Water-based inner cabin coating based on nano titanium dioxide and phosphorus-nitrogen synergistic flame-retardant system and preparation method of water-based inner cabin coating

Abstract

The invention relates to the technical field of ship inner cabin coatings, and particularly discloses a water-based inner cabin coating based on nano titanium dioxide and a phosphorus-nitrogen synergistic flame-retardant system and a preparation method of the water-based inner cabin coating. The water-based inner cabin coating based on the nano titanium dioxide and the phosphorus-nitrogen synergistic flame-retardant system is prepared from the following raw materials in parts by weight: 5 to 10 parts of nano titanium dioxide, 10 to 15 parts of a phosphorus-nitrogen composite flame retardant, 60 to 70 parts of water-based acrylate resin and 5 to 10 parts of filler, the phosphorus-nitrogen composite flame retardant is prepared from melamine phosphate and triphenyl phosphate; the coating prepared by the invention has a relatively good flame-retardant effect under the synergistic effect of all the components.

Description

Technical Field

[0001] The present application relates to the technical field of ship interior coatings, and in particular to a water-based interior coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system and a preparation method thereof. Background Art

[0002] Currently, fire-retardant coatings for confined spaces such as ship interiors primarily use organic solvent-based coatings. These not only pose environmental concerns but also generate toxic gases in the presence of high temperatures or fire, posing a threat to personnel safety. Water-based coatings, due to their environmentally friendly and low-pollution properties, have gained widespread adoption in various interior coating applications. They align with modern society's pursuit of green solutions, effectively reducing the volatilization of organic solvents and minimizing harm to the environment and human health. While also meeting the basic needs of interior decoration and protection, they are gaining an increasingly important position in the market.

[0003] Existing solutions enhance flame retardancy by adding inorganic flame retardants, such as aluminum hydroxide and magnesium hydroxide. However, excessive inorganic fillers can easily affect the coating's rheological properties and workability. Halogen flame retardants are also unsuitable for the enclosed spaces of ship cabins, where low smoke and low toxicity are essential during fires. Summary of the Invention

[0004] In order to improve the flame retardant effect of existing interior cabin coatings, the present application provides a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system and a preparation method thereof.

[0005] In the first aspect, the present application provides a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system, which adopts the following technical solution: A water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system comprises the following raw materials in parts by weight: 5-10 parts of nano-titanium dioxide, 10-15 parts of a phosphorus-nitrogen composite flame retardant, 60-70 parts of a water-based acrylic resin, and 5-10 parts of a filler; the phosphorus-nitrogen composite flame retardant comprises melamine phosphate and triphenyl phosphate.

[0006] By adopting this technical solution and using a water-based acrylic resin as the coating base, the VOC emissions associated with solvent-based coatings can be reduced, making it suitable for the enclosed environments of ship interiors. The use of a water-based acrylic resin can also improve the coating's weather resistance and adhesion, thereby extending its durability within ship interiors.

[0007] Melamine phosphate and triphenyl phosphate decompose at high temperatures to form a dense carbon layer that isolates heat and oxygen, providing a flame retardant effect. Titanium dioxide catalyzes the cross-linking of acrylic resin at high temperatures, promoting the formation of a more stable carbon layer and enhancing its mechanical strength and thermal stability. Nano-titanium dioxide particles are evenly dispersed in the coating, slowing heat conduction and the diffusion of combustible gases. It synergizes with the flame retardant to enhance the coating's flame retardancy.

[0008] Melamine phosphate decomposes to produce non-flammable gas, forming a gas-phase flame retardant. Triphenyl phosphate can decompose into phosphoric acid derivatives at high temperatures, catalyzing the dehydration of the polymer into carbon, forming a solid-phase flame retardant. The phosphorus-nitrogen composite flame retardant covers different combustion stages through gas-solid dual-phase flame retardancy, and nano-titanium dioxide further strengthens the carbon layer, forming a multi-level protection of gas dilution-free radical inhibition-physical barrier. The flame retardant efficiency is significantly higher than that of a single flame retardant component, effectively improving the flame retardant effect of the coating.

