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

Abstract

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

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to an anti-aging heat-insulating and sound-insulating composite material and a preparation method thereof. Background Art

[0002] With the increasing demand for high-performance materials in the modern industrial and construction fields, the application scope of heat-insulating and sound-insulating composite materials is becoming increasingly wide. However, traditional heat-insulating and sound-insulating materials have significant deficiencies in flame retardancy and waterproof performance, which limits their use in complex environments. For example, although polyurethane materials have good mechanical properties and heat-insulating effects, they are prone to burning at high temperatures, and toxic gases will be generated during the combustion process. In addition, when traditional composite materials are subjected to mechanical damage or long-term exposure to a humid environment, their performance is likely to decline. In recent years, significant progress has been made in the application research of composite materials in the field of heat-insulating and sound-insulating. By combining the excellent properties of different materials, composite materials can achieve both heat-insulating and sound-insulating effects. For example, the heat-insulating and sound-insulating properties of PVC / NBR / OMMT composite materials are significantly improved by adding organic montmorillonite. In addition, by introducing nanomaterials such as titanium dioxide microspheres or SiO hollow microspheres modified with silane coupling agents into the composite materials, the anti-aging performance and heat-insulating and sound-insulating effects of the materials can be further enhanced. However, existing composite materials still face some challenges in practical applications. Therefore, developing a composite material with good anti-aging performance, heat-insulating and sound-insulating properties is of great significance for meeting the needs of the modern industrial and construction fields. 2 Chinese Patent No. CN119285887A discloses an environmentally friendly building energy-saving sound-insulating material and a preparation method thereof. The environmentally friendly building energy-saving sound-insulating material comprises the following raw materials in parts by weight: 100-120 parts of modified polyether polyol, 140-150 parts of isocyanate, 8-12 parts of modified hollow glass microspheres, 5-8 parts of modified sericite, 3-5 parts of ammonium polyphosphate, 2-4 parts of foaming agent, 1-3 parts of stabilizer, and 0.1-0.5 part of catalyst. The environmentally friendly building energy-saving sound-insulating material has excellent heat-insulating and flame-retardant properties, but poor waterproof performance.

[0003] Summary of the Invention In view of the deficiencies of the prior art, the purpose of the present invention is to provide an anti-aging heat-insulating and sound-insulating composite material and a preparation method thereof.

[0004] To achieve the above purpose, the present invention is realized through the following technical solutions:

[0005] An anti-aging heat-insulating and sound-insulating composite material, comprising the following raw materials in parts by weight: ​10-20 parts of diatom mud, 10-15 parts of ceramic hollow microspheres, 6-10 parts of ceramic fibers, 10-15 parts of environmental protection sound-absorbing cotton, 2-4 parts of antioxidant, 4-6 parts of modified flame retardant, 60-80 parts of modified waterproof agent, 150-200 parts of DMF; The modified flame retardant is prepared by the following method: S1: 2-Benzyloxy-5-hydroxybenzaldehyde reacts with 4,4'-diaminodiphenyl ether under the action of the 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 the protection of nitrogen, 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 16-20 h, then intermediate 2 is added as a capping agent and the reaction continues for 4-6 h, and the modified flame retardant is obtained after post-treatment.

[0006] In step S1, the feeding mass ratio of 2-benzyloxy-5-hydroxybenzaldehyde to 4,4'-diaminodiphenyl ether is (8-10):(3-5).

[0007] In step S2, the feeding mass ratio of p-iodophenol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and tetrakis(triphenylphosphine)palladium is (3-4):(2-5):(0.5-0.8).

[0008] In step S3, the feeding mass ratio of intermediate 1, 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, and intermediate 2 is 10:(5-6):(0.8-1).

[0009] The antioxidant is one of N-isopropyl-N'-phenyl-p-phenylenediamine, N-N'-diphenyl-p-phenylenediamine, and 4,4'-bis(α,α-dimethylbenzyl)diphenylamine.

