Anti-aging thermal and sound insulation composite material and preparation method thereof

Abstract

The application discloses an anti-aging heat-insulating and sound-insulating composite material and a preparation method thereof, and belongs to the technical field of high polymer materials. The anti-aging heat-insulating and sound-insulating composite material comprises the following raw materials in parts by weight: 10-20 parts of seaweed mud, 10-15 parts of ceramic hollow microbeads, 6-10 parts of ceramic fiber, 10-15 parts of environment-friendly sound-absorbing cotton, 2-4 parts of anti-aging agent, 4-6 parts of modified flame retardant, 60-80 parts of modified waterproof agent and 150-200 parts of DMF; the anti-aging heat-insulating and sound-insulating composite material prepared by the application has excellent flame-retardant performance and waterproof performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to an anti-aging heat and sound insulation composite material and a preparation method thereof. BACKGROUND

[0002] With the increasing demand for high-performance materials in modern industry and construction, the application range of heat and sound insulation composite materials is increasingly wide. However, traditional heat and sound insulation materials have significant shortcomings in terms of flame retardant performance and waterproof performance, which limits their use in complex environments. For example, although polyurethane materials have good mechanical properties and heat insulation effect, they are easily flammable at high temperatures and produce toxic gases during combustion. In addition, traditional composite materials are prone to performance degradation when subjected to mechanical damage or long-term exposure to humid environments. In recent years, significant progress has been made in the application research of composite materials in the field of heat and sound insulation. Composite materials can achieve heat and sound insulation effects by combining the excellent properties of different materials. For example, PVC / NBR / OMMT composite materials significantly improve the heat and sound insulation performance of the material by adding organic montmorillonite. In addition, by introducing nano materials such as titanium dioxide microspheres or SiO2 hollow microspheres modified by silane coupling agent into the composite material, the anti-aging performance and heat and sound insulation effect of the material can be further enhanced. However, existing composite materials still face some challenges in practical application, therefore, developing a composite material with good anti-aging performance, heat and sound insulation performance is of great significance to meet the needs of modern industry and construction.

[0003] The Chinese invention patent with publication number CN119285887A discloses an environmentally friendly building energy-saving sound insulation material and a preparation method thereof, the environmentally friendly building energy-saving sound insulation material comprises the following raw materials by weight: modified polyether polyol 100-120 parts, isocyanate 140-150 parts, modified hollow glass microbeads 8-12 parts, modified sericite 5-8 parts, ammonium polyphosphate 3-5 parts, foaming agent 2-4 parts, stabilizer 1-3 parts, catalyst 0.1-0.5 parts, the environmentally friendly building energy-saving sound insulation material has excellent heat insulation and flame retardant performance, but the waterproof performance is poor. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application aims to provide an anti-aging heat and sound insulation composite material and a preparation method thereof.

[0005] To achieve the above-mentioned purpose, the present application realizes the following technical scheme:

[0006] An anti-aging heat and sound insulation composite material comprises the following raw materials by weight:

[0007] Seaweed mud 10-20 parts, ceramic hollow microsphere 10-15 parts, ceramic fiber 6-10 parts, environmentally friendly sound-absorbing cotton 10-15 parts, antioxidant 2-4 parts, modified flame retardant 4-6 parts, modified waterproof agent 60-80 parts, DMF 150-200 parts;

[0008] The modified flame retardant is prepared by the following method:

[0009] S1: 2-benzyloxy-5-hydroxybenzaldehyde is reacted with 4,4'-diamino diphenyl ether under the action of a catalyst of glacial acetic acid to obtain an intermediate 1;

[0010] S2: p-iodophenol is reacted with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide under the action of tetrakis(triphenylphosphine)palladium to generate an intermediate 2;

[0011] S3: under nitrogen protection, the intermediate 1 is reacted with 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide under the action of triethylamine for 16-20 h, then the intermediate 2 is added as a capping agent to continue the reaction for 4-6 h, and post-processing is performed to obtain the modified flame retardant.

[0012] In step S1, the mass ratio of 2-benzyloxy-5-hydroxybenzaldehyde to 4,4'-diamino diphenyl ether is (8-10):(3-5).

[0013] In step S2, the mass ratio of p-iodophenol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis(triphenylphosphine)palladium is (3-4):(2-5):(0.5-0.8).

[0014] In step S3, the mass ratio of the intermediate 1, 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, and the intermediate 2 is 10:(5-6):(0.8-1).

[0015] The antioxidant is one of N-isopropyl-N'-phenyl-p-phenylenediamine, N-N'-diphenyl-p-phenylenediamine, and 4,4'-bis(alpha,alpha-dimethylbenzyl) diphenylamine.

[0016] The modified waterproof agent is prepared by the following method:

[0017] S1: under nitrogen protection, 1,3-bis(2-isocyanato-2-propyl)benzene and polytetrahydrofuran ether diol are reacted under the action of a catalyst of dibutyltin dilaurate to obtain a polyurethane prepolymer;

[0018] S2: adding octamethylcyclotetrasiloxane, dodecyl(methyl)dimethoxysilane into the reactor, stirring and heating to 80-100℃, then adding tetramethylammonium hydroxide, reacting for 2-4h, adding fluorine-containing organosiloxane, continuing to heat to 110-120℃, reacting for 1-3h to obtain long-chain fluorine-containing organosiloxane;

[0019] S3: under nitrogen protection, polyurethane prepolymer and bis(2-amino-3-methylphenyl) disulfide are subjected to chain extension reaction under the action of catalyst dibutyltin dilaurate to obtain polyurethane emulsion; then long-chain fluorine-containing organosiloxane is added for post-chain extension reaction, triethylamine is added for neutralization, and then deionized water is added for emulsification to obtain modified waterproof agent.

[0020] In step S1, the mass ratio of 1,3-bis(2-isocyanate-2-propyl) benzene to polytetrahydrofuran ether diol is (4-6):(6-10).

[0021] In step S2, the mass ratio of octamethylcyclotetrasiloxane, dodecyl(methyl)dimethoxysilane and fluorine-containing organosiloxane is 10:(1-5):(2-6).

[0022] In step S3, the mass ratio of polyurethane prepolymer, bis(2-amino-3-methylphenyl) disulfide and long-chain fluorine-containing organosiloxane is (15-20):1:(3-6).

[0023] The preparation process of the fluorine-containing organosiloxane is as follows:

[0024] The methylene in diethyl malonate undergoes nucleophilic substitution reaction with iodine atoms in 1-iodo-1H,1H,2H,2H-perfluorooctane to generate diethyl malonate substituted with fluorine-containing groups, sulfuric acid is added for hydrolysis, then the product reacts with thionyl chloride to generate acyl chloride product, and finally the acyl chloride reacts with amino groups in 3-aminopropyl triethoxysilane to generate fluorine-containing organosiloxane, and the reaction equation is as follows:

[0025] .

[0026] A preparation method of an anti-aging heat-insulating and sound-insulating composite material, comprising the following steps:

[0027] (1) weighing according to parts by weight: 10-20 parts of seaweed mud, 10-15 parts of ceramic hollow microbeads, 6-10 parts of ceramic fiber, 10-15 parts of environment-friendly sound-absorbing cotton, 2-4 parts of anti-aging agent, 4-6 parts of modified flame retardant, 60-80 parts of modified waterproof agent, 150-200 parts of DMF;

[0028] (2) Pulverize the seaweed mud and ceramic fiber, add ceramic hollow microspheres and stir to obtain mixture A; stir and mix the antioxidant, modified flame retardant, modified waterproofing agent and DMF to obtain mixture B; mix mixture A and B with ultrasonic treatment to obtain mixture C.

[0029] (3) Apply mixture C evenly to both sides of the surface of the environmentally friendly sound-absorbing cotton and dry it to obtain an anti-aging heat insulation and sound insulation composite material.

