High-efficiency composite flame retardant for thermosetting polymer foaming resin and application of high-efficiency composite flame retardant

Abstract

The flame retardant comprises a component A and a component B. The component A is a low-temperature gas-phase type flame retardant, and the component B comprises a medium-temperature intumescent flame retardant, a high-temperature skeleton type flame retardant, an active hydrogen-containing flame retardant and fluorosiloxane, by weight percentage, the content of the component A in the component B is 1-10%, and the content of the component B in the component B is 1-10%. The flame retardant comprises the following components in percentage by weight: 1-10% of low-temperature gas-phase flame retardant, 10-40% of medium-temperature intumescent flame retardant, 50-80% of high-temperature skeleton flame retardant, 2-8% of active hydrogen-containing flame retardant and 0.3-2% of fluorosiloxane. All the components of the efficient composite flame retardant prepared through fluorosiloxane surface modification achieve efficient gradient synergistic flame retardance in different temperature zones of 150-800 DEG C, the fireproof grade of the foaming material prepared from the efficient composite flame retardant reaches the A2 grade, and the foaming material is excellent in strength, stability, waterproofness, heat preservation performance and the like.

Description

[0001] This application claims priority to Chinese Patent Application No. 202411122533.7, filed on August 15, 2024, entitled "A High-Efficiency Composite Flame Retardant for Thermosetting Polymer Foaming Resin and Its Application", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This invention belongs to the field of new materials technology, specifically relating to a high-efficiency composite flame retardant for thermosetting polymer foam resins and its application. Background Technology

[0003] Thermosetting polymer foam resins are widely used in construction, packaging, and automotive industries due to their advantages such as light weight, heat insulation, and sound absorption. However, their flammability poses a significant fire hazard, making the development of highly efficient flame retardants crucial to improving their flame-retardant properties.

[0004] Currently, there are two main methods for producing flame-retardant thermosetting polymer foam resins: adding flame retardants and modifying the resin matrix. Adding flame retardants is the most direct method. Common flame retardants include halogenated flame retardants, phosphorus-based flame retardants, and inorganic flame retardants. Halogenated flame retardants have high flame-retardant efficiency, but produce a large amount of toxic fumes during combustion, resulting in poor environmental performance. Phosphorus-based flame retardants can reduce the material's burning rate, but they have a certain impact on the material's mechanical properties and thermal stability. Inorganic flame retardants, such as aluminum hydroxide and magnesium hydroxide, are environmentally friendly and non-toxic, but their flame-retardant efficiency is relatively low, requiring large amounts to achieve the desired effect, which significantly increases the material's weight and reduces other properties. Modifying the resin matrix involves introducing flame-retardant groups into the resin molecular chain through chemical methods to improve the material's flame retardancy. However, this method is complex, costly, and may alter the material's original excellent properties.

[0005] Existing flame-retardant technologies share some common problems. First, their flame-retardant effects are not ideal, making it difficult to meet increasingly stringent fire safety standards. Second, the addition of flame retardants often reduces the mechanical properties of materials, such as tensile strength and elastic modulus. Third, some flame retardants have poor compatibility with resins, easily leading to poor material processing performance, affecting material molding quality and production efficiency. Furthermore, from an environmental perspective, some flame retardants release toxic and harmful gases when burning, posing a threat to the environment and human health, which is inconsistent with the trend of green development.

[0006] In summary, existing thermosetting polymer foam resin flame retardant technologies suffer from low flame retardant efficiency, decreased material performance, and poor environmental performance, making it difficult to meet market demands for high-performance, environmentally friendly flame retardant materials. Therefore, developing a high-efficiency, environmentally friendly composite flame retardant with good resin compatibility is of great significance. Summary of the Invention

[0007] The present invention aims to provide a high-efficiency, environmentally friendly composite flame retardant that is compatible with thermosetting polymer foaming resins, in order to overcome the problems of low flame retardant efficiency, decreased material performance and poor environmental performance of existing flame retardants.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is: a high-efficiency composite flame retardant for thermosetting polymer foaming resin, wherein the flame retardant comprises component A and component B, wherein component A is a low-temperature gas-phase flame retardant, and component B comprises a medium-temperature intumescent flame retardant, a high-temperature skeleton flame retardant, an active hydrogen-containing flame retardant, and a fluorosiloxane, and the weight percentage of each component is as follows:

[0009]

[0010] The active hydrogen flame retardant is a compound represented by Formula 1; or the active hydrogen flame retardant is one or both of hexa(4-DOPO hydroxymethylphenoxy)-cyclotriphosphazene and hexa(4-aminophenoxy)cyclotriphosphazene.