[0010] The modified waterproof agent is prepared by the following method: S1: Under the protection of nitrogen, 1,3-bis(2-isocyanato-2-propyl)benzene and polytetrahydrofuran ether diol react under the action of the catalyst dibutyltin dilaurate to obtain a polyurethane prepolymer; S2: Octamethylcyclotetrasiloxane and dodecyl(methyl)dimethoxysilane are added to the reactor, stirred and heated to 80-100 °C, then tetramethylammonium hydroxide is added, and the reaction is carried out for 2-4 h. Then, a fluorinated organosiloxane is added, and the temperature is further raised to 110-120 °C, and the reaction is carried out for 1-3 h to obtain a long-chain fluorinated organosiloxane; S3: Under nitrogen protection, a chain extension reaction is carried out between a polyurethane prepolymer and bis(2-amino-3-methylphenyl) disulfide under the action of a catalyst dibutyltin dilaurate to obtain a polyurethane emulsion; then a long-chain fluorinated organosiloxane is added for a post-chain extension reaction, triethylamine is added for neutralization, and then deionized water is added for emulsification to obtain a modified waterproofing agent.

[0011] In step S1, the feeding mass ratio of 1,3-bis(2-isocyanato-2-propyl)benzene to polytetrahydrofuran ether glycol is (4 - 6):(6 - 10).

[0012] In step S2, the feeding mass ratio of octamethylcyclotetrasiloxane, dodecyl(methyl)dimethoxysilane, and fluorinated organosiloxane is 10:(1 - 5):(2 - 6).

[0013] In step S3, the feeding mass ratio of the polyurethane prepolymer, bis(2-amino-3-methylphenyl) disulfide, and long-chain fluorinated organosiloxane is (15 - 20):1:(3 - 6).

[0014] The preparation process of the fluorinated organosiloxane is as follows: The methylene group in diethyl malonate undergoes a nucleophilic substitution reaction with the iodine atom in 1-iodo-1H,1H,2H,2H-perfluorooctane to form diethyl malonate substituted with a fluorinated group, which is hydrolyzed with sulfuric acid, then reacts with thionyl chloride to form an acyl chloride product, and finally the acyl chloride reacts with the amino group in 3-aminopropyltriethoxysilane to form a fluorinated organosiloxane. The reaction equation is shown as follows: .

[0015] A preparation method of an anti-aging heat-insulating and sound-insulating composite material includes the following steps: (1) Weigh by weight: 10 - 20 parts of diatomaceous earth, 10 - 15 parts of ceramic hollow microspheres, 6 - 10 parts of ceramic fibers, 10 - 15 parts of environmentally friendly sound-absorbing cotton, 2 - 4 parts of anti-aging agent, 4 - 6 parts of modified flame retardant, 60 - 80 parts of modified waterproofing agent, and 150 - 200 parts of DMF; (2) Crush the diatomaceous earth and ceramic fibers, and after crushing, add ceramic hollow microspheres and stir to obtain mixture A; stir and mix the anti-aging agent, modified flame retardant, modified waterproofing agent with DMF to obtain mixture B, and perform ultrasonic mixing treatment on mixture A and B to obtain mixture C; (3) Uniformly apply mixture C on both sides of the surface layer of the environmentally friendly sound-absorbing cotton, and dry to obtain the anti-aging heat-insulating and sound-insulating composite material.

[0016] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: (1) In the present 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 P-H 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 phosphoryl chloride of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide for polymerization to obtain a long-chain compound containing phosphorus-oxygen functional groups, and then intermediate 2 is added as a capping agent (the phenolic hydroxyl group of intermediate 2 reacts with the phosphoryl 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 performance is prepared.

[0017] (2) In the present invention, a polyurethane prepolymer is prepared from 1,3-bis(2-isocyanato-2-propyl)benzene and polytetrahydrofuran ether diol, and a long-chain fluorinated organosiloxane is prepared from methylcyclotetrasiloxane, dodecyl(methyl)dimethoxysilane, and fluorinated organosiloxane; then the polyurethane prepolymer and bis(2-amino-3-methylphenyl) disulfide are subjected to a chain extension reaction, and the long-chain fluorinated organosiloxane is added for a post-chain extension reaction to prepare a modified waterproofing agent.

[0018] (3) The modified flame retardant prepared in 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 crosslinks to form a stable structure at high temperatures, thereby playing a thermal protection role; at the same time, the further degradation of the N-containing structure can release incombustible gases, which act synergistically with phosphoric acid substances to cause the residual carbon to expand, and thus achieve excellent flame retardant effects.