[0030] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include:

[0031] (1) In this invention, the aldehyde group in 2-benzyloxy-5-hydroxybenzaldehyde reacts with the amino group in 4,4'-diaminodiphenyl ether to prepare intermediate 1; the iodine atom in p-iodophenol undergoes a substitution reaction with the pH in 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to prepare intermediate 2; then the phenolic hydroxyl group of intermediate 1 reacts with the phosphonic chloride of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide to polymerize and obtain a long-chain compound containing phosphorus and oxygen functional groups. Then, intermediate 2 is added as a capping agent (the phenolic hydroxyl group of intermediate 2 reacts with the phosphonic chloride of the long-chain compound to terminate the chain growth of the long-chain compound), and finally a flame retardant with good flame retardant properties is prepared.

[0032] (2) In this invention, a polyurethane prepolymer was prepared using 1,3-bis(2-isocyano-2-propyl)benzene and polytetrahydrofuran ether diol, and a long-chain fluorinated organosiloxane was prepared using methylcyclotetrasiloxane, dodecyl(methyl)dimethoxysilane and fluorinated organosiloxane; then, the polyurethane prepolymer and bis(2-amino-3-methylphenyl) disulfide were subjected to a chain extension reaction, and a long-chain fluorinated organosiloxane was added for a post-chain extension reaction to prepare a modified waterproofing agent.

[0033] (3) The modified flame retardant prepared by the present invention contains a phosphorus heterocyclic structure, which can release active substances such as phosphoric acid during combustion, promote the formation of a carbon layer on the surface of the substrate, and thus effectively inhibit flame propagation; the CH=N structure cross-links at high temperature to form a stable structure, thereby playing a role in thermal protection; at the same time, the further degradation of the N-containing structure can release non-combustible gas, which works synergistically with phosphoric acid substances to expand the residual carbon, thereby achieving excellent flame retardant effect.

[0034] (4) The modified waterproofing agent prepared in this invention contains long-chain fluorinated organosiloxanes. The long-chain fluorinated organosiloxane molecular chains have low surface energy and high flexibility, which makes the waterproofing agent form a dense hydrophobic film on the substrate surface, significantly increasing the contact angle between water and the substrate surface, preventing water molecules from penetrating, and improving the waterproofing performance of the material. Detailed Implementation

[0035] The application will be further described in connection with the following examples, but the application is not limited to these examples.

[0036] Example 1 Preparation of modified flame retardant:

[0037] S1: 300 g of anhydrous ethanol, 30 g of 4,4'-diamino diphenyl ether, 80 g of 2-benzyloxy-5-hydroxybenzaldehyde were added into a reactor, stirred and dissolved, heated to 50°C, then 2 ml of glacial acetic acid was added, refluxed for 5 h, after the reaction was completed, the reaction liquid was concentrated by half, cooled to 0°C and stood for 2 h, then filtered under suction to obtain white solid, then washed with anhydrous ethanol three times (30 g of anhydrous ethanol was used each time), and vacuum dried at 50°C for 5 h to obtain intermediate 1; the structural formula is as follows:

[0038] ;

[0039] The nuclear magnetic resonance hydrogen spectrum data thereof are as follows:

[0040] 1 H NMR (500 MHz, Chloroform-d) δ 8.57 (d, J = 0.5 Hz, 2H), 8.43 (s,2H), 7.45 – 7.37 (m, 4H), 7.38 – 7.32 (m, 4H), 7.31 – 7.23 (m, 2H), 7.14 –7.07 (m, 4H), 7.03 – 6.95 (m, 6H), 6.92 (d, J = 9.0 Hz, 2H), 6.75 (dd, J =9.0, 2.2 Hz, 2H), 5.09 (t, J = 0.8 Hz, 4H).

[0041] S2: 200 g of 1,4-dioxane, 30 g of p-iodophenol, 20 g of 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide were added into a reactor, stirred, heated to 100°C, then 5 g of tetrakis(triphenylphosphine)palladium was added, reacted for 10 h, cooled to room temperature, 150 ml of ethyl acetate and 150 ml of deionized water were added, the water phase was separated by extraction, then washed with deionized water until neutral, 50 g of anhydrous sodium sulfate was added and dried for 3 h, 60°C, 4 h of reduced pressure distillation, purified by silica gel column chromatography to obtain intermediate 2; the structural formula is as follows:

[0042] ;

[0043] The nuclear magnetic resonance hydrogen spectrum data thereof are as follows:

[0044] 1H NMR (500 MHz, Chloroform-d) δ 8.22 (dd, J = 7.4, 1.2 Hz, 1H), 8.04(dd, J = 7.0, 1.4 Hz, 1H), 7.95 – 7.88 (m, 1H), 7.82 (td, J = 7.1, 1.2 Hz,1H), 7.78 – 7.70 (m, 3H), 7.63 (td, J = 7.3, 1.4 Hz, 1H), 7.56 – 7.48 (m,1H), 7.48 – 7.40 (m, 2H), 6.91 – 6.85 (m, 2H).

[0045] S3: Add 350 ml of acetonitrile, 100 g of intermediate 1 and 50 g of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, 40 g of triethylamine into the reactor, stir, reflux for 20 h, then add 8 g of intermediate 2 as a capping agent and continue to react for 4 h, after the reaction is completed, 70°C, 3h, add 300 g of water, stir for 30 min, then filter, first wash with deionized water three times (20 g of deionized water each time), then wash with anhydrous ethanol three times (20 g of anhydrous ethanol each time), 60°C, 4h, vacuum drying to obtain the modified flame retardant.

[0046] Example 2 Preparation of modified flame retardant:

[0047] S1: Add 350 g of anhydrous ethanol, 40 g of 4,4'-diamino diphenyl ether, 90 g of 2-benzyloxy-5-hydroxybenzaldehyde into the reactor, stir to dissolve, heat to 55°C, then add 2.5 ml of glacial acetic acid, reflux for 4 h, after the reaction is completed, concentrate the reaction liquid by distillation to half, cool to 0°C, stand for 2 h, filter, then wash with anhydrous ethanol three times (30 g of anhydrous ethanol each time), 60°C, 4h, vacuum drying to obtain intermediate 1;

[0048] S2: Add 200 g of 1,4-dioxane, 35 g of p-iodophenol, 35 g of 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide into the reactor, stir, add 6 g of tetrakis(triphenylphosphine)palladium, reflux for 9 h, cool to room temperature, add 150 ml of ethyl acetate and 150 ml of deionized water, extract and separate the aqueous phase, then wash with deionized water until neutral, add 50 g of anhydrous sodium sulfate and dry for 3 h, 70°C, 3h, distillation under reduced pressure, purify by silica gel column chromatography to obtain intermediate 2;

[0049] S3: Under the protection of nitrogen, 350 ml of acetonitrile, 100 g of intermediate 1, 55 g of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, 50 g of triethylamine were added into the reactor, stirred, refluxed for 18 h, then 9 g of intermediate 2 was added as a capping agent to continue the reaction for 5 h, after the reaction was completed, 70 °C was reduced pressure distilled for 3 h, 300 g of water was added and stirred for 30 min, then filtered, washed with deionized water three times (20 g of deionized water was used each time), then washed with anhydrous ethanol three times (20 g of anhydrous ethanol was used each time), and 70 °C was vacuum dried for 3 h to obtain the modified flame retardant.