[0011]

[0012] R1 in Formula 1 is selected from alkyl, phenyl, and biphenyl groups having 1-5 carbon atoms.

[0013] The alkyl group having 1-5 carbon atoms is selected from: methyl, ethyl, tert-butyl.

[0014] Preferably, the active hydrogen-containing flame retardant is any one of the compounds shown in the following structures:

[0015]

[0016] Preferably, the low-temperature gas-phase flame retardant is one or more of chlorinated paraffin, tris(2-chloropropyl) phosphate, tris(β-chloroethyl) phosphate, dimethyl methylphosphonate, and diethyl ethylphosphonate.

[0017] Preferably, the medium-temperature intumescent flame retardant is one or more of the following: expandable graphite, graphene oxide, aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine, melamine cyanurate, melamine phosphate, aluminum diethylphosphonate, poly(2,6-dibromophenyl ether), decabromodiphenyl ether, decabromodiphenyl ethane, brominated polyethylene, borax decahydrate, and zinc borate.

[0018] Preferably, the high-temperature skeleton type flame retardant is one or more of the following: silicon dioxide, lead dioxide, antimony trioxide, ferric oxide, calcium carbonate, barium borate, barium sulfate, low-temperature glass powder, low-temperature ceramic powder, and manufactured sand.

[0019] Preferably, the fluorosiloxane is a hydroxyl-terminated fluorosiloxane with the following structure:

[0020]

[0021] Among them, the degree of polymerization n is greater than 5000.

[0022] Preferably, the preparation method of component B is as follows: A medium-temperature intumescent flame retardant and a high-temperature skeleton flame retardant are added to a mixing tank equipped with a double-layer stirrer according to weight percentage. The mixture is stirred and mixed at room temperature for 30-60 minutes. Then, a mixture containing an active hydrogen flame retardant, alcohol, and fluorosiloxane is sprayed at a uniform speed under stirring for 30-60 minutes. After spraying, stirring is continued for another 30-60 minutes. Then, the alcohol is recovered by vacuum distillation. When 90-95% of the alcohol has been recovered, the product is discharged to obtain component B.

[0023] Preferably, the mass percentages of the components in the mixture are as follows: 0.3-2% fluorosiloxane, 90-97.7% industrial alcohol, and 2-8% active hydrogen flame retardant.

[0024] The present invention relates to a high-efficiency composite flame retardant applied in thermosetting polymer resin foaming, including phenolic resin foaming, polyurethane resin foaming and synthetic resin foaming.

[0025] The active hydrogen in the active hydrogen-containing flame retardant (Formula 1) of this invention is hydroxyl active hydrogen.

[0026] Compared with the prior art, the present invention has the following advantages and effects:

[0027] 1. The high-efficiency composite flame retardant provided by this invention includes low-temperature gas-phase flame retardants, medium-temperature intumescent flame retardants, high-temperature skeleton flame retardants, active hydrogen-containing flame retardants, and fluorosiloxanes. The effective decomposition range of the decomposition products of this flame retardant is 150-800℃. Among them, the decomposition temperature of the low-temperature gas-phase flame retardant is below 250℃, the decomposition temperature of the medium-temperature intumescent flame retardant is 250-550℃, and the tolerance temperature of the high-temperature skeleton flame retardant is above 550℃, realizing the gradient synergistic flame retardancy of various flame retardants in different temperature ranges. The flame retardant mechanism of thermosetting polymer foam materials during combustion is as follows: ① The low-temperature gas-phase flame retardant decomposes upon heating. During the decomposition process, it absorbs a large amount of heat released by the free radical chain reaction of the foam material and generates a large amount of inert gas and water vapor. This lowers the surface temperature of the material's combustion and dilutes the concentration of combustible gases, making it difficult for the surface temperature and the concentration of combustible gases to reach the ignition point. ② The synergistic effect of the intumescent flame retardant in the medium-temperature zone: it expands upon contact with fire, continuously forming a fire-retardant porous insulating layer that can insulate against heat and oxygen, suppress smoke, and weaken and gradually terminate free radical chain reactions. ③ The skeletal flame retardant in the high-temperature zone is mostly an inorganic filler with a large specific heat capacity. Through its heat storage and heat conduction effects, it makes it difficult for the material to reach its decomposition temperature when exposed to fire. At the same time, it condenses with the decomposition residues of the flame retardants in the medium and low-temperature zones to form the material skeleton, enhancing the fire resistance of the material.