[0019] (4) The modified waterproofing agent prepared in the present invention contains a long-chain fluorinated organosiloxane. The molecular chain of the long-chain fluorinated organosiloxane has a low surface energy and high flexibility, enabling the waterproofing agent to form a dense hydrophobic film on the surface of the substrate, significantly increasing the contact angle between water and the substrate surface, preventing the penetration of water molecules, and improving the waterproof performance of the material. Detailed implementation manners

[0020] The following is further described in conjunction with embodiments, but the present invention is not limited to these embodiments.

[0021] Example 1 Preparation of modified flame retardant: S1: Add 300 g of absolute ethanol, 30 g of 4,4'-diaminodiphenyl ether, and 80 g of 2-benzyloxy-5-hydroxybenzaldehyde into the reactor, stir to dissolve, heat up to 50 °C, then add 2 ml of glacial acetic acid, and reflux for 5 h. After the reaction is completed, concentrate the reaction solution by half through reduced pressure evaporation, cool down to 0 °C, stand for 2 h, filter to obtain a white solid, then wash it three times with absolute ethanol (30 g of absolute ethanol is used each time), and dry it under vacuum at 50 °C for 5 h to obtain Intermediate 1; its structural formula is as follows: ;

[0022] The data of its nuclear magnetic resonance hydrogen spectrum are as follows: 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). S2: Add 200 g of 1,4-dioxane, 30 g of p-iodophenol, and 20 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the reactor, stir, heat up to 100 °C, then add 5 g of tetrakis(triphenylphosphine)palladium, react for 10 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 it with deionized water until neutral, add 50 g of anhydrous sodium sulfate and dry for 3 h, distill under reduced pressure at 60 °C for 4 h, and purify by silica gel column chromatography to obtain Intermediate 2; its structural formula is as follows: ;

[0023] The data of its nuclear magnetic resonance hydrogen spectrum are as follows: 11H 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). S3: Under nitrogen protection, add 350 ml of acetonitrile, 100 g of intermediate 1, 50 g of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, and 40 g of triethylamine into the reactor, stir, and reflux for 20 h. Then add 8 g of intermediate 2 as a capping agent and continue the reaction for 4 h. After the reaction is completed, distill under reduced pressure at 70 °C for 3 h, add 300 g of water, stir for 30 min, filter, wash three times with deionized water (20 g of deionized water each time), then wash three times with absolute ethanol (20 g of absolute ethanol each time), and dry in vacuo at 60 °C for 4 h to obtain the modified flame retardant.

[0024] Example 2 Preparation of the modified flame retardant: S1: Add 350 g of absolute ethanol, 40 g of 4,4'-diaminodiphenyl ether, and 90 g of 2-benzyloxy-5-hydroxybenzaldehyde into the reactor, stir to dissolve, heat up to 55 °C, then add 2.5 ml of glacial acetic acid, and reflux for 4 h. After the reaction is completed, concentrate the reaction solution by half through reduced pressure distillation, cool to 0 °C, stand for 2 h, filter to obtain a white solid, then wash three times with absolute ethanol (30 g of absolute ethanol each time), and dry in vacuo at 60 °C for 4 h to obtain intermediate 1; S2: Add 200 g of 1,4-dioxane, 35 g of p-iodophenol, and 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, distill under reduced pressure at 70 °C for 3 h, and purify by silica gel column chromatography to obtain intermediate 2; S3: Under nitrogen protection, add 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, and 50 g of triethylamine into the reactor. Stir and reflux for 18 h, then add 9 g of Intermediate 2 as a capping agent and continue the reaction for 5 h. After the reaction is completed, distill under reduced pressure at 70 °C for 3 h, add 300 g of water, stir for 30 min, then filter, wash three times with deionized water (20 g of deionized water each time), and then wash three times with absolute ethanol (20 g of absolute ethanol each time). Dry in vacuum at 70 °C for 3 h to obtain the modified flame retardant.

