: Add the acrylic emulsion, calcium carbonate, sepiolite fiber, aluminum hydroxide synergist flame retardant, colorant, wetting agent, dispersant, thickener and preservative measured by weight into a high-speed mixer and mechanically stir and mix them evenly at a speed of 300-500 r / min to form a mixture. The second step is to adjust the rotation speed to 100-200 r / min, and continue to add defoamer while stirring. After adding the defoamer, stir for 10-20 minutes and let it stand to defoam.

[0018] Compared with the prior art, the present invention has the following beneficial effects: This invention prepares a synergistic flame retardant for aluminum hydroxide by modifying the surface of aluminum hydroxide with a macromolecular nitrogen-phosphorus flame retardant. The macromolecular nitrogen-phosphorus flame retardant, acting as an organic layer, forms a transition structure at the interface between aluminum hydroxide and acrylic resin, effectively improving the interfacial compatibility between the two. This promotes the uniform dispersion of aluminum hydroxide in the sealing material. The advantage of aluminum hydroxide as an inorganic additive can be utilized to strengthen the sealing material and improve its toughness. Secondly, the macromolecular nitrogen-phosphorus flame retardant exhibits excellent synergistic flame retardant effects, rapidly forming an expanding carbon layer during combustion to isolate heat and oxygen. Simultaneously, aluminum hydroxide, as an inorganic flame retardant, works synergistically with the macromolecular nitrogen-phosphorus flame retardant to effectively improve the flame retardant properties of the material, achieving a significant enhancement of the material's fire resistance and flame retardant performance with only a small amount added. Detailed Implementation

[0019] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0020] Preparation Example Preparation of aluminum hydroxide synergistic flame retardant: Step A: Add 3.5g of aluminum hydroxide to a 60% (v / v) ethanol aqueous solution and disperse it evenly by ultrasonication. Then add 0.8g of 3-chloropropyltrimethoxysilane to the formed uniform dispersion. After the addition is complete, adjust the pH to 4, adjust the temperature to 70℃, keep it warm and stir for 6 hours, and then cool down and discharge the material to obtain halogenated modified aluminum hydroxide. Step B: Add 0.6 g of [(6-oxo-6H-dibenzo[c,e][1,2]oxophosphoric acid bis(2-hydroxyethyl) ester]succinate and 0.29 g of 2-chloroethyl isocyanate to 1,4-dioxane. After the addition is complete, stir mechanically until homogeneous. Then, add 0.01 g of dibutyltin dilaurate. After the addition is complete, control the temperature at 65℃ and stir for 8 hours. Then, evaporate to remove the solvent, collect the crude product, and purify it to obtain the oxophosphoric acid bis(2-hydroxyethyl) derivative. Step C: Add 2.5g of halomodified aluminum hydroxide to N,N-dimethylformamide and disperse it evenly by ultrasonication. Then add 0.2g of piperazine to the formed dispersion, followed by 0.1g of triethylamine. Turn on the heater and raise the temperature to 75℃. After stirring for 3 hours, add 1.6g of oxophosphorus hexane derivative. After the addition is complete, adjust the temperature to 85℃ and continue stirring for 12 hours. Then stop the heating and discharge the material. Example

[0021] This embodiment provides a red intumescent fireproof sealing material, comprising the following raw materials measured in parts by weight: 45 parts acrylic emulsion; 1 part calcium carbonate; 5 parts sepiolite fiber; Three parts of aluminum hydroxide synergistic flame retardant; Two portions of iron oxide red; 0.5 parts of alkyl polyoxyethylene ether; BYK-346 0.5 copies; NYK-065 0.1 copies; 0.5 parts of sodium hydroxyethyl cellulose; 0.1 part of methylisothiazolinone; The method for preparing the sealing material includes the following steps: Step 1: Add the acrylic emulsion, calcium carbonate, sepiolite fiber, aluminum hydroxide synergistic flame retardant, iron oxide red, alkyl polyoxyethylene ether, BYK-346, sodium hydroxyethyl cellulose and methylisothiazolinone measured by weight into a high-speed mixer and mechanically stir and mix them evenly at a speed of 300 r / min to form a mixture. Step 2: Adjust the speed to 100r / min, and continue to add NYK-065 while stirring. After adding, stir for 20 minutes and let stand to defoam.

