A high flash point fire-retardant coating based on heat-resistant phenyl phosphine oxide and a preparation method thereof

Abstract

The application discloses a high-flash-point fireproof coating based on heat-resistant phenyl phosphine oxide and a preparation method thereof, and relates to the technical field of fireproof and flame-retardant coating.The high-flash-point fireproof coating based on heat-resistant phenyl phosphine oxide comprises the following components in parts: heat-resistant phenyl phosphine oxide 10-15 parts, cobalt isooctoate 1-3 parts, methyl ethyl ketone peroxide 0.2-1 part, epoxy resin 140-160 parts and curing agent 90-110 parts; the epoxy resin is epoxy resin 828 or epoxy resin 815 or epoxy resin C 14 H 20 O4.The heat-resistant phenyl phosphine oxide contains phosphorus with flame-retardant effect and has a high thermal decomposition temperature; as a flame-retardant additive, the heat-resistant phenyl phosphine oxide can improve the thermal stability of the coating, thereby avoiding early degradation of the polymer and improving the flash point of the coating, and the flash point is greater than 60 DEG C.

Description

Technical Field

[0001] This invention relates to the field of fire-retardant coating technology, and more specifically to a high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide and its preparation method. Background Technology

[0002] Fire-retardant coatings can be applied to the surface of combustible substrates to reduce the flammability of the coated material, inhibit the rapid spread of fire, and thus improve the fire resistance of the coated material. When applied to the surface of combustible substrates, they can alter the surface combustion characteristics of the material, inhibiting the rapid spread of fire; or they can be applied to building components to improve the fire resistance of the components. Existing fire-retardant coatings are classified according to element type into halogen-based, organophosphorus-based and halogen-phosphorus-based, nitrogen-based, silicon-based, aluminum-magnesium-based, and molybdenum-based coatings, among others.

[0003] Epoxy resin is a common base material for fire-retardant coatings, and its fire-retardant effect mainly comes from flame-retardant additives. The use of flame retardants can significantly delay ignition time, thereby preventing the spread of flames. When organophosphorus and halogen-phosphorus flame retardants are added as phosphorus-containing compounds, they usually produce acidic substances, leading to premature degradation of the polymer and resulting in problems such as a lower flash point of the coating.

[0004] Therefore, there is an urgent need to develop a fire-retardant coating with high thermal stability and high flash point. Summary of the Invention

[0005] 1. The technical problem that the invention aims to solve

[0006] To address the problem that adding phosphorus-containing flame-retardant additives to fire-retardant coatings in existing technologies often produces acidic substances, causing early polymer degradation and thus lowering the flash point of the coating, this invention proposes a high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide and its preparation method. The heat-resistant phenylphosphine oxide contains phosphorus with flame-retardant properties, thereby avoiding early polymer degradation and improving the flash point of the coating.

[0007] 2. Technical Solution

[0008] To achieve the above objectives, the technical solution provided by the present invention is as follows:

[0009] A high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide comprises 10-15 parts heat-resistant phenylphosphine oxide, 1-3 parts cobalt isooctanoate, 0.2-1 parts methyl ethyl ketone peroxide, 140-160 parts epoxy resin, and 90-110 parts curing agent; wherein the epoxy resin is epoxy resin 828, epoxy resin 815, or epoxy resin C. 14 H 20O4. The heat-resistant phenylphosphine oxide contained in it contains phosphorus with flame-retardant properties. It has a high thermal decomposition temperature and, as a flame-retardant additive, can improve the thermal stability of the coating, thereby avoiding early degradation of the polymer and increasing the flash point of the coating to above 60°C.

[0010] A further technical solution involves adding heat-resistant phenylphosphine oxide, which has flame-retardant properties. Its chemical formula is:

[0011] This chemical formula contains phosphorus, which has flame-retardant properties, at the intermediate position, and exhibits high thermal stability.

[0012] A further technical solution, the reaction formula for this heat-resistant phenylphosphine oxide is:

[0013]

[0014] It is prepared by reacting 4-chlorophenyldichlorophosphine with 2-hydroxyethyl methacrylate. The entire reaction process does not require the addition of a catalyst, is easy to control, and has low risk.