[0050] Example 3: Preparation of a modified flame retardant

[0051] S1: 400 g of anhydrous ethanol, 50 g of 4,4'-diamino diphenyl ether, 100 g of 2-benzyloxy-5-hydroxybenzaldehyde were added into the reactor, stirred and dissolved, heated to 60 °C, then 3 ml of glacial acetic acid was added, refluxed for 3 h, after the reaction was completed, the reaction liquid was concentrated by distillation to half, cooled to 0 °C and stood for 2 h, then filtered, washed with anhydrous ethanol three times (30 g of anhydrous ethanol was used each time), and 70 °C was vacuum dried for 3 h to obtain intermediate 1;

[0052] S2: 210 g of 1,4-dioxane, 40 g of p-iodophenol, 50 g of 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide were added into the reactor, stirred, 8 g of tetrakis(triphenylphosphine)palladium was added, refluxed for 8 h, cooled to room temperature, 150 ml of ethyl acetate and 150 ml of deionized water were added, the water phase was extracted and separated, then washed with deionized water until neutral, 50 g of anhydrous sodium sulfate was added and dried for 3 h, 80 °C was reduced pressure distilled for 2 h, purified by silica gel column chromatography to obtain intermediate 2;

[0053] S3: Under the protection of nitrogen, 350 ml of acetonitrile, 100 g of intermediate 1, 55 g of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, 50 g of triethylamine were added into the reactor, stirred, refluxed for 18 h, then 9 g of intermediate 2 was added as a capping agent to continue the reaction for 5 h, after the reaction was completed, 70 °C was reduced pressure distilled for 3 h, 300 g of water was added and stirred for 30 min, then filtered, washed with deionized water three times (20 g of deionized water was used each time), then washed with anhydrous ethanol three times (20 g of anhydrous ethanol was used each time), and 70 °C was vacuum dried for 3 h to obtain the modified flame retardant.

[0054] Example 4: Preparation of a fluorine-containing organosiloxane

[0055] S1 : 200 mL of tetrahydrofuran, 60 g of diethyl malonate were added to the reactor, cooled to 0°C, 15 g of sodium hydride was slowly added, the temperature was kept below 10°C, stirred for 2 h, warmed to 65°C, 120 g of 1-iodo-1H, 1H, 2H, 2H-perfluorooctane (CAS No.: 2043-57-4) at 45°C was added dropwise, the dropwise addition was completed in 20 min, and the reaction was kept at 65°C for 8 h, 120 g of deionized water and 65 g of 37 wt% sulfuric acid were added, and the hydrolysis reaction was carried out at 70°C for 3 h, and 2 h of distillation at 60°C under reduced pressure to obtain diethyl malonate substituted with fluorine-containing groups;

[0056] S2: 300 mL of tetrahydrofuran, 100 g of diethyl malonate substituted with fluorine-containing groups, 120 g of sulfoxide chloride were added to the reactor, stirred, and refluxed for 5 h, and 3 h of distillation at 60°C under reduced pressure to obtain the acyl chloride product;

[0057] S3: 200 mL of toluene, 50 g of acyl chloride product, 35 g of 3-aminopropyl triethoxysilane were added to the reactor, stirred, then 30 g of triethylamine was added, refluxed for 15 h, after the reaction was completed, 3 h of distillation at 70°C under reduced pressure, 180 g of deionized water was added, stirred and pulped for 20 min, filtered, washed with 50 g of deionized water, and vacuum dried at 65°C for 10 h to obtain a fluorine-containing organosiloxane.

[0058] Example 5 Preparation of modified waterproofing agent:

[0059] S1 : 200 g of DMSO, 40 g of 1,3-bis(2-isocyanato-2-propyl)benzene were sequentially added to the reactor under nitrogen protection, stirred and dissolved, warmed to 80°C, then 60 g of polytetrahydrofuran ether diol (PTMG-1000) was slowly added dropwise, the dropwise addition was completed in 20 min, 1.6 g of catalyst dibutyltin dilaurate was added, and the reaction was carried out for 10 h to obtain a polyurethane prepolymer;

[0060] S2: 100 g of octamethylcyclotetrasiloxane, 10 g of dodecyl(methyl)dimethoxysilane were added to the reactor, stirred and warmed to 80°C, then 1.8 g of tetramethylammonium hydroxide was added, and the reaction was carried out for 4 h, 20 g of fluorine-containing organosiloxane (prepared in Example 4) was added, and the temperature was further increased to 110°C, and the reaction was carried out for 3 h, and the tetramethylammonium hydroxide was decomposed at 140°C for 20 min to obtain a long-chain fluorine-containing organosiloxane;

[0061] S3: Under nitrogen protection, 300 g of DMSO, 150 g of polyurethane prepolymer, 10 g of bis(2-amino-3-methylphenyl) disulfide were added into a reactor, stirred, and heated to 80°C, 1.5 g of dibutyl tin dilaurate was slowly added, and reacted for 4 h to obtain a polyurethane emulsion; then cooled to 60°C, 30 g of long-chain fluorine-containing organosiloxane was added, and reacted for another 2 h; after the reaction was completed, the solvent was removed by evaporation, 120 g of acetone was added to adjust the viscosity, poured into an emulsification barrel, 40 g of triethylamine was slowly added under high-speed stirring (3000 r / min) for 10 min, and then 200 g of deionized water was added for shearing emulsification for 20 min to obtain a modified waterproof agent.

[0062] Example 6: Preparation of a modified waterproof agent

[0063] S1: Under nitrogen protection, 200 g of DMSO, 50 g of 1,3-bis(2-isocyanyl-2-propyl) benzene were sequentially added into a reactor, stirred and dissolved, heated to 90°C, and then 80 g of polytetramethylene glycol (PTMG-1000) was slowly added dropwise for 20 min, 2 g of dibutyl tin dilaurate was added after the dropping was completed, and reacted for 8 h to obtain a polyurethane prepolymer;

[0064] S2: 100 g of octamethylcyclotetrasiloxane, 30 g of dodecyl(methyl)dimethoxysilane were added into a reactor, stirred and heated to 90°C, then 4 g of tetramethylammonium hydroxide was added, and reacted for 3 h; 40 g of fluorine-containing organosiloxane (prepared in Example 4) was added, and then heated to 120°C, and reacted for 2 h; the temperature was increased to 140°C, and tetramethylammonium hydroxide was decomposed for 20 min to obtain a long-chain fluorine-containing organosiloxane;

[0065] S3: Under nitrogen protection, 350 g of DMSO, 180 g of polyurethane prepolymer, 10 g of bis(2-amino-3-methylphenyl) disulfide were added into a reactor, stirred, and heated to 90°C, 2 g of dibutyl tin dilaurate was slowly added, and reacted for 3 h to obtain a polyurethane emulsion; then cooled to 60°C, 45 g of long-chain fluorine-containing organosiloxane was added, and reacted for another 1.5 h; after the reaction was completed, the solvent was removed by evaporation, 120 g of acetone was added to adjust the viscosity, poured into an emulsification barrel, 40 g of triethylamine was slowly added under high-speed stirring (3000 r / min) for 10 min, and then 200 g of deionized water was added for shearing emulsification for 20 min to obtain a modified waterproof agent.

[0066] Example 7: Preparation of a modified waterproof agent

[0067] S1: Under nitrogen protection, 200 g of DMSO, 60 g of 1,3-bis(2-isocyanyl-2-propyl) benzene were sequentially added into the reactor, stirred and dissolved, and then heated to 100°C. Then 100 g of polytetramethylene glycol (PTMG-1000) was slowly added dropwise for 20 min. After the dropwise addition was completed, 2.4 g of dibutyl tin dilaurate was added, and the reaction was carried out for 6 h to obtain a polyurethane prepolymer;

[0068] S2: 100 g of octamethylcyclotetrasiloxane and 50 g of dodecyl(methyl)dimethoxysilane were added into the reactor, stirred and heated to 100°C. Then 4 g of tetramethylammonium hydroxide was added, and the reaction was carried out for 2 h. Then 60 g of the fluorine-containing organosiloxane prepared in Example 4 was added, and the temperature was further increased to 120°C. The reaction was carried out for 2 h, and then the temperature was increased to 140°C. Tetramethylammonium hydroxide was decomposed for 20 min to obtain a long-chain fluorine-containing organosiloxane.