[0028] 2. The high-efficiency composite flame retardant provided by the present invention includes a thermal expansion type flame retardant and a high-temperature skeleton type flame retardant, which are surface modified by hydroxyl-terminated fluorosiloxanes. Since the hydroxyl-terminated fluorosiloxanes have a flexible hydroxyl-terminated structure, the fluorosiloxanes will be uniformly adsorbed on the surface of the flame retardant and are not easy to migrate. At the same time, the fluorosiloxanes also endow the solid flame retardant with low surface free energy. This enables the following properties to be achieved: ① Improved compatibility between solid flame retardants and polymer materials, allowing solid flame retardants to be uniformly dispersed in polymer materials, while liquid flame retardants can slowly migrate into fluorosiloxanes, preventing their migration and loss, thus improving the stability and lifespan of the flame retardants; ② Fluorosiloxanes maintain the stability of the foam material, improving its water resistance and mechanical properties; ③ The encapsulation of fluorosiloxanes significantly reduces the decomposition rate of the flame retardant, increases the amount of carbon deposits on the foam material after heating, and improves the flame retardant's flame retardant duration; ④ After high-temperature decomposition, fluorosiloxanes cover the surface of the residual carbon with a layer of flake-like silica, hindering the transfer of matter and heat; ⑤ Solid flame retardants modified with fluorosiloxanes are easily migrated to the surface of the foam material at high temperatures, thereby improving the flame retardant effect; ⑥ The encapsulation of solid flame retardants with fluorosiloxanes can prevent powdered flame retardants such as polyphosphates and aluminum hydroxide from reacting with acidic or alkaline substances in the environment, thus improving the lifespan of the flame retardants.

[0029] 3. An active hydrogen flame retardant containing hydroxyl active hydrogen and phosphorus (referring to the active hydrogen flame retardant with the structure shown in Formula 1) is used. The phosphorus-containing groups decompose upon heating to generate phosphoric acid, polymetaphosphoric acid, etc., which cover the material surface to form a glassy protective layer, isolating oxygen. The phosphide further vaporizes to generate PO· free radicals, capturing H· / OH· free radicals in the combustion chain reaction and interrupting the combustion chain. The hydroxyl active hydrogen undergoes a condensation reaction with the active groups in the resin matrix, promoting cross-linking into char. At high temperatures, phosphorus catalyzes the graphitization of the char layer, forming a dense, high-strength expanded char layer, effectively blocking the diffusion of heat and combustible gases. Simultaneously, the hydroxyl groups in the molecule can prevent the material from being oxidized by oxidants, including oxygen, protecting the material itself. The -Si-O- chains of the terminal hydroxyl fluorosiloxane form hydrogen bonds with the hydroxyl groups of the active hydrogen flame retardant, fixing the flame retardant's position and reducing migration. The SiO2 generated by the decomposition of the fluorosiloxane at high temperatures covers the char layer surface, enhancing the barrier effect.

[0030] 4. Phosphate ester type flame retardants containing active hydrogen, such as hexa(4-DOPOhydroxymethylphenoxy)-cyclotriphosphazene and hexa(4-aminophenoxy)cyclotriphosphazene, are used. This type of flame retardant reacts during the mixing process with thermosetting polymer resin, preventing the migration of liquid gaseous flame retardants in the molded material and ensuring long-term fire resistance. At the same time, it can form a continuous, uniform and dense expanded char layer during heating, improving the flame retardant effect.

[0031] 5. The high-efficiency composite flame retardant of the present invention is applied to thermosetting polymer foam materials to achieve temperature gradient synergistic flame retardancy, thereby improving the fire rating of the foam material from Class B to Class A, without significantly affecting the original excellent performance of the material. Both the energy-saving effect and the fire resistance performance can meet the current urgent needs of the industry and have broad prospects for promotion and application. Attached Figure Description

[0032] Figure 1 This is the NMR spectrum of the active hydrogen-containing flame retardant 1 described in this invention. Detailed Implementation

[0033] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0034] Preparation Example 1

[0035] Synthesis of active hydrogen flame retardant 1:

[0036]

[0037] A1: Add 20 g of starting material 1, 12.31 g of starting material 2, 38.87 g of cesium carbonate, and 300 mL of tert-amyl alcohol to a nitrogen-filled reaction flask. Replace the air in the reaction system three times with nitrogen. Under nitrogen protection, add 2.73 g of Pd(DBA)₂ and 1.56 g of triphenylphosphine. Heat to 100 °C and react for 6 hours under nitrogen protection. After the reaction is complete, cool to room temperature, add 150 mL of water, extract three times with ethyl acetate (150 mL each time), wash once with 300 mL of saturated brine, and then dry with 15 g of anhydrous sodium sulfate. Finally, extract 15.19 g of intermediate 1 by column chromatography (ethyl acetate and petroleum ether as eluents). The purity was 99.8% as determined by liquid chromatography and 441 M / Z+1 by mass spectrometry.