[0025] Example 3 Preparation of modified flame retardant: S1: Add 400 g of absolute ethanol, 50 g of 4,4'-diaminodiphenyl ether, and 100 g of 2-benzyloxy-5-hydroxybenzaldehyde into the reactor. Stir to dissolve, heat up to 60 °C, then add 3 ml of glacial acetic acid, and reflux for 3 h. After the reaction is completed, concentrate the reaction solution by half through vacuum distillation, cool down to 0 °C, stand for 2 h, filter to obtain a white solid, and then wash three times with absolute ethanol (30 g of absolute ethanol each time). Dry in vacuum at 70 °C for 3 h to obtain Intermediate 1; S2: Add 210 g of 1,4-dioxane, 40 g of p-iodophenol, and 50 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the reactor. Stir, add 8 g of tetrakis(triphenylphosphine)palladium, and reflux for 8 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, distill under reduced pressure at 80 °C for 2 h, and purify by silica gel column chromatography to obtain Intermediate 2; S3: Under nitrogen protection, add 350 ml of acetonitrile, 100 g of Intermediate 1, 60 g of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, and 60 g of triethylamine into the reactor. Stir and reflux for 16 h, then add 10 g of Intermediate 2 as a capping agent and continue the reaction for 6 h. After the reaction is completed, distill under reduced pressure at 70 °C for 3 h, add 300 g of water, stir for 30 min, then filter, wash three times with deionized water (20 g of deionized water each time), and then wash three times with absolute ethanol (20 g of absolute ethanol each time). Dry in vacuum at 80 °C for 2 h to obtain the modified flame retardant.

[0026] Example 4 Preparation of fluorinated organosiloxane: S1: Add 200 mL of tetrahydrofuran and 60 g of diethyl malonate to the reactor, cool down to 0 °C, slowly add 15 g of sodium hydride, keep the temperature below 10 °C, stir for 2 h, heat up to 65 °C, dropwise add 120 g of 1-iodo-1H,1H,2H,2H-perfluorooctane (CAS No.: 2043-57-4) at 45 °C, complete the dropwise addition in 20 min, keep the temperature for reaction for 8 h after the dropwise addition, add 120 g of deionized water and 65 g of 37 wt% sulfuric acid, carry out hydrolysis reaction at 70 °C for 3 h, and carry out vacuum distillation at 60 °C for 2 h to obtain diethyl malonate substituted with fluorine-containing groups; S2: Add 300 mL of tetrahydrofuran, 100 g of diethyl malonate substituted with fluorine-containing groups, and 120 g of thionyl chloride to the reactor, stir, and carry out reflux reaction for 5 h, carry out vacuum distillation at 60 °C for 3 h to obtain an acyl chloride product; S3: Add 200 ml of toluene, 50 g of acyl chloride product, 35 g of 3-aminopropyltriethoxysilane to the reactor, stir, then add 30 g of triethylamine, carry out reflux reaction for 15 h, after the reaction is completed, carry out vacuum distillation at 70 °C for 3 h, add 180 g of deionized water, stir and make a slurry for 20 min, filter, wash with 50 g of deionized water, and carry out vacuum drying at 65 °C for 10 h to obtain fluorine-containing organosiloxane.

[0027] Example 5 Preparation of modified waterproof agent: S1: Under nitrogen protection, add 200 g of DMSO and 40 g of 1,3-bis(2-isocyanato-2-propyl)benzene to the reactor in sequence, stir and dissolve, heat up to 80 °C, then slowly dropwise add 60 g of polytetrahydrofuran ether diol (PTMG-1000), complete the dropwise addition in 20 min, add 1.6 g of catalyst dibutyltin dilaurate after the dropwise addition, and react for 10 h to obtain a polyurethane prepolymer; S2: Add 100 g of octamethylcyclotetrasiloxane and 10 g of dodecyl(methyl)dimethoxysilane to the reactor, stir and heat up to 80 °C, then add 1.8 g of tetramethylammonium hydroxide, react for 4 h, add 20 g of fluorine-containing organosiloxane (prepared in Example 4), continue to heat up to 110 °C, react for 3 h, heat up to 140 °C to decompose tetramethylammonium hydroxide for 20 min to obtain long-chain fluorine-containing organosiloxane; S3: Under nitrogen protection, add 300 g of DMSO, 150 g of polyurethane prepolymer, and 10 g of bis(2-amino-3-methylphenyl) disulfide to the reactor, stir, heat up to 80 °C, slowly add 1.5 g of dibutyltin dilaurate, react for 4 h to obtain a polyurethane emulsion; then cool down to 60 °C, add 30 g of long-chain fluorinated organosiloxane, continue to react for 2 h. After the reaction is completed, remove the solvent by reduced distillation, add 120 g of acetone to adjust the viscosity, pour it into an emulsifying barrel, slowly add 40 g of triethylamine under high-speed stirring (3000 r / min) to neutralize for 10 min, and then add 200 g of deionized water to shear and emulsify for 20 min to obtain the modified waterproof agent.