[0069] S3: Under nitrogen protection, 400 g of DMSO, 200 g of the polyurethane prepolymer, and 10 g of bis(2-amino-3-methylphenyl) disulfide were added into the reactor, stirred, and heated to 100°C. Then 2 g of dibutyl tin dilaurate was slowly added, and the reaction was carried out for 2 h to obtain a polyurethane emulsion. Then the temperature was decreased to 60°C, 60 g of the long-chain fluorine-containing organosiloxane was added, and the reaction was further carried out for 2 h. After the reaction was completed, the solvent was removed by evaporation. Then 150 g of acetone was added to adjust the viscosity. The mixture was poured into an emulsifying barrel, and 40 g of triethylamine was slowly added under high-speed stirring (3000 r / min) for 10 min. Then 200 g of deionized water was added, and the mixture was sheared and emulsified for 20 min to obtain a modified waterproof agent.

[0070] Example 8: Preparation of an anti-aging, heat-insulating and sound-insulating composite material

[0071] (1) The following components were weighed: 100 g of seaweed mud, 100 g of ceramic hollow microbeads, 60 g of ceramic fiber, 100 g of environmentally friendly sound-absorbing cotton, 20 g of anti-aging agent (N-isopropyl-N'-phenyl-p-phenylenediamine), 40 g of modified flame retardant (prepared in Example 1), 600 g of modified waterproof agent (prepared in Example 5), and 1500 g of DMF.

[0072] (2) The seaweed mud and ceramic fiber were pulverized to a particle size of less than 150 microns. After pulverization, the ceramic hollow microbeads were added and stirred at a stirring rate of 800 r / min for 20 min to obtain a mixture A. The anti-aging agent, modified flame retardant, and modified waterproof agent were mixed with DMF at a stirring rate of 600 r / min for 15 min to obtain a mixture B. The mixture A and B were subjected to ultrasonic mixing treatment for 20 min to obtain a mixture C, and the ultrasonic frequency was 3000 HZ.

[0073] (3) Using hot melt adhesive coating machine, evenly coat mixture C on both sides of the surface layer of the environment-friendly sound-absorbing cotton, the coating thickness is 1 mm (1 mm on both sides, the same below), and 100°C drying for 2h to obtain the anti-aging heat and sound insulation composite material.

[0074] Example 9 Preparation of anti-aging heat and sound insulation composite material:

[0075] (1) Take: seaweed mud 150g, ceramic hollow microsphere 120g, ceramic fiber 80g, environment-friendly sound-absorbing cotton 120g, anti-aging agent (N-N'-diphenyl-p-phenylenediamine) 30g, modified flame retardant (prepared in example 2) 50g, modified waterproof agent (prepared in example 6) 700g, DMF 1800g;

[0076] (2) Crush the seaweed mud and ceramic fiber, the particle size after crushing is less than 150 microns, then add the ceramic hollow microspheres for stirring, the stirring rate is 800r / min, and stirring for 20min to obtain mixture A; Stir and mix the anti-aging agent, modified flame retardant, modified waterproof agent and DMF, the stirring rate is 600r / min, and stirring for 15min to obtain mixture B, ultrasonic mixing treatment of mixture A and B for 20min to obtain mixture C, the ultrasonic frequency is 3000HZ;

[0077] (3) Using hot melt adhesive coating machine, evenly coat mixture C on both sides of the surface layer of the environment-friendly sound-absorbing cotton, the coating thickness is 1 mm, 100°C drying for 2h to obtain the anti-aging heat and sound insulation composite material.

[0078] Example 10 Preparation of anti-aging heat and sound insulation composite material:

[0079] (1) Take: seaweed mud 200g, ceramic hollow microsphere 150g, ceramic fiber 100g, environment-friendly sound-absorbing cotton 150g, anti-aging agent (4,4'-bis (α, α-dimethylbenzyl) diphenylamine) 40g, modified flame retardant (prepared in example 3) 60g, modified waterproof agent (prepared in example 7) 800g, DMF 2000g;

[0080] (2) Crush the seaweed mud and ceramic fiber, the particle size after crushing is less than 150 microns, then add the ceramic hollow microspheres for stirring, the stirring rate is 800r / min, and stirring for 20min to obtain mixture A; Stir and mix the anti-aging agent, modified flame retardant, modified waterproof agent and DMF, the stirring rate is 600r / min, and stirring for 15min to obtain mixture B, ultrasonic mixing treatment of mixture A and B for 30min to obtain mixture C, the ultrasonic frequency is 3000HZ;

[0081] (3) Using a hot melt adhesive coater, evenly coat the mixture C on both sides of the environment-friendly sound-absorbing cotton surface layer, with a coating thickness of 1 mm, and dry at 100°C for 2 h to obtain the anti-aging heat and sound insulation composite material.

[0082] Comparative Example 1

[0083] An anti-aging heat and sound insulation composite material, the raw material composition and process are basically the same as those of Example 9, except that no modified flame retardant is added to the composition.

[0084] Comparative Example 2

[0085] An anti-aging heat and sound insulation composite material, the raw material composition and process are basically the same as those of Example 9, except that the modified flame retardant is replaced by an equal weight of a modified flame retardant prepared by the following method:

[0086] S1: Add 350 g of anhydrous ethanol, 40 g of 4,4'-diamino diphenyl ether, and 90 g of 2-benzyloxy-5-hydroxybenzaldehyde to a reactor, stir and dissolve, heat to 55°C, then add 2.5 ml of glacial acetic acid, reflux for 4 h, after the reaction is completed, concentrate the reaction liquid to half by distillation, cool to 0°C and stand for 2 h, then filter the white solid, wash with anhydrous ethanol three times (30 g of anhydrous ethanol each time), and vacuum dry at 60°C for 4 h to obtain intermediate 1;

[0087] S2: Under nitrogen protection, add 350 ml of acetonitrile, 100 g of intermediate 1, 55 g of phenyl phosphorodichloridate, and 50 g of triethylamine to a reactor, stir, and reflux for 18 h, after the reaction is completed, distill at 70°C for 3 h under reduced pressure, add 300 g of water and stir for 30 min, then filter, wash with deionized water three times (20 g of deionized water each time), then wash with anhydrous ethanol three times (20 g of anhydrous ethanol each time), and vacuum dry at 70°C for 3 h to obtain the modified flame retardant.

[0088] Comparative Example 3

[0089] An anti-aging heat and sound insulation composite material, the raw material composition and process are basically the same as those of Example 9, except that the modified flame retardant is replaced by an equal weight of a modified flame retardant prepared by the following method:

[0090] S1: Add 350 g of anhydrous ethanol, 40 g of 4,4'-diamino diphenyl ether, and 90 g of 2-benzyloxy-5-hydroxybenzaldehyde to a reactor, stir and dissolve, heat to 55°C, then add 2.5 ml of glacial acetic acid, reflux for 4 h, after the reaction is completed, concentrate the reaction liquid to half by distillation, cool to 0°C and stand for 2 h, then filter the white solid, wash with anhydrous ethanol three times (30 g of anhydrous ethanol each time), and vacuum dry at 60°C for 4 h to obtain intermediate 1;

[0091] S2: 350 ml of acetonitrile, 100 g of intermediate 1, 55 g of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, 50 g of triethylamine were added into the reactor under nitrogen protection, stirred, refluxed for 18 h, then 20 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added to continue the reaction for 5 h, after the reaction was completed, 70°C was distilled under reduced pressure for 3 h, 300 g of water was added and stirred for 30 min, then filtered, washed with deionized water three times (20 g of deionized water was used each time), then washed with anhydrous ethanol three times (20 g of anhydrous ethanol was used each time), and vacuum dried at 70°C for 3 h to obtain the modified flame retardant.