[0009] Preferably, the mass ratio of melamine phosphate to triphenyl phosphate is 1:(0.8-1.2).

[0010] Preferably, the acrylate resin is pre-grafted with the epoxy resin, and the grafting method comprises the following specific steps: mixing the epoxy resin with the solvent and heating it, and then adding methyl methacrylate, butyl acrylate, styrene, acrylamide, and an initiator under the protection of nitrogen to react and obtain the epoxy-acrylate grafted resin.

[0011] By adopting this technical solution, grafting acrylates onto epoxy resins improves the coating's corrosion resistance, impact resistance, and adhesion, enabling it to better protect the interior cabin. This reduces the adhesion loss associated with acrylic resins alone in the humid environment of ship interiors, reduces blistering and flaking, and prolongs the coating's durability. The epoxy resin provides strength, while the acrylate segments provide flexibility. The grafting creates a rigid and flexible coating structure that withstands the mechanical wear and tear of ship interiors.

[0012] Preferably, the epoxy-acrylate graft resin comprises the following raw materials in parts by weight: 30-50 parts of epoxy resin, 20-30 parts of methyl methacrylate, 15-25 parts of butyl acrylate, 8-15 parts of styrene, 1-3 parts of acrylamide, 0.5-0.8 parts of initiator, and 40-60 parts of solvent.

[0013] Preferably, the temperature of the reaction is 110-120°C.

[0014] Preferably, the filler is a mixture of multi-walled carbon nanotubes and nano-silicon dioxide.

[0015] By employing this technical solution, multi-walled carbon nanotubes (MWCNTs) can block the diffusion of heat and combustible gases, slowing the spread of flames and reducing the rate of heat release. The nano-silica melts to form a silicate glass layer that coats the carbon layer, enhancing its thermal and oxygen insulation properties. The MWCNTs' network skeleton combines with the melted nano-silica coating to form a denser dual-physical barrier coating.

[0016] Preferably, the filler is pre-surface-modified, comprising the following specific steps: The filler is mixed with the acid solution, stirred evenly, filtered, washed and dried to obtain the pretreated filler; the silane coupling agent, water and anhydrous ethanol are mixed and heated, and the pretreated filler is added and mixed to react, filtered, washed with water and dried to obtain the surface-modified filler.

[0017] By adopting the above technical solution, the surface of the filler is acidified in advance and then subjected to silanization surface treatment, which can promote the uniform dispersion of multi-walled carbon nanotubes and nano-silica in the coating system and reduce the agglomeration of nanoparticles.

[0018] Preferably, the mass ratio of the silane coupling agent, the acid solution and the filler is (0.5-0.8):(4-5):1.

[0019] Preferably, the acid solution is one of sulfuric acid and nitric acid.

[0020] In a second aspect, the present application provides a method for preparing a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system, using the following technical solution: A method for preparing a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system comprises the following specific steps: mixing nano-titanium dioxide, a phosphorus-nitrogen composite flame retardant, a water-based acrylic resin, and a filler, and stirring the mixture to obtain a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system.

[0021] By adopting the above technical solution, the prepared interior cabin coating has a good flame retardant effect under the synergistic effect of various components, and is more suitable for the closed interior environment of the ship.

[0022] In summary, this application has the following beneficial effects: 1. Because this application uses a water-based acrylic resin as the coating base, it is suitable for the enclosed environment of a ship's interior. The use of a water-based acrylic resin can improve the coating's weather resistance and adhesion, thereby extending the coating's durability within the ship's interior. The use of a combination of melamine phosphate and triphenyl phosphate as a flame retardant ingredient, synergistically enhancing the coating's flame retardancy with nano-titanium dioxide, mitigates the inadequate flame retardancy of a single flame retardant ingredient.

[0023] 2. In this application, acrylic resin is pre-grafted with epoxy resin to enhance the corrosion resistance and adhesion effect of the coating, reduce blistering and peeling of the coating, and reduce the problem of decreased adhesion of a single acrylic resin in the humid environment of the ship's interior cabin, thereby adapting to the mechanical wear requirements of the ship's interior cabin. DETAILED DESCRIPTION

[0024] The present application is further described in detail below with reference to the embodiments.