[0028] Example 6 Preparation of modified waterproof agent: S1: Under nitrogen protection, add 200 g of DMSO and 50 g of 1,3-bis(2-isocyanato-2-propyl)benzene to the reactor in sequence, stir to dissolve, heat up to 90 °C, and then slowly dropwise add 80 g of polytetrahydrofuran ether diol (PTMG-1000) dropwise for 20 min. After dropping, add 2 g of the catalyst dibutyltin dilaurate and react for 8 h to obtain a polyurethane prepolymer; S2: Add 100 g of octamethylcyclotetrasiloxane and 30 g of dodecyl(methyl)dimethoxysilane to the reactor, stir and heat up to 90 °C, then add 4 g of tetramethylammonium hydroxide, react for 3 h, add 40 g of fluorinated organosiloxane (prepared in Example 4), continue to heat up to 120 °C, react for 2 h, and heat up to 140 °C to decompose tetramethylammonium hydroxide for 20 min to obtain a long-chain fluorinated organosiloxane; S3: Under nitrogen protection, add 350 g of DMSO, 180 g of polyurethane prepolymer, and 10 g of bis(2-amino-3-methylphenyl) disulfide to the reactor, stir, heat up to 90 °C, slowly add 2 g of dibutyltin dilaurate, react for 3 h to obtain a polyurethane emulsion; then cool down to 60 °C, add 45 g of long-chain fluorinated organosiloxane, continue to react for 1.5 h. After the reaction is completed, remove the solvent by reduced distillation, add 120 g of acetone to adjust the viscosity, pour it into an emulsifying barrel, slowly add 40 g of triethylamine under high-speed stirring (3000 r / min) to neutralize for 10 min, and then add 200 g of deionized water to shear and emulsify for 20 min to obtain the modified waterproof agent.

[0029] Example 7 Preparation of modified waterproof agent: S1: Under nitrogen protection, add 200 g of DMSO and 60 g of 1,3-bis(2-isocyanato-2-propyl)benzene to the reactor in sequence, stir to dissolve, heat up to 100 °C, and then slowly dropwise add 100 g of polytetrahydrofuran ether diol (PTMG-1000) dropwise for 20 min. After dropping, add 2.4 g of the catalyst dibutyltin dilaurate and react for 6 h to obtain a polyurethane prepolymer; S2: Add 100 g of octamethylcyclotetrasiloxane and 50 g of dodecyl(methyl)dimethoxysilane into the reactor, stir and heat up to 100 °C, then add 4 g of tetramethylammonium hydroxide, react for 2 h, add 60 g of fluorinated organosiloxane (prepared in Example 4), continue to heat up to 120 °C, react for 2 h, heat up to 140 °C to decompose tetramethylammonium hydroxide for 20 min to obtain long-chain fluorinated organosiloxane; S3: Under nitrogen protection, add 400 g of DMSO, 200 g of polyurethane prepolymer, and 10 g of bis(2-amino-3-methylphenyl) disulfide into the reactor, stir, heat up to 100 °C, slowly add 2 g of dibutyltin dilaurate, react for 2 h to obtain a polyurethane emulsion; then cool down to 60 °C, add 60 g of long-chain fluorinated organosiloxane, continue to react for 2 h. After the reaction is completed, remove the solvent by reduced pressure distillation, add 150 g of acetone to adjust the viscosity, pour it into an emulsifying bucket, slowly add 40 g of triethylamine to neutralize for 10 min under high-speed stirring (3000 r / min), and then add 200 g of deionized water for shear emulsification for 20 min to obtain the modified waterproof agent.

[0030] Example 8 Preparation of anti-aging heat-insulating and sound-insulating composite material: (1) Weigh: 100 g of diatomaceous earth, 100 g of ceramic hollow microspheres, 60 g of ceramic fiber, 100 g of environmentally friendly sound-absorbing cotton, 20 g of antioxidant (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; (2) Crush the diatomaceous earth and ceramic fiber, and the particle size after crushing is less than 150 microns. After crushing, add ceramic hollow microspheres and stir at a stirring rate of 800 r / min for 20 min to obtain mixture A; stir and mix the antioxidant, modified flame retardant, modified waterproof agent and DMF at a stirring rate of 600 r / min for 15 min to obtain mixture B. Ultrasonically mix mixtures A and B for 20 min to obtain mixture C, and the ultrasonic frequency is 3000 HZ; (3) Use a hot melt adhesive coater to evenly coat mixture C on both sides of the surface of the environmentally friendly sound-absorbing cotton, with a coating thickness of 1 mm (1 mm for both sides, the same below), and dry at 100 °C for 2 h to obtain the anti-aging heat-insulating and sound-insulating composite material.