[0038] A2: 15.19 g of intermediate 1, 7.07 g of pentanoic anhydride, and 200 mL of dried toluene were added to a nitrogen-filled reaction flask. Then, 13.67 g of starting material 3 was added, and the reaction was carried out at 50 °C for 6 h. The reaction system was washed twice with 2 mol / L sodium hydroxide solution, and then twice with 2 mol / L hydrochloric acid. The organic phase was washed with 300 mL of saturated brine, dried over 15 g of anhydrous sodium sulfate, and the solvent was evaporated. Finally, 23.12 g of flame retardant 1 containing active hydrogen was obtained by column chromatography (using ethyl acetate and petroleum ether as eluents). The purity was 99.8% as determined by liquid chromatography, and the mass spectrometry result was M / Z+1:783.

[0039] Structural characterization tests were performed on the product (containing active hydrogen flame retardant 1): NMR spectroscopy was used. Figure 1 As shown, the mass spectrometry data is described above.

[0040] Preparation Example 2

[0041] The synthesis of the active hydrogen flame retardant 2 was carried out by referring to the synthesis method of Preparation Example 1, except that raw material 2 was replaced with... The rest was the same as in Preparation Example 1, and the structure was characterized by mass spectrometry M / Z+1: 845.

[0042] Preparation Example 3

[0043] The synthesis of the active hydrogen flame retardant 3 was carried out by referring to the synthesis method of Preparation Example 1, except that raw material 2 was replaced with... The rest was the same as in Preparation Example 1, and the structure was characterized by mass spectrometry M / Z+1: 921.

[0044] Preparation Example 4

[0045] The synthesis of the active hydrogen flame retardant 3 was carried out by referring to the synthesis method of Preparation Example 1, except that raw material 2 was replaced with... The rest was the same as in Preparation Example 1, and the structure was characterized by mass spectrometry M / Z+1: 797.

[0046] Example 1

[0047] A high-efficiency composite flame retardant for thermosetting polymer foam resins includes component A and component B. Component A is a low-temperature gas-phase flame retardant, and the preparation method of component B includes the following steps:

[0048] Add 9g of expandable graphite, 1g of graphene oxide, 10g of melamine, 10g of ammonium polyphosphate, 10g of decabromodiphenyl ethane, 60g of lead dioxide, and 60g of barium sulfate to a mixing tank equipped with a double-layer stirrer. Stir at room temperature for 30 minutes to obtain a mixture. Then, while stirring, spray a mixture of 8g of hexa(4-DOPOhydroxymethylphenoxy)-cyclotriphosphazene, 90g of industrial alcohol, and 2g of hydroxyl-terminated fluorosiloxane at a uniform speed into the above mixture for 30 minutes. After spraying, continue stirring for 30 minutes. Then, when 90% of the alcohol is recovered by vacuum distillation, the product is obtained as component B.

[0049] Example 2

[0050] A high-efficiency composite flame retardant for thermosetting polymer foam resins includes component A and component B. Component A is a low-temperature gas-phase flame retardant, and the preparation method of component B includes the following steps:

[0051] Add 9g of expandable graphite, 1g of graphene oxide, 10g of aluminum hydroxide, 10g of melamine phosphate, 10g of decabromodiphenyl ether, 60g of antimony trioxide, and 60g of ferric oxide to a mixing tank equipped with a double-layer stirrer. Stir and mix at room temperature for 60 minutes. Then, while stirring, spray a mixture of 3.4g of hexa(4-aminophenoxy)cyclotriphosphazene, 96.09g of industrial alcohol, and 0.51g of hydroxyl-terminated fluorosiloxane at a uniform speed into the above mixture for 30 minutes. After spraying, continue stirring for 60 minutes. Then, when the 95% alcohol is recovered by vacuum distillation, the product is obtained as component B.