[0025] All raw materials in the examples are commercially available. Example

[0026] Example 1 This embodiment provides a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system. The coating comprises the following raw materials, by weight: 8 kg of nano-titanium dioxide, 13 kg of a phosphorus-nitrogen composite flame retardant, 65 kg of a water-based acrylic resin, and 8 kg of filler. The phosphorus-nitrogen composite flame retardant is a mixture of melamine phosphate and triphenyl phosphate, with a mass ratio of melamine phosphate to triphenyl phosphate of 1:1. The nano-titanium dioxide has an average particle size of 50 nm, and the viscosity of the water-based acrylic resin is 500 cps / 25°C. The filler is multi-walled carbon nanotubes with an average inner diameter of 4 nm and an average outer diameter of 10 nm.

[0027] The preparation method of a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system comprises the following specific steps: mixing nano-titanium dioxide, a phosphorus-nitrogen composite flame retardant, a water-based acrylic resin, and a filler, and dispersing the mixture at a high speed of 1200 r / min to obtain a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system.

[0028] Example 2 The difference between Example 2 and Example 1 is that the amount of nano-titanium dioxide used in the water-based interior cabin paint raw material based on the nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system is 5 kg, the amount of phosphorus-nitrogen composite flame retardant used is 15 kg, the amount of water-based acrylic resin used is 70 kg, and the amount of filler used is 5 kg.

[0029] Example 3 The difference between Example 3 and Example 1 is that the amount of nano-titanium dioxide used in the water-based interior cabin paint raw material based on the nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system is 10 kg, the amount of phosphorus-nitrogen composite flame retardant used is 10 kg, the amount of water-based acrylic resin used is 60 kg, and the amount of filler used is 10 kg.

[0030] Example 4 The difference between Example 4 and Example 1 is that the mass ratio of melamine phosphate to triphenyl phosphate in the phosphorus-nitrogen composite flame retardant is 1:0.8.

[0031] Example 5 The difference between Example 5 and Example 1 is that the mass ratio of melamine phosphate to triphenyl phosphate in the phosphorus-nitrogen composite flame retardant is 1:1.2.

[0032] Example 6 Example 6 differs from Example 1 in that the raw materials for the water-based interior cabin coating based on the nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system include an acrylate resin pre-grafted with an epoxy resin. The epoxy-acrylate grafted resin comprises the following raw materials by weight: 40 kg of epoxy resin, 25 kg of methyl methacrylate, 20 kg of butyl acrylate, 12 kg of styrene, 2 kg of acrylamide, 0.65 kg of initiator, and 50 kg of solvent. The epoxy resin is SM6101 from Sanmu Co., Ltd., the initiator is dibenzoyl peroxide, and the solvent is propylene glycol methyl ether.

[0033] The preparation method of a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system comprises the following specific steps: S1: Mix the epoxy resin and solvent and heat to 115°C. Under the protection of nitrogen, add methyl methacrylate, butyl acrylate, styrene, acrylamide, and initiator, and react at 115°C for 4 hours to obtain epoxy-acrylate grafted resin.

[0034] S2: Nano-titanium dioxide, phosphorus-nitrogen composite flame retardant, epoxy-acrylate grafted resin, and filler are mixed and dispersed at a high speed of 1200 r / min to obtain a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system.

[0035] Example 7 The difference between Example 7 and Example 6 is that the amount of epoxy resin used in the epoxy-acrylate graft resin raw material is 30 kg, the amount of methyl methacrylate used is 30 kg, the amount of butyl acrylate used is 15 kg, the amount of styrene used is 15 kg, the amount of acrylamide used is 3 kg, the amount of initiator used is 0.5 kg, and the amount of solvent used is 40 kg.

[0036] Example 8 The difference between Example 8 and Example 6 is that the amount of epoxy resin used in the epoxy-acrylate graft resin raw material is 50 kg, the amount of methyl methacrylate used is 20 kg, the amount of butyl acrylate used is 25 kg, the amount of styrene used is 8 kg, the amount of acrylamide used is 1 kg, the amount of initiator used is 0.8 kg, and the amount of solvent used is 60 kg.