[0031] Example 9 Preparation of anti-aging heat-insulating and sound-insulating composite material: (1) Weigh: 150 g of diatomaceous earth, 120 g of ceramic hollow microspheres, 80 g of ceramic fiber, 120 g of environmentally friendly sound-absorbing cotton, 30 g of antioxidant (N-N'-diphenyl-p-phenylenediamine), 50 g of modified flame retardant (prepared in Example 2), 700 g of modified waterproof agent (prepared in Example 6), and 1800 g of DMF; (2) Crush the diatom mud and ceramic fiber. After crushing, the particle size is less than 150 microns. After crushing, add ceramic hollow microspheres and stir at a stirring rate of 800 r / min for 20 min to obtain mixture A; stir and mix the antioxidant, modified flame retardant, modified waterproofing agent with DMF at a stirring rate of 600 r / min for 15 min to obtain mixture B. Ultrasonically mix mixtures A and B for 20 min to obtain mixture C, with an ultrasonic frequency of 3000 HZ; (3) Use a hot melt adhesive coater to evenly coat mixture C on both sides of the surface layer of the environmentally friendly sound-absorbing cotton. The coating thickness is 1 mm, and dry it at 100 °C for 2 h to obtain the anti-aging heat-insulating and sound-insulating composite material.

[0032] Example 10 Preparation of anti-aging heat-insulating and sound-insulating composite material: (1) Weigh: 200 g of diatom mud, 150 g of ceramic hollow microspheres, 100 g of ceramic fiber, 150 g of environmentally friendly sound-absorbing cotton, 40 g of antioxidant (4,4'-bis(α,α-dimethylbenzyl)diphenylamine), 60 g of modified flame retardant (prepared in Example 3), 800 g of modified waterproofing agent (prepared in Example 7), 2000 g of DMF; (2) Crush the diatom mud and ceramic fiber. After crushing, the particle size is less than 150 microns. After crushing, add ceramic hollow microspheres and stir at a stirring rate of 800 r / min for 20 min to obtain mixture A; stir and mix the antioxidant, modified flame retardant, modified waterproofing agent with DMF at a stirring rate of 600 r / min for 15 min to obtain mixture B. Ultrasonically mix mixtures A and B for 30 min to obtain mixture C, with an ultrasonic frequency of 3000 HZ; (3) Use a hot melt adhesive coater to evenly coat mixture C on both sides of the surface layer of the environmentally friendly sound-absorbing cotton. The coating thickness is 1 mm, and dry it at 100 °C for 2 h to obtain the anti-aging heat-insulating and sound-insulating composite material.

[0033] Comparative Example 1 An anti-aging heat-insulating and sound-insulating composite material, the raw material composition and process are basically the same as those in Example 9, the difference is that the modified flame retardant is not added in the components.

[0034] Comparative Example 2 An anti-aging heat-insulating and sound-insulating composite material, the raw material composition and process are basically the same as those in Example 9, the difference is that the modified flame retardant is replaced with an equal weight of modified flame retardant prepared by the following method: S1: Add 350 g of absolute ethanol, 40 g of 4,4'-diaminodiphenyl ether, and 90 g of 2-benzyloxy-5-hydroxybenzaldehyde into the reactor, stir to dissolve, heat up to 55 °C, then add 2.5 ml of glacial acetic acid, and reflux for 4 h. After the reaction is completed, concentrate the reaction solution to half by reduced distillation, cool down to 0 °C, stand for 2 h, filter to obtain a white solid, then wash it three times with absolute ethanol (30 g of absolute ethanol each time), and dry it in vacuum at 60 °C for 4 h to obtain Intermediate 1; S2: Under nitrogen protection, add 350 ml of acetonitrile, 100 g of Intermediate 1, 55 g of phenylphosphoryl dichloride, and 50 g of triethylamine into the reactor, stir, and reflux for 18 h. After the reaction is completed, distill under reduced pressure at 70 °C for 3 h, add 300 g of water, stir for 30 min, then filter, wash it three times with deionized water (20 g of deionized water each time), and then wash it three times with absolute ethanol (20 g of absolute ethanol each time), and dry it in vacuum at 70 °C for 3 h to obtain the modified flame retardant.