[0052] Example 3

[0053] A high-efficiency composite flame retardant for thermosetting polymer foam resins includes component A and component B. Component A is a low-temperature gas-phase flame retardant, and the preparation method of component B includes the following steps:

[0054] Add 10g magnesium hydroxide, 10g ammonium polyphosphate, 10g melamine cyanurate, 10g brominated polyethylene, and 120g silica to a mixing tank with a double-layer stirrer and stir for 30 minutes at room temperature. Then, while stirring, spray a mixture of 8g hexa(4-DOPO hydroxymethylphenoxy)-cyclotriphosphazene, 90g industrial alcohol, and 2g hydroxyl-terminated fluorosiloxane at a uniform speed into the above mixture for 30 minutes. After spraying, continue stirring for 30 minutes. Then, when 90% alcohol is recovered by vacuum distillation, the product is obtained as component B.

[0055] Example 4

[0056] A high-efficiency composite flame retardant for thermosetting polymer foam resins includes component A and component B. Component A is a low-temperature gas-phase flame retardant, and the preparation method of component B includes the following steps:

[0057] Add 9g of expandable graphite, 1g of graphene oxide, 10g of melamine phosphate, 10g of poly(2,6-dibromophenyl ether), 10g of aluminum diethylphosphonate, and 120g of silica to a mixing tank equipped with a double-layer stirrer. Stir and mix at room temperature for 30 minutes. Then, while stirring, spray a mixture of 8g of hexa(4-DOPOhydroxymethylphenoxy)-cyclotriphosphazene, 90g of industrial alcohol, and 2g of hydroxyl-terminated fluorosiloxane at a uniform speed into the above mixture for 30 minutes. After spraying, continue stirring for another 30 minutes. Then, when 90% of the alcohol is recovered by vacuum distillation, the product is obtained as component B.

[0058] Example 5

[0059] A high-efficiency composite flame retardant for thermosetting polymer foam resins includes component A and component B. Component A is a low-temperature gas-phase flame retardant, and the preparation method of component B includes the following steps:

[0060] Add 10g of melamine cyanurate, 10g of ammonium polyphosphate, 10g of decabromodiphenyl ether, 10g of aluminum hydroxide, 60g of ferric oxide, and 60g of calcium carbonate to a mixing tank equipped with a double-layer stirrer. Stir and mix at room temperature for 30 minutes. Then, while stirring, spray a mixture of 4g of hexa(4-DOPOhydroxymethylphenoxy)-cyclotriphosphazene and 2g of hexa(4-aminophenoxy)-cyclotriphosphazene with 93g of industrial alcohol and 1g of hydroxyl-terminated fluorosiloxane at a uniform speed into the above mixture for 30 minutes. After spraying, continue stirring for 30 minutes. Then, when 90% of the alcohol is recovered by vacuum distillation, the product is obtained as component B.

[0061] Example 6

[0062] A high-efficiency composite flame retardant for thermosetting polymer foam resins includes component A and component B. Component A is a low-temperature gas-phase flame retardant, and the preparation method of component B includes the following steps:

[0063] Add 9g of expandable graphite, 1g of graphene oxide, 10g of magnesium hydroxide, 10g of brominated polyethylene, 10g of melamine, 60g of lead dioxide, and 60g of barium sulfate to a mixing tank equipped with a double-layer stirrer. Stir and mix at room temperature for 30 minutes. Then, while stirring, spray a mixture of 8g of hexa(4-DOPOhydroxymethylphenoxy)-cyclotriphosphazene, 90g of industrial alcohol, and 2g of hydroxyl-terminated fluorosiloxane at a uniform speed into the above mixture for 30 minutes. After spraying, continue stirring for 30 minutes. Then, when 90% of the alcohol is recovered by vacuum distillation, the product is obtained as component B.

[0064] Example 7

[0065] A high-efficiency composite flame retardant for thermosetting polymer foam resins includes component A and component B. Component A is a low-temperature gas-phase flame retardant, and the preparation method of component B includes the following steps:

[0066] Add 9g of expandable graphite, 1g of graphene oxide, 10g of melamine, 10g of ammonium polyphosphate, 10g of decabromodiphenyl ethane, 60g of lead dioxide, and 60g of barium sulfate to a mixing tank equipped with a double-layer stirrer. Stir at room temperature for 30 minutes to obtain a mixture. Then, while stirring, spray a mixture of 8g of active hydrogen flame retardant 1 (the active hydrogen flame retardant 1 prepared in Preparation Example 1), 90g of industrial alcohol, and 2g of hydroxyl-terminated fluorosiloxane at a uniform speed into the above mixture for 30 minutes. After spraying, continue stirring for 30 minutes. Then, when 90% of the alcohol is recovered by vacuum distillation, the product is obtained as component B.