[0037] Example 9 Example 9 differs from Example 6 in that the filler in the waterborne interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system is a mixture of multi-walled carbon nanotubes and nano-silicon dioxide, with a mass ratio of 1:1. The average particle size of the nano-silicon dioxide is 50 nm.

[0038] Example 10 The difference between Example 10 and Example 9 is that the filler in the raw material of the water-based interior cabin coating based on the nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system has been surface-modified in advance.

[0039] The preparation method of a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system comprises the following specific steps: S1: Pour 85% by mass nitric acid aqueous solution into the filler, mix and stir evenly, filter, wash and dry to obtain the pretreated filler; mix the silane coupling agent, water and anhydrous ethanol and heat it to 50°C, then add the pretreated filler and mix and react for 2 hours. The mass ratio of silane coupling agent, nitric acid aqueous solution, water, anhydrous ethanol and filler is 0.6:3:0.6:0.6:1. After filtering, the product is washed with water and dried to obtain a surface-modified filler.

[0040] S2: Mix the epoxy resin and the solvent and heat to 115°C. Under the protection of nitrogen, add methyl methacrylate, butyl acrylate, styrene, acrylamide, and an initiator, and react at 115°C for 4 hours to obtain an epoxy-acrylate grafted resin.

[0041] S3: Nano-titanium dioxide, phosphorus-nitrogen composite flame retardant, epoxy-acrylate grafted resin, and surface-modified filler are mixed and dispersed at a high speed of 1200 r / min to obtain a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system.

[0042] Example 11 The difference between Example 11 and Example 10 is that no acid treatment is performed during the surface modification process of the filler.

[0043] The preparation method of a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system comprises the following specific steps: S1: Mix silane coupling agent, water and anhydrous ethanol and heat to 50°C, then add filler and mix and react for 2 hours. The mass ratio of silane coupling agent, water, anhydrous ethanol and filler is 0.6:0.6:0.6:1. After filtering, the product is washed with water and dried to obtain a surface-modified filler.

[0044] S2: Mix the epoxy resin and the solvent and heat to 115°C. Under the protection of nitrogen, add methyl methacrylate, butyl acrylate, styrene, acrylamide, and an initiator, and react at 115°C for 4 hours to obtain an epoxy-acrylate grafted resin.

[0045] S3: Nano-titanium dioxide, phosphorus-nitrogen composite flame retardant, epoxy-acrylate grafted resin, and surface-modified filler are mixed and dispersed at a high speed of 1200 r / min to obtain a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system.

[0046] Comparative Example Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the water-based interior cabin coating based on the nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system originally used an equal amount of melamine phosphate instead of the phosphorus-nitrogen composite flame retardant.

[0047] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the water-based interior cabin coating based on the nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system originally used an equal amount of triphenyl phosphate instead of the phosphorus-nitrogen composite flame retardant.

[0048] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that nano-titanium dioxide is not originally used in the water-based interior cabin coating based on the nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system.

[0049] Performance testing The following performance tests were conducted on the water-based interior cabin coatings based on the nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system provided in Examples 1-11 and Comparative Examples 1-2 of the present application. The specific test results are shown in Table 1.

[0050] Detection method 1. Oxygen Index The oxygen index of the water-based interior cabin coating prepared in this application was tested with reference to the standard of GB / T5454-1997 "Textile combustion performance test - oxygen index method".

[0051] 2. Smoke density Refer to the standard GB8323.2-2008 "Plastic Smoke Generation Part 2: Single Chamber Test Method for Determination of Smoke Density" and record the maximum smoke density and the time to reach the maximum smoke density.

[0052] 3. Impact strength Referring to the standard of GB / T1732-2020 "Determination of impact resistance of paint films", the impact resistance of the water-based interior cabin coating prepared in this application was tested.