[0015] A further technical solution involves the preparation process of heat-resistant phenylphosphine oxide as follows:

[0016] a. Add 0.1-0.3 mol of 2-hydroxyethyl methacrylate and 80-100 ml of ethyl acetate to a 500 ml three-necked flask and stir at 400-600 r / min for 10 min;

[0017] b. In a salt-ice bath, add dropwise an equal amount of 4-chlorophenyldichlorophosphine to 2-hydroxyethyl methacrylate, stir for 10–14 h, and maintain at 0 °C;

[0018] c. Wash three times with ethyl acetate, filter, and obtain heat-resistant phenylphosphine oxide.

[0019] A further technical solution is that the curing agent is one or more of aliphatic amines, aromatic amines, amino polyamides and dicyandiamides. When the curing agent is a mixture of aliphatic amines, aromatic amines, amino polyamides and dicyandiamides, the mass ratio is 1:1:2:2.

[0020] A method for preparing one or more high flash point fire-retardant coatings based on heat-resistant phenylphosphine oxide includes the following steps:

[0021] Step A: Add heat-resistant phenylphosphine oxide to epoxy resin and stir, then add an appropriate amount of dispersant and mix evenly to obtain mixture a;

[0022] Step B: Add cobalt isooctanoate and methyl ethyl ketone peroxide to mixture a, and stir until homogeneous to obtain mixture b;

[0023] Step C: Add the curing agent to mixture b, mix thoroughly, and obtain a high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide.

[0024] A further preparation method is as follows: in step A, the heat-resistant phenylphosphine oxide and epoxy resin are vigorously stirred in a high-speed homogenizer for 30-50 min, the dispersant is toluene or xylene, and the amount of dispersant added is 25% of the amount of epoxy resin. The mixture a is obtained after ultrasonic treatment at 150-170W for 15-25 min; the mixture b is obtained after stirring for 30 min in step B.

[0025] 3. Beneficial effects

[0026] Compared with the prior art, the technical solution provided by this invention has the following advantages:

[0027] The present invention relates to a high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide and its preparation method. The heat-resistant phenylphosphine oxide in the coating contains phosphorus with flame-retardant properties and has a high thermal decomposition temperature. As a flame-retardant additive, it can improve the thermal stability and flash point of the coating, with a flash point greater than 60°C, thereby avoiding early thermal degradation of the polymer. Attached Figure Description

[0028] Figure 1 This invention provides a comparison of the fire-retardant effects of high flash point fire-retardant coatings based on heat-resistant phenylphosphine oxide. Detailed Implementation

[0029] To further understand the content of this invention, the invention will be described in detail below.

[0030] The following detailed description of exemplary embodiments of the invention is taken with reference to the accompanying drawings, which form part of the description and illustrate exemplary embodiments in which the invention may be practiced. While these exemplary embodiments have been described in sufficient detail to enable those skilled in the art to practice the invention, it should be understood that other embodiments may be implemented and various changes may be made to the invention without departing from the spirit and scope thereof. The more detailed description of embodiments of the invention below is not intended to limit the scope of the claimed invention, but is merely illustrative and not restrictive of the description of the features and characteristics of the invention, to suggest the best mode for carrying out the invention, and is sufficient to enable those skilled in the art to practice the invention. Therefore, the scope of the invention is defined only by the appended claims.

[0031] According to the national standard GB / T13690-92 "Classification and Marking of Commonly Used Hazardous Chemicals", liquids with a flash point below 60℃ are classified as hazardous materials, posing safety hazards during transportation and storage, thus limiting the application of paint thinners as a marketable commodity. Therefore, this invention refers to a flash point (closed cup) > 60℃ as a high flash point. The epoxy resin used in this invention is epoxy resin 828 (molecular formula C...). 54 H 60 O9 (flash point 78℃) or epoxy resin 815 (molecular formula C) 25 H 35 ClO5, flash point 192.4℃), epoxy resin (C 14 H 20 In addition to methyl ethyl ketone peroxide (MEK, flash point 118.3℃), other types of epoxy resins with flash points higher than 60℃ can also be used in the fire-retardant coatings of this invention. The addition of MEK is relatively small and has almost no effect on the flash point of the fire-retardant coating. Furthermore, aliphatic amines (flash point greater than 140℃), aromatic amines (flash point greater than 100℃), amino polyamides (flash point 110℃), and dicyandiamides (flash point 92.8℃) all produce fire-retardant coatings with flash points above 60℃, which are high flash point fire-retardant coatings based on heat-resistant phenylphosphine oxide.