[0092] Comparative Example 4

[0093] An anti-aging heat-insulating and sound-insulating composite material, the raw material composition and process are basically the same as those of Example 9, except that the modified flame retardant is replaced by an equal weight of a modified flame retardant prepared by the following method:

[0094] S1: 350 g of anhydrous ethanol, 40 g of 4,4'-diaminodiphenylmethane, 90 g of 2-benzyloxy-5-hydroxybenzaldehyde were added into the reactor, stirred and dissolved, then the temperature was raised to 55°C, 2.5 ml of glacial acetic acid was added, refluxed for 4 h, after the reaction was completed, the reaction solution was concentrated by distillation to half, the temperature was lowered to 0°C, and then stood for 2 h, filtered, then washed with anhydrous ethanol three times (30 g of anhydrous ethanol was used each time), and vacuum dried at 60°C for 4 h to obtain intermediate 1;

[0095] S2: 200 g of 1,4-dioxane, 35 g of p-iodophenol, 35 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were added into the reactor, stirred, 6 g of tetrakis(triphenylphosphine)palladium was added, refluxed for 9 h, cooled to room temperature, 150 ml of ethyl acetate and 150 ml of deionized water were added, the aqueous phase was extracted and separated, then washed with deionized water until neutral, 50 g of anhydrous sodium sulfate was added and dried for 3 h, 70°C was distilled under reduced pressure for 3 h, purified by silica gel column chromatography to obtain intermediate 2;

[0096] S3: 350 ml of acetonitrile, 100 g of intermediate 1, 55 g of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, 50 g of triethylamine were added into the reactor under nitrogen protection, stirred, refluxed for 18 h, then 9 g of intermediate 2 was added as a capping agent to continue the reaction for 5 h, after the reaction was completed, 70°C was distilled under reduced pressure for 3 h, 300 g of water was added and stirred for 30 min, then filtered, washed with deionized water three times (20 g of deionized water was used each time), then washed with anhydrous ethanol three times (20 g of anhydrous ethanol was used each time), and vacuum dried at 70°C for 3 h to obtain the modified flame retardant.

[0097] Comparative Example 5

[0098] An anti-aging thermal and sound insulation composite material, the raw material composition and process are basically the same as those of Example 9, except that the modified flame retardant is replaced by an equal weight of a modified flame retardant prepared by the following method:

[0099] S1: 350g of anhydrous ethanol, 40g of 4,4'-diamino diphenyl ether, 90g of vanillin were added to the reactor, stirred and dissolved, heated to 55℃, then 2.5ml of glacial acetic acid was added, refluxed for 4h, after the reaction was completed, the reaction liquid was concentrated by half, cooled to 0℃ and stood for 2h, then filtered, washed with anhydrous ethanol three times (30g of anhydrous ethanol was used each time), and vacuum dried at 60℃ for 4h to obtain intermediate 1;

[0100] S2: 200g of 1,4-dioxane, 35g of p-iodophenol, 35g of 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide were added to the reactor, stirred, 6g of tetrakis(triphenylphosphine)palladium was added, refluxed for 9h, cooled to room temperature, 150ml of ethyl acetate and 150ml of deionized water were added, the aqueous phase was separated by extraction, then washed with deionized water until neutral, 50g of anhydrous sodium sulfate was added and dried for 3h, 70℃ reduced pressure distillation for 3h, purified by silica gel column chromatography to obtain intermediate 2;

[0101] S3: Under nitrogen protection, 350ml of acetonitrile, 100g of intermediate 1, 55g of 3,9- dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, 50g of triethylamine were added to the reactor, stirred, refluxed for 18h, then 9g of intermediate 2 was added as a capping agent and reacted for 5h, after the reaction was completed, 70℃ reduced pressure distillation for 3h, 300g of water was added and stirred for 30min, then filtered, washed with deionized water three times (20g of deionized water was used each time), then washed with anhydrous ethanol three times (20g of anhydrous ethanol was used each time), and vacuum dried at 70℃ for 3h to obtain the modified flame retardant.

[0102] Comparative Example 6

[0103] An anti-aging thermal and sound insulation composite material, the raw material composition and process are basically the same as those of Example 9, except that the modified waterproof agent is replaced by an equal weight of the commercially available waterproof agent UNIDYNE XF-5007.

[0104] Comparative Example 7

[0105] An anti-aging thermal and sound insulation composite material, the raw material composition and process are basically the same as those of Example 9, except that the modified waterproof agent is replaced by an equal weight of a modified waterproof agent prepared by the following method:

[0106] S1: Under nitrogen protection, 200 g of DMSO and 50 g of 1,3-bis(2-isocyanyl-2-propyl) benzene were sequentially added into a reactor, stirred and dissolved, and then heated to 90°C. Then 80 g of polytetramethylene glycol (PTMG-1000) was slowly added dropwise for 20 min. After the dropwise addition was completed, 2 g of a catalyst dibutyltin dilaurate was added, and the reaction was carried out for 8 h to obtain a polyurethane prepolymer.

[0107] S2: Under nitrogen protection, 350 g of DMSO, 180 g of the polyurethane prepolymer, and 10 g of bis(2-amino-3-methylphenyl) disulfide were added into a reactor, stirred, and heated to 90°C. Then 2 g of dibutyltin dilaurate was slowly added, and the reaction was carried out for 3 h to obtain a polyurethane emulsion. Then the temperature was lowered to 60°C, 45 g of the fluorine-containing organosiloxane (prepared in Example 4) was added, and the reaction was continued for 1.5 h. After the reaction was completed, the solvent was removed by evaporation, 120 g of acetone was added to adjust the viscosity, and then the mixture was poured into an emulsifying barrel. Then 40 g of triethylamine was slowly added under high-speed stirring (3000 r / min) for 10 min, and then 200 g of deionized water was added for shearing emulsification for 20 min to obtain a modified waterproofing agent.

[0108] Comparative Example 8

[0109] An anti-aging thermal and sound insulation composite material, the raw material composition and process are basically the same as those of Example 9, except that the modified waterproofing agent is replaced by an equal weight of a modified waterproofing agent prepared by the following method:

[0110] S1: Under nitrogen protection, 200 g of DMSO and 50 g of 1,3-bis(2-isocyanyl-2-propyl) benzene were sequentially added into a reactor, stirred and dissolved, and then heated to 90°C. Then 80 g of polytetramethylene glycol (PTMG-1000) was slowly added dropwise for 20 min. After the dropwise addition was completed, 2 g of a catalyst dibutyltin dilaurate was added, and the reaction was carried out for 8 h to obtain a polyurethane prepolymer.

[0111] S2: 200 g of deionized water, 100 g of octamethylcyclotetrasiloxane, and 1 g of tetramethylammonium hydroxide were added into a reactor, and the reaction was carried out at 100°C for 1 h. Then the temperature was lowered to 60°C, 10 g of N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, 20 g of vinyltrimethoxysilane, 0.2 g of a long carbon chain trimethoxysilane, and 1 g of tetramethylammonium hydroxide were added, the temperature was raised to 120°C, and the reaction was carried out for 2 h. Then the temperature was lowered to 80°C, vacuum was applied for 30 min, 50 ml of isopropyl alcohol was added, and stirring was carried out for 30 min. Then glacial acetic acid was added to adjust the pH to neutral to obtain a modified silicone.

[0112] S3: under nitrogen protection, 350 g of DMSO, 180 g of polyurethane prepolymer, 10 g of bis(2-amino-3-methylphenyl) disulfide were added into a reactor, stirred, heated to 90°C, 2 g of dibutyl tin dilaurate was slowly added, reacted for 3 h to obtain a polyurethane emulsion; then cooled to 60°C, 45 g of modified silicone was added, and the reaction was continued for 1.5 h; after the reaction was completed, the solvent was removed by evaporation, 1020 g of acetone was added to adjust the viscosity, poured into an emulsification barrel, slowly added 40 g of triethylamine under high-speed stirring (3000 r / min) for 10 min, then 200 g of deionized water was added for shearing emulsification for 20 min, to obtain a modified waterproof agent.