[0053] Table 1: Performance test results data table Performance test results indicate that the water-based interior cabin coating prepared in this application, based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system, exhibits excellent flame retardancy, significantly reducing the maximum smoke density during combustion and significantly prolonging the time to reach maximum smoke density. The coating also maintains excellent impact resistance, extending the coating's durability. Comparative Examples 1-2 show that the flame retardancy of coatings prepared using either melamine phosphate or triphenyl phosphate alone is significantly reduced. Comparative Example 3 demonstrates that the use of nano-titanium dioxide synergizes with melamine phosphate and triphenyl phosphate, significantly enhancing the coating's flame retardancy.

[0054] It can be seen from Examples 6-8 that in the water-based interior cabin coating raw materials based on the nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system, the acrylic resin is pre-grafted with the epoxy resin, which can significantly improve the strength of the coating and better adapt to the mechanical wear requirements of the ship's interior cabin.

[0055] Examples 9 and 10 demonstrate that pre-treatment of the filler surface with acidification followed by silanization promotes uniform dispersion of the filler in the coating system, thereby slowing flame spread, enhancing thermal and oxygen insulation, and improving the flame retardancy of the coating. In Example 11, the filler was not acidified, and performance testing indicates that the filler surface modification effect was significantly reduced.

[0056] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system, characterized in that: The invention comprises the following raw materials in parts by weight: 5-10 parts of nano titanium dioxide, 10-15 parts of phosphorus-nitrogen composite flame retardant, 60-70 parts of waterborne acrylic resin and 5-10 parts of filler; the phosphorus-nitrogen composite flame retardant comprises melamine phosphate and triphenyl phosphate.

2. The water-based interior cabin coating based on nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system according to claim 1, characterized in that: The mass ratio of the melamine phosphate to triphenyl phosphate is 1:(0.8-1.2).

3. The water-based interior cabin coating based on nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system according to claim 1, characterized in that: The acrylate resin is pre-grafted with the epoxy resin. The grafting method comprises the following specific steps: mixing the epoxy resin with a solvent and heating it; then adding methyl methacrylate, butyl acrylate, styrene, acrylamide and an initiator under the protection of nitrogen and reacting them to obtain an epoxy-acrylate grafted resin.

4. The water-based interior cabin coating based on nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system according to claim 3, characterized in that: The epoxy-acrylate graft resin comprises the following raw materials in parts by weight: 30-50 parts of epoxy resin, 20-30 parts of methyl methacrylate, 15-25 parts of butyl acrylate, 8-15 parts of styrene, 1-3 parts of acrylamide, 0.5-0.8 parts of initiator and 40-60 parts of solvent.

5. The water-based interior cabin coating based on nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system according to claim 3, characterized in that: The reaction temperature is 110-120℃.

6. The water-based interior cabin coating based on nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system according to claim 1, characterized in that: The filler is a mixture of multi-walled carbon nanotubes and nano silicon dioxide.

7. The water-based interior cabin coating based on nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system according to claim 6, characterized in that: The filler is pre-surface modified, comprising the following specific steps: The filler is mixed with the acid solution, stirred evenly, filtered, washed and dried to obtain the pretreated filler; the silane coupling agent, water and anhydrous ethanol are mixed and heated, and the pretreated filler is added and mixed to react, filtered, washed with water and dried to obtain the surface-modified filler.

8. The water-based interior cabin coating based on nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system according to claim 6, characterized in that: The mass ratio of the silane coupling agent, the acid solution and the filler is (0.5-0.8): (4-5):

1.

9. The water-based interior cabin coating based on nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system according to claim 6, characterized in that: The acid solution is one of sulfuric acid and nitric acid.

10. A method for preparing a water-based interior cabin coating based on a nano-titanium dioxide and phosphorus-nitrogen synergistic flame retardant system according to any one of claims 1 to 9, characterized in that: The method comprises the following specific steps: mixing nano titanium dioxide, phosphorus-nitrogen composite flame retardant, water-based acrylic resin and filler, and stirring evenly to obtain a water-based interior cabin coating based on a nano titanium dioxide and phosphorus-nitrogen synergistic flame retardant system.

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