[0032] The high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide of the present invention comprises the following components: 10-15 parts heat-resistant phenylphosphine oxide, 1-3 parts cobalt isooctanoate, 0.2-1 parts methyl ethyl ketone peroxide, 140-160 parts epoxy resin, and 90-110 parts curing agent. The epoxy resin serves as the film-forming agent; the heat-resistant phenylphosphine oxide provides flame retardancy; the curing agent cures the epoxy resin into a film; and additives may also be added, including pigments and fillers to adjust color, defoamers to remove air bubbles during stirring, and inorganic fillers to improve strength. First, the amount of heat-resistant phenylphosphine oxide added is determined. In this composition, when the amount of heat-resistant phenylphosphine oxide added exceeds 15 parts, the viscosity of the epoxy resin becomes too high, which is not conducive to subsequent coating.

[0033] Example 1

[0034] This embodiment of the high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide comprises the following components in parts by weight: 10 parts heat-resistant phenylphosphine oxide, 1 part cobalt isooctanoate, 0.2 parts methyl ethyl ketone peroxide, 140 parts epoxy resin, and 90 parts curing agent. The epoxy resin is epoxy resin 828 (molecular formula C...). 54 H 60 O9 (flash point 78℃).

[0035] In this embodiment, the curing agent is an aliphatic amine.

[0036] The heat-resistant phenylphosphine oxide in it has flame-retardant properties, and its chemical formula is:

[0037] This chemical formula contains phosphorus, which has flame-retardant properties, at the intermediate position, and exhibits high thermal stability.

[0038] The reaction formula for this heat-resistant phenylphosphine oxide is:

[0039]

[0040] It is prepared by reacting 4-chlorophenyldichlorophosphineamine with 2-hydroxyethyl methacrylate. The entire reaction process requires no catalyst, is easy to control, and carries low risk. The heat-resistant phenylphosphine oxide prepared under the above reaction conditions has a conversion rate of over 95%, as measured and calculated.

[0041] In this embodiment, the preparation process of heat-resistant phenylphosphine oxide is as follows:

[0042] a. Add 0.1 mol of 2-hydroxyethyl methacrylate and 80 ml of ethyl acetate to a 500 ml three-necked flask and stir at 400 r / min for 10 min;

[0043] b. In a salt-ice bath, add dropwise an equal amount of 4-chlorophenyldichlorophosphine to 2-hydroxyethyl methacrylate, stir for 10 hours, and maintain at 0°C;

[0044] c. Wash three times with ethyl acetate, filter, and obtain heat-resistant phenylphosphine oxide.

[0045] The preparation method of the high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide in this embodiment includes the following steps:

[0046] Step A: Add heat-resistant phenylphosphine oxide to epoxy resin and stir vigorously in a high-speed homogenizer for 30 minutes. Then add toluene at 25% of the amount of epoxy resin and sonicate at 150W for 15 minutes to obtain mixture a.

[0047] Step B: Add cobalt isooctanoate and methyl ethyl ketone peroxide to mixture a, stir for 30 minutes until homogeneous to obtain mixture b;

[0048] Step C: Add the curing agent to mixture b, mix thoroughly, and obtain a high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide.

[0049] Example 2

[0050] The high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide in this embodiment has the same basic components and preparation steps as in Example 1, with the following differences or improvements:

[0051] The high flash point coating of this embodiment comprises the following components in parts by weight: 12 parts heat-resistant phenylphosphine oxide, 2 parts cobalt isooctanoate, 0.5 parts methyl ethyl ketone peroxide, 150 parts epoxy resin, and 100 parts curing agent. The epoxy resin is epoxy resin 815 (molecular formula C). 25 H 35 ClO5 (flash point 192.4℃).

[0052] In this embodiment, the curing agent is an aromatic amine.

[0053] In this embodiment, the preparation process of heat-resistant phenylphosphine oxide is as follows:

[0054] a. Add 0.3 mol of 2-hydroxyethyl methacrylate and 100 ml of ethyl acetate to a 500 ml three-necked flask and stir at 600 r / min for 10 min;

[0055] b. In a salt-ice bath, add dropwise an equal amount of 4-chlorophenyldichlorophosphine to 2-hydroxyethyl methacrylate, stir for 14 hours, and maintain at 0°C;

[0056] c. Wash three times with ethyl acetate, filter, and obtain heat-resistant phenylphosphine oxide.