[0113] Comparative Example 9

[0114] An anti-aging thermal and sound insulation composite material, the raw material composition and process are basically the same as those of Example 9, except that the modified waterproof agent is replaced by an equal weight of a modified waterproof agent prepared by the following method:

[0115] S1: under nitrogen protection, 200 g of DMSO, 50 g of 1,3-bis(2-isocyanate-2-propyl) benzene were sequentially added into a reactor, stirred and dissolved, heated to 90°C, then 80 g of polytetramethylene glycol (PTMG-1000) was slowly added dropwise, the dropping was completed in 20 min, 2 g of dibutyl tin dilaurate was added as a catalyst, and the reaction was carried out for 8 h to obtain a polyurethane prepolymer;

[0116] S2: 100 g of octamethylcyclotetrasiloxane, 30 g of dodecyl(methyl)dimethoxysilane were added into a reactor, stirred and heated to 90°C, then 4 g of tetramethylammonium hydroxide was added, the reaction was carried out for 3 h, 40 g of fluorine-containing organosiloxane (prepared in Example 4) was added, the temperature was further increased to 120°C, the reaction was carried out for 2 h, the temperature was increased to 140°C, and tetramethylammonium hydroxide was decomposed for 20 min to obtain a long-chain fluorine-containing organosiloxane;

[0117] S3: under nitrogen protection, 350 g of DMSO, 180 g of polyurethane prepolymer, 10 g of 4'4-dithiodianiline were added into a reactor, stirred, heated to 90°C, 2 g of dibutyl tin dilaurate was slowly added, reacted for 3 h to obtain a polyurethane emulsion; then cooled to 60°C, 45 g of long-chain fluorine-containing organosiloxane was added, and the reaction was continued for 1.5 h; after the reaction was completed, the solvent was removed by evaporation, 1020 g of acetone was added to adjust the viscosity, poured into an emulsification barrel, slowly added 40 g of triethylamine under high-speed stirring (3000 r / min) for 10 min, then 200 g of deionized water was added for shearing emulsification for 20 min, to obtain a modified waterproof agent.

[0118] Comparative Example 10

[0119] An anti-aging heat-insulating and sound-insulating composite material, the raw material composition and process are basically the same as those of Example 9, except that the modified waterproof agent is replaced by an equal weight of a modified waterproof agent prepared by the following method:

[0120] S1: Under nitrogen protection, 200 g of DMSO and 50 g of 1,3-bis(2-isocyanyl-2-propyl) benzene were sequentially added to the reactor, stirred and dissolved, and then heated to 90°C. Then 80 g of polytetramethylene glycol (PTMG-1000) was slowly added dropwise, and the dropping was completed after 20 min. Then 2 g of a catalyst, dibutyltin dilaurate, was added, and the reaction was carried out for 8 h to obtain a polyurethane prepolymer.

[0121] S2: 100 g of octamethylcyclotetrasiloxane and 30 g of dodecyl(methyl)dimethoxysilane were added to the reactor, stirred and heated to 90°C. Then 4 g of tetramethylammonium hydroxide was added, and the reaction was carried out for 3 h. Then 40 g of a fluorine-containing organosiloxane (prepared in Example 4) was added, and the temperature was further increased to 120°C. The reaction was carried out for 2 h, and then the temperature was increased to 140°C to decompose the tetramethylammonium hydroxide for 20 min to obtain a long-chain fluorine-containing organosiloxane.

[0122] S3: Under nitrogen protection, 350 g of DMSO, 180 g of the polyurethane prepolymer, and 45 g of the long-chain fluorine-containing organosiloxane were added to the reactor, and the temperature was increased to 90°C. Then 2 g of dibutyltin dilaurate was slowly added, and the reaction was carried out for 3 h. After the reaction was completed, the solvent was removed by evaporation, 120 g of acetone was added to adjust the viscosity, and then the mixture was poured into an emulsifying barrel. Then 40 g of triethylamine was slowly added under high-speed stirring (3000 r / min) for 10 min, and then 200 g of deionized water was added for shearing emulsification for 20 min to obtain the modified waterproof agent.

[0123] Comparative Example 11

[0124] S1: Under nitrogen protection, 200 g of DMSO and 50 g of 1,3-bis(2-isocyanyl-2-propyl) benzene were sequentially added to the reactor, stirred and dissolved, and then heated to 90°C. Then 80 g of polytetramethylene glycol (PTMG-1000) was slowly added dropwise, and the dropping was completed after 20 min. Then 2 g of a catalyst, dibutyltin dilaurate, was added, and the reaction was carried out for 8 h to obtain a polyurethane prepolymer.

[0125] S2: 100 g of octamethylcyclotetrasiloxane and 30 g of dodecyl(methyl)dimethoxysilane were added to the reactor, stirred and heated to 90°C. Then 4 g of tetramethylammonium hydroxide was added, and the reaction was carried out for 3 h. Then 40 g of a fluorine-containing organosiloxane (prepared in Example 4) was added, and the temperature was further increased to 120°C. The reaction was carried out for 2 h, and then the temperature was increased to 140°C to decompose the tetramethylammonium hydroxide for 20 min to obtain a long-chain fluorine-containing organosiloxane.

[0126] S3: Under nitrogen protection, 350 g of DMSO, 180 g of polyurethane prepolymer, 10 g of bis(2-amino-3-methylphenyl) disulfide were added to the reactor, stirred, and heated to 90°C. 2 g of dibutyltin dilaurate was slowly added, and the reaction was carried out for 3 h to obtain a polyurethane emulsion. Then, the temperature was lowered to 60°C, 45 g of long-chain fluorine-containing organosiloxane was added, and the reaction was continued for 1.5 h. After the reaction was completed, the solvent was removed by evaporation, 120 g of acetone was added to adjust the viscosity, and the mixture was poured into an emulsification barrel. After 40 g of triethylamine was slowly added under high-speed stirring (3000 r / min) for 10 min, 200 g of deionized water was added, and the mixture was sheared and emulsified for 20 min to obtain a modified waterproof agent.

[0127] Comparative Example 12

[0128] An anti-aging thermal and sound insulation composite material, the raw material composition and process are basically the same as those of Example 9, except that the modified waterproof agent is replaced by an equal weight of a modified waterproof agent prepared by the following method:

[0129] (1) 3 kg of non-ionic diol Ymer-N120 was vacuum dried at a temperature of 100°C for 3 h. Under nitrogen protection, 0.1 kg of dibutyltin dilaurate was added, and stirred at a temperature of 90°C for 15 min. 2 kg of hexamethylene diisocyanate, 2 kg of isophorone diisocyanate, and 2 kg of hydroxyethyl methacrylate were added in sequence under stirring. The temperature was lowered to 70°C, and the stirring was continued for 2 h. After ether precipitation, the mixture was vacuum dried at a temperature of 50°C for 20 h to obtain a pre-prepared polyurethane dispersion;

[0130] (2) 10 kg of dimethyldiethoxysilane, 5 kg of 1,3-bis(aminopropyl)tetramethyldisiloxane, and 6 kg of octamethylcyclotetrasiloxane were mixed uniformly. 0.18 kg of tetramethylammonium hydroxide was added, and the mixture was reacted at a temperature of 100°C for 10 h. The temperature was lowered to 40°C, and 60 kg of acetone was added and stirred uniformly. 2 kg of triethylamine was added, and the pre-prepared polyurethane dispersion was added under nitrogen protection during stirring. The reaction was carried out for 4 h, and the temperature was lowered to room temperature. 40 kg of water was added dropwise and stirred uniformly to obtain a waterproof agent.

[0131] Comparative Example 13

[0132] An environmentally friendly building energy-saving sound insulation material was prepared by using the raw material composition, ratio, and method of Example 4 of the Chinese invention patent with publication number CN119285887A.