[0022] The solid content of the acrylic emulsion is 50%; the preparation method of the aluminum hydroxide synergistic flame retardant is shown in the preparation example, and the same applies below. Example

[0023] This embodiment provides a red intumescent fireproof sealing material, comprising the following raw materials measured in parts by weight: 46 parts acrylic emulsion; 2 parts calcium carbonate; Six parts sepiolite fiber; Six parts of aluminum hydroxide synergistic flame retardant; 3 portions of iron oxide red; 0.6 parts of alkyl polyoxyethylene ether; BYK-346 0.8 copies; NYK-065 0.3 copies; 1 part sodium hydroxyethyl cellulose; 0.2 parts of methylisothiazolinone; The method for preparing the sealing material includes the following steps: Step 1: Add the acrylic emulsion, calcium carbonate, sepiolite fiber, aluminum hydroxide synergistic flame retardant, iron oxide red, alkyl polyoxyethylene ether, BYK-346, sodium hydroxyethyl cellulose and methylisothiazolinone measured by weight into a high-speed mixer and mechanically stir and mix them evenly at a speed of 400 r / min to form a mixture. Step 2: Adjust the speed to 150r / min, and continue to add NYK-065 while stirring. After adding, stir for 15 minutes and let stand to defoam. Example

[0024] Red intumescent fire-resistant sealing material, comprising the following raw materials measured in parts by weight: 50 parts acrylic emulsion; 3 parts calcium carbonate; 7 parts sepiolite fiber; 6.5 parts of aluminum hydroxide synergistic flame retardant; 4 portions of iron oxide red; 1 part of alkyl polyoxyethylene ether; BYK-346 1 copy; NYK-065 0.5 copies; 1.5 parts of sodium hydroxyethyl cellulose; 0.3 parts of methylisothiazolinone; The method for preparing the sealing material includes the following steps: Step 1: Add the acrylic emulsion, calcium carbonate, sepiolite fiber, aluminum hydroxide synergistic flame retardant, iron oxide red, alkyl polyoxyethylene ether, BYK-346, sodium hydroxyethyl cellulose and methylisothiazolinone measured by weight into a high-speed mixer and mechanically stir and mix them evenly at a speed of 500 r / min to form a mixture. Step 2: Adjust the speed to 200r / min, and continue to add NYK-065 while stirring. After adding, stir for 10 minutes and let stand to defoam.

[0025] Comparative Example 1 The difference between this comparative example and Example 2 is that the aluminum hydroxide synergistic flame retardant is replaced with aluminum hydroxide, otherwise they are the same.

[0026] Comparative Example 2 The difference between this comparative example and Example 2 is that the aluminum hydroxide synergistic flame retardant is removed; otherwise, they are the same.

[0027] The sealing materials provided in the above embodiments and comparative examples were poured into a mold, cured, and made into test samples that meet the test specifications. Performance tests were then conducted, and the test methods are as follows: (1) Tensile properties were tested in accordance with GB / T 1040.1-2025; (2) Refer to GB / T 2406.2-2009 to conduct the limiting oxygen index test and evaluate the fire resistance and flame retardant performance; The performance test data above are shown in Table 1.

[0028] Table 1 Performance Test Results

[0029] As can be seen from the above, the sealing material prepared in the embodiments of the present invention has good toughness and fire-retardant properties. After replacing the aluminum hydroxide synergistic flame retardant with aluminum hydroxide, on the one hand, due to the interface problem, aluminum hydroxide cannot be evenly dispersed and can not effectively exert its own advantages. On the other hand, it cannot utilize the advantages of macromolecular nitrogen and phosphorus flame retardants. Therefore, the various properties show a significant decrease.