[0067] Examples 8-10

[0068] In Examples 8-10, a high-efficiency composite flame retardant for thermosetting polymer foam resin was prepared sequentially. The preparation method was the same as in Example 7, except that the active hydrogen flame retardant 1 was replaced sequentially with the active hydrogen flame retardant 2-active hydrogen flame retardant 4 prepared in Examples 2-4. The rest remained the same as in Example 7.

[0069] Comparative Example 1

[0070] A high-efficiency composite flame retardant for thermosetting polymer foam resin, prepared according to the method of Embodiment 7, except that the active hydrogen-containing flame retardant is replaced with... The rest remains the same as in Example 7.

[0071] Comparative Example 2

[0072] A high-efficiency composite flame retardant for thermosetting polymer foam resin, prepared according to the method of Embodiment 7, except that the active hydrogen-containing flame retardant is replaced with... The rest remains the same as in Example 7.

[0073] Comparative Example 3

[0074] A high-efficiency composite flame retardant for thermosetting polymer foam resin is prepared according to the method of Example 7, except that the active hydrogen flame retardant is replaced with flame retardant DOPO, and the rest is the same as in Example 7.

[0075] Application Example 1

[0076] A polymeric composite foam material comprises a polymeric foam material and a composite flame retardant. The polymeric foam material is a polyurethane foam material, and the composite flame retardant includes component B, which is the high-efficiency flame retardant of Example 1, and component A, which is chlorinated paraffin. The mass ratio of the polyurethane foam material, flame retardant component A, and component B is 30:2:68.

[0077] The polyurethane foam material is composed of the following raw materials in the following mass ratio: 100 parts polyether polyol, 4 parts triethylenediamine A33, 22 parts foaming agent 141b, 4 parts silicone oil 6950, and 160 parts isocyanate MDI.

[0078] The polyurethane composite foam material is prepared as follows: Polyether polyol, triethylenediamine, blowing agent 141b, silicone oil, flame retardant component A, and 2 / 5 of the composite flame retardant component B are mixed evenly. Simultaneously, isocyanate MDI and 3 / 5 of the composite flame retardant component B are mixed evenly. Then, the two mixtures are stirred for 15 seconds using a high-speed disperser, poured into a mold, and sealed for 10 minutes. Finally, the polyurethane foam material is cured at 50°C for 4 hours.

[0079] Application Example 2

[0080] A polymeric composite foam material comprises a polymeric foam material and a composite flame retardant. The polymeric foam material is a polyurethane foam material, and the composite flame retardant includes component B, which is the high-efficiency flame retardant of Example 2, and component A, which is tris(2-chloropropyl) phosphate. The mass ratio of the polyurethane foam material, flame retardant component A, and component B is 26.5:1.5:72.

[0081] The composition and preparation of the polyurethane composite foam material are the same as in Application Example 1.

[0082] Application Example 3

[0083] A polymeric composite foam material comprises a polymeric foam material and a composite flame retardant. The polymeric foam material is a polyurethane foam material, and the composite flame retardant includes component B, which is the high-efficiency flame retardant of Example 3, and component A, which is tris(β-chloroethyl) phosphate. The mass ratio of the polyurethane foam material, flame retardant component A, and component B is 23:1:76.

[0084] The composition and preparation of the polyurethane composite foam material are the same as in Application Example 1.

[0085] Application Example 4

[0086] A polymeric composite foam material comprises a polymeric foam material and a composite flame retardant. The polymeric foam material is a phenolic foam material, and the composite flame retardant includes component B, which is the high-efficiency flame retardant of Example 4, and component A, which is dimethyl methylphosphonate. The mass ratio of the phenolic foam material, flame retardant component A, and component B is 30:2:68.

[0087] The phenolic foam material is composed of the following raw materials in the following mass ratio: 100 parts of methyl phenolic resin, 4 parts of silicone oil, 8 parts of n-pentane and 8 parts of p-toluenesulfonic acid.

[0088] The preparation of polymer composite foam material is as follows: Weigh each raw material according to the above weight ratio, mix the first-stage phenolic resin, organosilicon oil, n-pentane, p-toluenesulfonic acid, flame retardant component A and flame retardant component B evenly at high speed, and then inject them into the mold. Expand and foam at 60°C, and then cure and demold to obtain the composite foam material.