[0133] The seaweed mud used in embodiments 8-10 and comparative examples 1-12 is model B717, purchased from Changbai Korean Autonomous County Beijiang Diatomite New Material Technology Co., Ltd.; the ceramic hollow microsphere is model E-SPHERES, purchased from Dalian Yibang Technology Co., Ltd.; the ceramic fiber is model 1050, purchased from Shandong Luyang Energy-saving Material Co., Ltd.; and the environmentally friendly sound-absorbing cotton is model ME64-30T, specifications: 1200*600*30mm, purchased from Shengbo (Beijing) Acoustic Technology Co., Ltd. When the environmentally friendly sound-absorbing cotton is weighed, the cutting thickness is 8mm, the width is 350mm, and the length is changed according to the weight. The water used in the present application is deionized water.

[0134] The anti-aging thermal and sound insulation composite materials prepared in embodiments 8-10 and comparative example 1-13 are subjected to water absorption rate testing, and the experimental method is based on ASTM D570-98.

[0135] The anti-aging thermal and sound insulation composite materials prepared in embodiments 8-10 and comparative example 1-13 are subjected to vertical burning (UL-94) and smoldering time testing, and the horizontal and vertical burning tester is used to test the vertical burning level according to the ASTM-D3801:2010 standard, the sample size is 127mm*13mm*10mm, and the test results are shown in Table 1.

[0136] Table 1

[0137]

[0138] As can be seen from Table 1 embodiments 8, 9 and 10, the anti-aging thermal and sound insulation composite materials prepared in the present application have a water absorption rate of less than 1.35%, a flame retardant level of V-0, and good flame retardant performance and waterproof performance.

[0139] Comparative example 1 is a comparative example without adding a modified flame retardant. As can be seen from the data in Table 1, the water absorption rate is 1.26%, the combustion level (UL-94) is V-2, and when no modified flame retardant is added, the anti-aging thermal and sound insulation composite material prepared has poor flame retardant performance.

[0140] Comparative Example 2 is a comparative example different from Example 9, the difference is that 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide in step S3 in the preparation process of the modified flame retardant is replaced by phenylphosphonic dichloride, and it can be seen from the data in Table 1 that the water absorption rate is 1.30%, and the combustion rating (UL-94) is V-1 level, which is due to the fact that the spirocyclic phosphate molecule contains two phosphorus heterocycles, which can form a dense and continuous carbon layer during combustion, and these functional groups can synergistically release non-combustible gases, further diluting the concentration of combustible gases, thereby inhibiting combustion, while the carbon layer formed by phenylphosphonic dichloride is relatively less dense, so the flame retardant effect is relatively poor.

[0141] Comparative Example 3 is a comparative example different from Example 9, the difference is that the intermediate 2 prepared in step S2 of the modified flame retardant is replaced by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and it can be seen from the data in Table 1 that the water absorption rate is 1.27%, and the combustion rating (UL-94) is V-1 level, which is due to the fact that the intermediate 2 prepared in step S2 contains 4-hydroxyphenyl groups, and the hydroxyl group can be dehydrated to form a stable aromatic ring structure at high temperature, enhancing the stability of the carbon layer and improving the flame retardant ability.

[0142] Comparative Example 4 is a comparative example different from Example 9, the difference is that 4,4'-diamino diphenyl ether in step S1 of the modified flame retardant is replaced by 4,4'-diamino diphenyl methane, and it can be seen from the data in Table 1 that the water absorption rate is 1.33%, and the combustion rating (UL-94) is V-1 level, and the flame retardant performance is relatively poor. The difference between 4,4'-diamino diphenyl ether and 4,4'-diamino diphenyl methane is the ether bond and methylene between the benzene rings. Although both the ether bond and the methylene can increase the flexibility of the polymer chain, the ether bond has better flexibility due to its higher rotational freedom and smaller internal rotation potential barrier; while the methylene has a simple structure and flexible rotation, the repeated occurrence of methylene units in the polymer chain can increase the flexibility of the molecular chain, making the entire molecular chain more easily bent and deformed, providing flexibility to the polymer chain. The flexibility of the ether bond is slightly worse than that of the methylene, so the introduction of the ether bond can significantly improve the flexibility and solubility of the molecular chain, and thus improve the flame retardant performance of the modified flame retardant.

[0143] Comparative Example 5 is a comparative example different from Example 9, the difference is that 2-benzyloxy-5-hydroxybenzaldehyde in step S1 of the modified flame retardant is replaced by vanillin, and it can be seen from the data in Table 1 that the water absorption rate is 1.25%, and the combustion rating (UL-94) is V-1 level, and the flame retardant performance is not as good as that of the composite material prepared in Example 9.

[0144] Comparative Example 6 is a comparative example different from Example 9, the difference being that the modified waterproofing agent is replaced by a commercially available waterproofing agent UNIDYNE XF-5007, and from the data in Table 1 it can be seen that the water absorption is 4.28% and the combustion rating (UL-94) is V-0, indicating that the waterproofing effect of this waterproofing agent is general.

[0145] Comparative Example 7 is a comparative example different from Example 9, the difference being that the long-chain fluorine-containing organosiloxane added in step S3 in the preparation of the modified waterproofing agent is replaced by fluorine-containing organosiloxane (prepared in Example 4), and from the data in Table 1 it can be seen that the water absorption is 2.76% and the combustion rating (UL-94) is V-0.

[0146] Comparative Example 8 is a comparative example different from Example 9, the difference being that the long-chain fluorine-containing organosiloxane added in step S2 in the preparation of the modified waterproofing agent is different, and from the data in Table 1 it can be seen that the water absorption is 5.74% and the combustion rating (UL-94) is V-0, indicating that the waterproofing effect is general, which is due to the high stability and chemical inertness of the molecular structure of the fluorine-containing silane, which makes it not easy to be affected by external factors during use. This stability makes the waterproofing performance of the fluorine-containing silane have good durability.

[0147] Comparative Example 9 is a comparative example different from Example 9, the difference being that the bis(2-amino-3-methylphenyl) disulfide in step S3 in the preparation of the modified waterproofing agent is replaced by 4'4-dithiodianiline, and from the data in Table 1 it can be seen that the water absorption is 1.31% and the combustion rating (UL-94) is V-0.

[0148] Comparative Example 10 is a comparative example different from Example 9, the difference being that no bis(2-amino-3-methylphenyl) disulfide is added in step S3 in the preparation of the modified waterproofing agent, and from the data in Table 1 it can be seen that the water absorption is 1.48% and the combustion rating (UL-94) is V-0.

[0149] Comparative Example 11 is different from Example 9, the difference is that the fluorine-containing organosiloxane in the preparation process step S2 of the modified waterproof agent is replaced by perfluorodecyltrimethoxysilane, and from the data in Table 1, it can be seen that the water absorption rate is 2.86%, and the combustion rating (UL-94) is V-0 level. The main reason why the waterproof performance of perfluorodecyltrimethoxysilane (APTS) is not as good as the fluorine-containing organosiloxane prepared in this application is the difference in molecular structure and surface energy. APTS molecules only contain one perfluoroalkyl chain, which can provide certain hydrophobicity, but the waterproof layer formed is relatively thin, and the surface energy is relatively high. In contrast, the fluorine-containing organosiloxane of the present application contains two alkyl chains, and is connected by a malonamide structure. This structure makes the waterproof layer formed on the surface thicker and denser, with lower surface energy, which can more effectively repel water molecules, thereby providing better waterproof performance.

[0150] Comparative Example 12 is different from Example 9, the difference is that the preparation method of the modified waterproof agent is different, from the data in Table 1, it can be seen that the water absorption rate is 4.92%, and the combustion rating (UL-94) is V-0 level, the waterproof effect is not as good as the modified waterproof agent prepared in this application, this is due to the strong electronegativity of fluorine atom, which can form strong hydrogen bond repulsion with hydrogen atom in water molecule, this effect makes water droplets cannot form effective adhesion when contacting the material surface, thereby improving the waterproof effect.