[0035] Comparative Example 3 An anti-aging, heat-insulating and sound-insulating composite material has the same raw material composition and process as in Example 9, except that the modified flame retardant is replaced with a modified flame retardant prepared by the following method with the same weight: S1: Add 350 g of absolute ethanol, 40 g of 4,4'-diaminodiphenyl ether, and 90 g of 2-benzyloxy-5-hydroxybenzaldehyde into the reactor, stir to dissolve, heat up to 55 °C, then add 2.5 ml of glacial acetic acid, and reflux for 4 h. After the reaction is completed, concentrate the reaction solution to half by reduced distillation, cool down to 0 °C, stand for 2 h, filter to obtain a white solid, then wash it three times with absolute ethanol (30 g of absolute ethanol each time), and dry it in vacuum at 60 °C for 4 h to obtain Intermediate 1; S2: Under nitrogen protection, add 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, and 50 g of triethylamine into the reactor, stir, and reflux for 18 h, then add 20 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and continue the reaction for 5 h. After the reaction is completed, distill under reduced pressure at 70 °C for 3 h, add 300 g of water, stir for 30 min, then filter, wash it three times with deionized water (20 g of deionized water each time), and then wash it three times with absolute ethanol (20 g of absolute ethanol each time), and dry it in vacuum at 70 °C for 3 h to obtain the modified flame retardant.

[0036] Comparative Example 4 An anti-aging, heat-insulating and sound-insulating composite material has the same raw material composition and process as in Example 9, except that the modified flame retardant is replaced with a modified flame retardant prepared by the following method with the same weight: S1: Add 350 g of absolute ethanol, 40 g of 4,4'-diaminodiphenylmethane, and 90 g of 2-benzyloxy-5-hydroxybenzaldehyde into the reactor, stir to dissolve, heat up to 55 °C, then add 2.5 ml of glacial acetic acid, and reflux for 4 h. After the reaction is completed, concentrate the reaction solution by half through reduced-pressure evaporation, cool down to 0 °C, stand for 2 h, filter to obtain a white solid, then wash it three times with absolute ethanol (30 g of absolute ethanol each time), and dry it under vacuum at 60 °C for 4 h to obtain Intermediate 1; S2: Add 200 g of 1,4-dioxane, 35 g of p-iodophenol, and 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 it with deionized water until neutral, add 50 g of anhydrous sodium sulfate and dry for 3 h, distill under reduced pressure at 70 °C for 3 h, and purify by silica gel column chromatography to obtain Intermediate 2; S3: Under nitrogen protection, add 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, and 50 g of triethylamine into the reactor, stir, and reflux for 18 h. Then add 9 g of Intermediate 2 as a capping agent and continue to react for 5 h. After the reaction is completed, distill under reduced pressure at 70 °C for 3 h, add 300 g of water, stir for 30 min, then filter, wash it three times with deionized water (20 g of deionized water each time), and then wash it three times with absolute ethanol (20 g of absolute ethanol each time), and dry it under vacuum at 70 °C for 3 h to obtain the modified flame retardant.

[0037] Comparative Example 5 An anti-aging heat-insulating and sound-insulating composite material, the raw material composition and process are basically the same as those in Example 9, the difference is that the modified flame retardant is replaced with an equal weight of the modified flame retardant prepared by the following method: S1: Add 350 g of absolute ethanol, 40 g of 4,4'-diaminodiphenyl ether, and 90 g of vanillin into the reactor, stir to dissolve, heat up to 55 °C, then add 2.5 ml of glacial acetic acid, and reflux for 4 h. After the reaction is completed, concentrate the reaction solution by half through reduced-pressure evaporation, cool down to 0 °C, stand for 2 h, filter to obtain a white solid, then wash it three times with absolute ethanol (30 g of absolute ethanol each time), and dry it under vacuum at 60 °C for 4 h to obtain Intermediate 1; S2: Add 200 g of 1,4-dioxane, 35 g of p-iodophenol, and 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, distill under reduced pressure at 70 °C for 3 h, and purify by silica gel column chromatography to obtain intermediate 2; S3: Under nitrogen protection, add 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, and 50 g of triethylamine into the reactor, stir, reflux for 18 h, then add 9 g of intermediate 2 as a capping agent and continue to react for 5 h. After the reaction is completed, distill under reduced pressure at 70 °C for 3 h, add 300 g of water, stir for 30 min, filter, wash three times with deionized water (20 g of deionized water each time), then wash three times with absolute ethanol (20 g of absolute ethanol each time), and dry in vacuum at 70 °C for 3 h to obtain the modified flame retardant.