[0089] Application Example 5

[0090] A polymeric composite foam material comprises a polymeric foam material and a composite flame retardant. The polymeric foam material is a phenolic foam material, and the composite flame retardant includes component B, which is the high-efficiency flame retardant of Example 5, and component A, which is diethyl ethylphosphonate. The mass ratio of the phenolic foam material, flame retardant component A, and component B is 26.5:1.5:72.

[0091] The composition and preparation of the phenolic composite foam material are the same as in Application Example 4.

[0092] Application Example 6

[0093] A polymeric composite foam material comprises a polymeric foam material and a composite flame retardant. The polymeric foam material is a phenolic foam material, and the composite flame retardant includes component B, which is the high-efficiency flame retardant of Example 6, and component A, which consists of chlorinated paraffin, tris(2-chloropropyl) phosphate, and dimethyl methylphosphonate (mass ratio 1:2:2). The mass ratio of the phenolic foam material, flame retardant component A, and component B is 23:1:76.

[0094] The composition and preparation of the phenolic composite foam material are the same as in Application Example 4.

[0095] Application Example 7

[0096] A polymeric composite foam material comprises a polymeric foam material and a composite flame retardant. The polymeric foam material is a polyurethane foam material, and the composite flame retardant includes component B, which is the high-efficiency flame retardant of Example 7, and component A, which is chlorinated paraffin. The mass ratio of the polyurethane foam material, flame retardant component A, and component B is 30:2:68.

[0097] The polyurethane foam material is composed of the following raw materials in the following mass ratio: 100 parts polyether polyol, 4 parts triethylenediamine A33, 22 parts foaming agent 141b, 4 parts silicone oil 6950, and 160 parts isocyanate MDI.

[0098] The polyurethane composite foam material is prepared as follows: Polyether polyol, triethylenediamine, blowing agent 141b, silicone oil, flame retardant component A, and 2 / 5 of the composite flame retardant component B are mixed evenly. Simultaneously, isocyanate MDI and 3 / 5 of the composite flame retardant component B are mixed evenly. Then, the two mixtures are stirred for 15 seconds using a high-speed disperser, poured into a mold, and sealed for 10 minutes. Finally, the polyurethane foam material is cured at 50°C for 4 hours.

[0099] Application Examples 8-10

[0100] In Application Examples 8-10, a polymer composite foam material was prepared by referring to the preparation method of Application Example 7, except that component B in the composite flame retardant was replaced with the high-efficiency flame retardant prepared in Examples 8-10, and the rest was the same as in Application Example 7.

[0101] Comparative Application Examples 1-3

[0102] In Comparative Application Examples 1-3, a polymer composite foam material was prepared. Referring to the preparation method of Application Example 7, component B in the composite flame retardant was replaced with the high-efficiency flame retardant prepared in Comparative Examples 1-3. The rest was the same as in Application Example 7.

[0103] Performance evaluation experiment: The polymer composite foam materials obtained from Application Examples 1-6 above were subjected to performance tests, and the test results are shown in Table 1. As can be seen from the table, all polymer composite foam materials achieved a flame retardant rating of A2, and all other indicators met the requirements.

[0104] Table 1. Performance evaluation table for the two materials.

[0105]

[0106] Note: *Flame retardancy testing is conducted and judged according to the methods specified in the national standard GB8624-2012. The A2 grade of non-flammability test is determined by mass loss ≤50%, furnace temperature rise ≤50℃, and continuous burning time ≤20s.

[0107] As shown in the table, the overall density of polyurethane and phenolic composite foam materials made with the flame retardant obtained in this invention is ≥90 kg / m³. 3 It has a compressive strength ≥0.1MPa, good mechanical strength, and can pass the non-combustibility test of GB 8624-2012 "Classification of Combustion Performance of Building Materials and Products". The mass loss is less than 50%, the temperature rise in the furnace is less than 50℃, and the open flame time is less than 20 seconds.

[0108] The polymer composite foam materials obtained from Application Examples 7-10 and Comparative Application Examples 1-2 were subjected to performance tests (test methods are as described above), and the test results are shown in Table 2. All polymer composite foam materials achieved a flame retardancy rating of A2, and all other indicators met the requirements.

[0109] Table 2.