[0151] Comparative Example 13 is an environmentally friendly building energy-saving sound insulation material prepared by using the raw materials of Example 4 of Chinese invention patent CN119285887A and the process of this application, from the data in Table 1, it can be seen that the water absorption rate is 10.36%, and the combustion rating (UL-94) is V-0 level, the waterproof effect is not as good as this application.

[0152] According to ASTM D2343 standard, the tensile properties of the anti-aging thermal and sound insulation composite before and after damage were tested, and the experimental results are shown in Table 2.

[0153] The specific method of the damage test is as follows: use a square iron block of 1.5 cm*0.5 cm to uniformly impact the composite (every 8 cm 2 The impact pressure is 0.35 MPa each time, and the tensile property test is carried out after 24 h of placement after impact.

[0154] Table 2

[0155]

[0156] As can be seen from Table 2, the anti-aging thermal and sound insulation composite material prepared in Examples 8-10 of the present application has a tensile property greater than 12.5 MPa, and the tensile property after the breaking test is still greater than 10.2 MPa, indicating that the anti-aging thermal and sound insulation composite material prepared in the present application has excellent tensile property and excellent self-repairing performance. Bis(2-amino-3-methylphenyl) disulfide (APDS) exhibits stronger self-repairing ability than 4'4-dithiodianiline (DTDA), and the main reason is that the structure of APDS contains not only dynamic disulfide bond, but also amino and methyl substituents, which can form additional hydrogen bonds or other interactions with other components in polyurethane, thereby enhancing the synergistic effect between molecules and improving the repair efficiency. In addition, the disulfide bond of APDS can undergo dynamic exchange reaction under mild conditions (such as lower temperature), and the activity of this reaction is higher, which can quickly repair the broken chemical bonds. In contrast, although DTDA also contains disulfide bond, its structure is relatively simple, mainly relies on the dynamic exchange of disulfide bond to realize self-repairing, and lacks additional synergistic effect, so it performs slightly inferior in terms of self-repairing efficiency and mechanical property improvement.

[0157] The above is only the preferred embodiment of the present application, and is not used to limit the present application; but for the ordinary skilled in the art, within the scope of the technical scheme of the present application, some minor changes, modifications and equivalent changes of the above disclosed technical content can be made, which are equivalent embodiments of the present application; at the same time, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present application are still within the protection scope of the technical scheme of the present application.

Claims

1. An anti-aging thermal and acoustic insulating composite material, characterized in that, The anti-aging heat and sound insulation composite material is prepared by the following method: (1) Take by weight parts: seaweed mud 10-20 parts, ceramic hollow microbeads 10-15 parts, ceramic fiber 6-10 parts, environmentally friendly sound-absorbing cotton 10-15 parts, anti-aging agent 2-4 parts, modified flame retardant 4-6 parts, modified waterproof agent 60-80 parts, DMF 150-200 parts; (2) The seaweed mud and ceramic fiber are crushed, and after crushing, the ceramic hollow microbeads are added for stirring to obtain a mixture A; the anti-aging agent, modified flame retardant, modified waterproof agent and DMF are stirred and mixed to obtain a mixture B, and the mixtures A and B are ultrasonic mixed to obtain a mixture C; (3) The mixture C is evenly applied on both sides of the surface layer of the environmentally friendly sound-absorbing cotton, and after drying, the anti-aging heat and sound insulation composite material is obtained; The modified flame retardant is prepared by the following method: S1: 2-benzyloxy-5-hydroxybenzaldehyde reacts with 4,4'-diamino diphenyl ether under the action of catalyst glacial acetic acid to obtain intermediate 1; S2: p-iodophenol reacts with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide under the action of tetrakis(triphenylphosphine)palladium to generate intermediate 2; S3: Under nitrogen protection, intermediate 1 reacts with 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide under the action of triethylamine for 16-20h, then intermediate 2 is added as a capping agent to continue reacting for 4-6h, and after treatment, the modified flame retardant is obtained; The modified waterproof agent is prepared by the following method: A1: Under nitrogen protection, 1,3-bis(2-isocyanato-2-propyl)benzene and polytetrahydrofuran ether diol react under the action of catalyst dibutyltin dilaurate to obtain a polyurethane prepolymer; A2: Octamethylcyclotetrasiloxane and dodecyl(methyl)dimethoxysilane are added to a reactor, stirred and heated to 80-100 DEG C, then tetramethylammonium hydroxide is added, and reacted for 2-4h, then fluorine-containing organosiloxane is added, and heated to 110-120 DEG C, and reacted for 1-3h to obtain long-chain fluorine-containing organosiloxane; A3: Under nitrogen protection, the polyurethane prepolymer and bis(2-amino-3-methylphenyl) disulfide are chain-extended under the action of catalyst dibutyltin dilaurate to obtain a polyurethane emulsion; then long-chain fluorine-containing organosiloxane is added for post-chain extension reaction, triethylamine is added for neutralization, then deionized water is added for emulsification to obtain the modified waterproof agent; The preparation process of the fluorine-containing organosiloxane is as follows: Diethyl malonate reacts with 1-iodo-1H,1H,2H,2H-perfluorooctane to generate diethyl malonate substituted with fluorine-containing groups, which is hydrolyzed and reacted with thionyl chloride to generate acyl chloride product, and finally the acyl chloride product reacts with 3-aminopropyl triethoxysilane to generate fluorine-containing organosiloxane.

2. The anti-aging thermal and acoustic insulation composite material according to claim 1, characterized in that, In step S1, the mass ratio of 2-benzyloxy-5-hydroxybenzaldehyde to 4,4'-diamino diphenyl ether is (8-10):(3-5).

3. The anti-aging thermal and acoustic insulation composite material according to claim 1, characterized in that, The mass ratio of the p-iodophenol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and tetrakis(triphenylphosphine)palladium in step S2 is (3-4):(2-5):(0.5-0.8).

4. The anti-aging thermal and acoustic insulation composite material according to claim 1, wherein, The mass ratio of the intermediate 1, 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, and intermediate 2 in step S3 is 10:(5-6):(0.8-1).

5. The anti-aging thermal and acoustic insulation composite material according to claim 1, wherein, The antioxidant is one of N-isopropyl-N'-phenyl-p-phenylenediamine, N-N'-diphenyl-p-phenylenediamine, and 4,4'-bis(alpha,alpha-dimethylbenzyl)diphenylamine.

6. The anti-aging thermal and acoustic insulation composite material according to claim 1, wherein, The mass ratio of the 1,3-bis(2-isocyanato-2-propyl)benzene and polytetrahydrofuran ether glycol in step A1 is (4-6):(6-10). The mass ratio of the octamethylcyclotetrasiloxane, dodecyl(methyl)dimethoxysilane, and fluorine-containing organosiloxane in step A2 is 10:(1-5):(2-6). The mass ratio of the polyurethane prepolymer, bis(2-amino-3-methylphenyl)disulfide, and long-chain fluorine-containing organosiloxane in step A3 is (15-20):1:(3-6).

7. A method of preparing the anti-aging thermal and acoustic insulating composite material according to any one of claims 1-6, characterized in that, The method comprises the following steps: (1) The following components are weighed by parts by weight: seaweed mud 10-20 parts, ceramic hollow microbeads 10-15 parts, ceramic fiber 6-10 parts, environmentally friendly sound-absorbing cotton 10-15 parts, antioxidant 2-4 parts, modified flame retardant 4-6 parts, modified waterproof agent 60-80 parts, and DMF 150-200 parts; (2) The seaweed mud and ceramic fiber are crushed, and the crushed ceramic hollow microbeads are stirred to obtain a mixture A; the antioxidant, modified flame retardant, modified waterproof agent, and DMF are stirred and mixed to obtain a mixture B, and the mixture A and B are ultrasonically mixed to obtain a mixture C; (3) The mixture C is evenly applied on both sides of the surface layer of the environmentally friendly sound-absorbing cotton, and then dried to obtain the anti-aging heat-insulating and sound-insulating composite material.

Images