[0057] In this embodiment, the preparation process of the fire-retardant coating includes the following steps:

[0058] A. Heat-resistant phenylphosphine oxide is added to epoxy resin, and then vigorously stirred in a high-speed homogenizer for 40 minutes. Then, toluene with a dosage of 25% of the epoxy resin dosage is added, and ultrasonic treatment at 170W for 15 minutes is performed to obtain mixture a.

[0059] B. Add cobalt isooctanoate and methyl ethyl ketone peroxide to the mixture and stir for 30 minutes to obtain mixture b;

[0060] C. Add the curing agent to the mixture and mix thoroughly to obtain a high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide.

[0061] Example 3

[0062] The high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide in this embodiment has the same basic components and preparation steps as in Example 1, with the difference or improvement being that it includes the following components in parts by weight: 15 parts heat-resistant phenylphosphine oxide, 3 parts cobalt isooctanoate, 1 part methyl ethyl ketone peroxide, 160 parts epoxy resin, and 110 parts curing agent, wherein the epoxy resin is epoxy resin (C 14 H 20 O4 (flash point is 118.3℃).

[0063] In this embodiment, the curing agent is a mixture of aliphatic amines, aromatic amines, amino polyamides and dicyandiamide, with a mass ratio of 1:1:2:2.

[0064] In this embodiment, the preparation process of heat-resistant phenylphosphine oxide is as follows:

[0065] a. Add 0.2 mol of 2-hydroxyethyl methacrylate and 90 ml of ethyl acetate to a 500 ml three-necked flask and stir at 500 r / min for 10 min;

[0066] b. In a salt-ice bath, add dropwise an equal amount of 4-chlorophenyldichlorophosphine to 2-hydroxyethyl methacrylate, stir for 12 hours, and maintain at 0°C;

[0067] c. Wash three times with ethyl acetate, filter, and obtain heat-resistant phenylphosphine oxide.

[0068] In this embodiment, the preparation process of the fire-retardant coating includes the following steps:

[0069] A. Heat-resistant phenylphosphine oxide is added to epoxy resin, and then vigorously stirred in a high-speed homogenizer for 50 minutes. Then, toluene with a dosage of 25% of the epoxy resin dosage is added, and ultrasonic treatment at 170W for 25 minutes is performed to obtain mixture a.

[0070] B. Add cobalt isooctanoate and methyl ethyl ketone peroxide to mixture a, and stir for 30 minutes to obtain mixture b;

[0071] C. Add the curing agent to mixture b, mix thoroughly, and obtain a high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide.

[0072] Comparative Example 1

[0073] The fire-retardant coating of this comparative example comprises the following components in parts by weight: 160 parts epoxy resin and 110 parts curing agent, wherein the curing agent is an aliphatic amine.

[0074] A curing agent is added to the epoxy resin, and after mixing, an epoxy resin coating is obtained.

[0075] Comparative Example 2

[0076] The fire-retardant coating of this embodiment comprises the following components in parts by weight: 15 parts of phosphorus-containing flame retardant, 160 parts of epoxy resin, and 110 parts of curing agent; the curing agent is an aromatic amine.

[0077] A curing agent is added to the epoxy resin, and after mixing, an epoxy resin coating is obtained.

[0078] Comparative Example 3

[0079] The fire-retardant coating of this embodiment comprises the following components in parts by weight: 15 parts of nitrogen-bromine organic framework material, 160 parts of epoxy resin, and 110 parts of curing agent.

[0080] The curing agent is a mixture of aliphatic amines, aromatic amines, amino polyamides, and dicyandiamide in a mass ratio of 1:1:2:2.

[0081] A curing agent is added to the epoxy resin, and after mixing, an epoxy resin coating is obtained.