[0110]

[0111]

[0112] Application Examples 7 to 10 (using the flame retardant optimized by this invention) showed superior performance compared to Application Example 1. Improved thermal conductivity indicates enhanced material insulation efficiency; reduced water absorption reflects significant hydrophobic modification effects; and increased compressive strength indicates a denser and more robust material structure. Regarding combustion performance, all application examples achieved zero open flame and better temperature rise control, verifying the synergistic effect of the flame retardant system.

[0113] Compared to comparative application examples 1-3 using flame retardants not specified in this invention, application examples 7-10 exhibit overwhelming advantages: lighter bulk density, simultaneous improvement in thermal insulation and mechanical properties, stricter control over water absorption, and significantly enhanced dimensional stability at both high and low temperatures. Particularly in the area of ​​combustion safety, the sustained open flame and higher temperature rise observed in the comparative group highlight the breakthrough progress of this invention in flame retardant molecular design—achieving a simultaneous leap in fire safety and physical properties through multiple synergistic mechanisms. This systematic advantage verifies the profound optimization effect of the gradient flame-retardant structure of this invention on the comprehensive performance of building energy-saving materials.

[0114] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A high-efficiency composite flame retardant for thermosetting polymer foam resins, characterized in that, The flame retardant comprises component A and component B. Component A is a low-temperature gas-phase flame retardant, and component B comprises a medium-temperature intumescent flame retardant, a high-temperature skeleton flame retardant, an active hydrogen-containing flame retardant, and a fluorosiloxane. The weight percentage of each component is as follows: The active hydrogen flame retardant is a compound represented by Formula 1; or the active hydrogen flame retardant is one or both of hexa(4-DOPO hydroxymethylphenoxy)-cyclotriphosphazene and hexa(4-aminophenoxy)cyclotriphosphazene. R1 in Formula 1 is selected from alkyl, phenyl, and biphenyl groups having 1-5 carbon atoms.

2. The high-efficiency composite flame retardant according to claim 1, characterized in that, The alkyl group having 1-5 carbon atoms is selected from: methyl, ethyl, tert-butyl.

3. The high-efficiency composite flame retardant according to claim 1, characterized in that, The active hydrogen-containing flame retardant is any one of the compounds shown in the following structures:

4. The high-efficiency composite flame retardant according to claim 1, characterized in that, The low-temperature gas-phase flame retardant is one or more of chlorinated paraffin, tris(2-chloropropyl) phosphate, tris(β-chloroethyl) phosphate, dimethyl methylphosphonate, and diethyl ethylphosphonate.

5. The high-efficiency composite flame retardant according to claim 1, characterized in that, The medium-temperature intumescent flame retardant is one or more of the following: expandable graphite, graphene oxide, aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine, melamine cyanurate, melamine phosphate, aluminum diethylphosphonate, poly(2,6-dibromophenyl ether), decabromodiphenyl ether, decabromodiphenyl ethane, brominated polyethylene, borax decahydrate, and zinc borate.

6. The high-efficiency composite flame retardant according to claim 1, characterized in that, The high-temperature skeleton type flame retardant is one or more of the following: silicon dioxide, lead dioxide, antimony trioxide, ferric oxide, calcium carbonate, barium borate, barium sulfate, low-temperature glass powder, low-temperature ceramic powder, and manufactured sand.

7. The high-efficiency composite flame retardant according to claim 1, characterized in that, The fluorosiloxane is a fluorosiloxane with terminal hydroxyl groups, and its structure is as follows: Among them, the degree of polymerization n is greater than 5000.

8. The high-efficiency composite flame retardant according to claim 1, characterized in that, The preparation method of component B is as follows: A medium-temperature intumescent flame retardant and a high-temperature skeleton flame retardant are added to a mixing tank equipped with a double-layer stirrer according to weight percentage. The mixture is stirred and mixed at room temperature for 30-60 minutes. Then, a mixture containing active hydrogen flame retardant, alcohol, and fluorosiloxane is sprayed at a uniform speed under stirring for 30-60 minutes. After spraying, stirring is continued for another 30-60 minutes. Then, the alcohol is recovered by vacuum distillation. When 90-95% of the alcohol has been recovered, the product is discharged to obtain component B.

9. The high-efficiency composite flame retardant according to claim 8, characterized in that, The mass percentages of the components in the mixture are as follows: 0.3-2% fluorosiloxane, 90-97.7% industrial alcohol, and 2-8% active hydrogen flame retardant.

10. The application of the high-efficiency composite flame retardant as described in claim 1, characterized in that, It is used in thermosetting polymer foaming, including phenolic resin foaming, polyurethane resin foaming, melamine resin foaming and its synthetic resin foaming.

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