[0030] This article uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of the present invention, including the best mode, and also to enable any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the present invention.

Claims

1. A red intumescent fireproof sealing material, characterized in that, Including the following raw materials measured in parts by weight: 45-50 parts acrylic emulsion; 1-3 parts calcium carbonate; 5-7 parts sepiolite fiber; 3-6.5 parts of aluminum hydroxide synergistic flame retardant; 2-4 parts colorant; 0.5-1 part wetting agent; Dispersant 0.5-1 part; 0.1-0.5 parts of defoamer; Thickener 0.5-1.5 parts; Preservative: 0.1-0.3 parts; The aluminum hydroxide synergistic flame retardant is aluminum hydroxide with surface-modified macromolecular nitrogen and phosphorus flame retardants.

2. The red intumescent fireproof sealing material according to claim 1, characterized in that, The acrylic emulsion has a solid content of 50%.

3. The red intumescent fireproof sealing material according to claim 1, characterized in that, The aluminum hydroxide synergistic flame retardant is prepared by the following method: Step 1: Organically modify aluminum hydroxide using a surface-modifying agent to obtain halogenated modified aluminum hydroxide; Step 2: Add halomodified aluminum hydroxide to N,N-dimethylformamide and disperse it evenly by ultrasonication. Then add piperazine to the formed dispersion, add the catalyst, turn on the heater, raise the temperature to 70-80℃, keep it warm and stir for 2-4 hours, then add the oxophosphorus hexane derivative. After the addition is complete, adjust the temperature to 85-95℃, continue stirring for 9-18 hours, then stop the heating and discharge the material.

4. The red intumescent fireproof sealing material according to claim 3, characterized in that, In step one, the surface modification agent is any one of 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, or 3-bromopropyltrimethoxysilane.

5. The red intumescent fireproof sealing material according to claim 3, characterized in that, In step two, the catalyst is triethylamine or triethylenediamine.

6. The red intumescent fireproof sealing material according to claim 3, characterized in that, In step two, the oxophosphorus hexane derivative is prepared using the following method: [(6-oxo-6H-dibenzo[c,e][1,2]oxophosphazenehexane-6-yl)methyl]succinate bis(2-hydroxyethyl) ester and 2-chloroethyl isocyanate were added to 1,4-dioxane. After the addition was complete, the mixture was mechanically stirred until homogeneous. Then, a tin catalyst was added. After the addition was complete, the temperature was controlled at 60-70℃ and stirred for 6-9 hours. The solvent was then evaporated to remove the solvent, and the crude product was collected and purified.

7. The red intumescent fireproof sealing material according to claim 6, characterized in that, The molar ratio of [(6-oxo-6H-dibenzo[c,e][1,2]oxophosphazenecyclo-6-yl)methyl]succinate bis(2-hydroxyethyl) ester and 2-chloroethyl isocyanate is 1:

2.

8. The red intumescent fireproof sealing material according to claim 6, characterized in that, The tin catalyst is any one of methyl tin mercaptan, octyl tin mercaptan, dibutyltin diacetate, stannous octoate, or dibutyltin dilaurate.

9. The red intumescent fireproof sealing material according to claim 1, characterized in that, The colorant is iron oxide red; the wetting agent is alkyl polyoxyethylene ether; the dispersant is BYK-346; the defoamer is NYK-065; the thickener is sodium hydroxyethyl cellulose; and the preservative is methylisothiazolinone.

10. A production process for the red intumescent fireproof sealing material as described in claim 1, characterized in that, Includes the following steps: Step 1: Add the acrylic emulsion, calcium carbonate, sepiolite fiber, aluminum hydroxide synergist flame retardant, colorant, wetting agent, dispersant, thickener and preservative measured by weight into a high-speed mixer and mechanically stir and mix them evenly at a speed of 300-500 r / min to form a mixture. The second step is to adjust the rotation speed to 100-200 r / min, and continue to add defoamer while stirring. After adding the defoamer, stir for 10-20 minutes and let it stand to defoam.

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