[0082] The parameters of fire-retardant coatings prepared in Examples 1-3 were compared with the requirements of national and industry standards for various parameters; maximum heat release rate - ISO 5660-1 / 2 / 3 / 4-2002; decomposition residue ratio - GB / T 27761-2011 Test method for weight loss and residue by thermogravimetric analysis; flash point GB / T 261-2008 Determination of flash point by Binsky-Martin closed cup method; temperature corresponding to maximum mass loss rate (temperature corresponding to maximum mass loss rate: GB / T27761-2011 Test method for weight loss and residue by thermogravimetric analysis).

[0083] The corresponding test results are shown in Table 1:

[0084] Table 1 shows the test results of various parameters of the fire-retardant coatings in Comparative Examples 1-3 and Experimental Examples 1-3.

[0085]

[0086] As shown in Table 1, the maximum heat release rate of the coatings prepared in Examples 1-3 is lower than that of Comparative Examples 1-3. The proportion of decomposition residue and the temperature corresponding to the maximum mass loss rate of the fire-retardant coatings prepared in Examples 1-3 are higher than those of Comparative Examples 1-3. This indicates that the fire-retardant coatings prepared in this invention have superior flame-retardant properties. The flash points of the fire-retardant coatings in Examples 1-3 are all >65℃, meeting the requirements for non-hazardous chemical identification in the "Regulations on the Safety Management of Hazardous Chemicals." They are high flash point fire-retardant coatings, belonging to non-hazardous chemicals, which is beneficial for the storage and transportation of fire-retardant coatings.

[0087] like Figure 1 As shown, the coatings prepared in Examples 1-3 uniformly layered and cover the substrate surface after combustion, thus isolating the fire source, further demonstrating that the coatings of the present invention have flame-retardant effects.

[0088] The present invention and its embodiments have been described above illustratively. This description is not restrictive, and the figures shown are only one embodiment of the present invention; the actual structure is not limited thereto. Therefore, if those skilled in the art are inspired by this description and design similar structures and embodiments without departing from the spirit of the present invention, such designs should fall within the protection scope of the present invention.

Claims

1. A high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide, characterized in that, Its components include 10-15 parts of heat-resistant phenylphosphine oxide, 1-3 parts of cobalt isooctanoate, 0.2-1 parts of methyl ethyl ketone peroxide, 140-160 parts of epoxy resin, and 90-110 parts of curing agent; wherein the epoxy resin is epoxy resin 828, epoxy resin 815, or epoxy resin C. 14 H 20 O4; The heat-resistant phenylphosphine oxide has flame-retardant properties, and its chemical formula is: 。 2. The high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide according to claim 1, characterized in that, The preparation process of the heat-resistant phenylphosphine oxide is as follows: a. Add 0.1~0.3 mol of 2-hydroxyethyl methacrylate and 80~100 ml of ethyl acetate to a 500 ml three-necked flask and stir at 400~600 r / min for 10 min; b. In a salt-ice bath, add dropwise an equal amount of 4-chlorophenyldichlorophosphine to 2-hydroxyethyl methacrylate, stir for 10-14 hours, and maintain at 0°C; c. Wash three times with ethyl acetate, filter, and obtain heat-resistant phenylphosphine oxide.

3. The high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide according to claim 1, characterized in that, The curing agent is one or more of aliphatic amines, aromatic amines, amino polyamides and dicyandiamide; when the curing agent is a mixture of aliphatic amines, aromatic amines, amino polyamides and dicyandiamides, the mass ratio is 1:1:2:

2.

4. A method for preparing a high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide according to any one of claims 1-3, characterized in that, Includes the following steps: Step A: Add heat-resistant phenylphosphine oxide to epoxy resin and stir, then add an appropriate amount of dispersant and mix evenly to obtain mixture a; Step B: Add cobalt isooctanoate and methyl ethyl ketone peroxide to mixture a, and stir until homogeneous to obtain mixture b; Step C: Add the curing agent to mixture b, mix thoroughly, and obtain a high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide.

5. The method for preparing a high flash point fire-retardant coating based on heat-resistant phenylphosphine oxide according to claim 4, characterized in that, In step A, the heat-resistant phenylphosphine oxide and epoxy resin are vigorously stirred in a high-speed homogenizer for 30-50 minutes. The dispersant is toluene or xylene, and the amount of dispersant added is 25% of the amount of epoxy resin. The mixture a is obtained after ultrasonic treatment at 150-170W for 15-25 minutes. In step B, the mixture b is obtained after stirring for 30 minutes.

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