[0038] Comparative Example 6 An anti-aging heat-insulating and sound-insulating composite material, the raw material composition and process are basically the same as those in Example 9, the difference is that the modified waterproofing agent is replaced with a commercially available waterproofing agent UNIDYNE XF-5007 of equal weight.

[0039] Comparative Example 7 An anti-aging heat-insulating and sound-insulating composite material, the raw material composition and process are basically the same as those in Example 9, the difference is that the modified waterproofing agent is replaced with a modified waterproofing agent prepared by the following method of equal weight: S1: Under nitrogen protection, add 200 g of DMSO and 50 g of 1,3-bis(2-isocyanato-2-propyl)benzene into the reactor in sequence, stir to dissolve, heat up to 90 °C, then slowly dropwise add 80 g of polytetrahydrofuran ether glycol (PTMG-1000) dropwise for 20 min. After dropping, add 2 g of catalyst dibutyltin dilaurate, and react for 8 h to obtain a polyurethane prepolymer; S2: Under nitrogen protection, add 350 g of DMSO, 180 g of polyurethane prepolymer, and 10 g of bis(2-amino-3-methylphenyl) disulfide into the reactor, stir, heat up to 90 °C, slowly add 2 g of dibutyltin dilaurate, react for 3 h to obtain a polyurethane emulsion; then cool down to 60 °C, add 45 g of fluorinated organosiloxane (prepared in Example 4), continue to react for 1.5 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, add 120 g of acetone to adjust the viscosity, pour it into an emulsifying barrel, slowly add 40 g of triethylamine under high-speed stirring (3000 r / min) to neutralize for 10 min, and then add 200 g of deionized water to shear and emulsify for 20 min to obtain the modified waterproof agent.

[0040] Comparative Example 8 An anti-aging heat-insulating and sound-insulating composite material, the raw material composition and process are basically the same as those in Example 9, the difference is that the modified waterproof agent is replaced with a modified waterproof agent prepared by the following method with the same weight: S1: Under nitrogen protection, add 200 g of DMSO and 50 g of 1,3-bis(2-isocyanato-2-propyl) benzene into the reactor in sequence, stir and dissolve, heat up to 90 °C, then slowly dropwise add 80 g of polytetrahydrofuran ether glycol (PTMG-1000) dropwise for 20 min. After dropping, add 2 g of the catalyst dibutyltin dilaurate and react for 8 h to obtain a polyurethane prepolymer; S2: Add 200 g of deionized water, 100 g of octamethylcyclotetrasiloxane, 1 g of tetramethylammonium hydroxide into the reactor, react at 100 °C for 1 h, cool down to 60 °C, add 10 g of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, 20 g of vinyltrimethoxysilane, 0.2 g of long-chain trimethoxysilane, 1 g of tetramethylammonium hydroxide, heat up to 120 °C and react for 2 h, cool down to 80 °C and react under vacuum for 30 min, add 50 ml of isopropanol, stir for 30 min, add glacial acetic acid to adjust the pH to neutral to obtain the modified organosilicon.

[0041] S3: Under nitrogen protection, add 350 g of DMSO, 180 g of polyurethane prepolymer, and 10 g of bis(2-amino-3-methylphenyl) disulfide into the reactor, stir, heat up to 90 °C, slowly add 2 g of dibutyltin dilaurate, react for 3 h to obtain a polyurethane emulsion; then cool down to 60 °C, add 45 g of the modified organosilicon, continue to react for 1.5 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, add 120 g of acetone to adjust the viscosity, pour it into an emulsifying barrel, slowly add 40 g of triethylamine under high-speed stirring (3000 r / min) to neutralize for 10 min, and then add 200 g of deionized water to shear and emulsify for 20 min to obtain the modified waterproof agent.

[0042] Comparative Example 9 An anti-aging, heat-insulating and sound-insulating composite material, the raw material composition and process are basically the same as those in Example 9, the difference is that the modified waterproof agent is replaced with a modified waterproof agent prepared by the following method with the same weight: S1: Under nitrogen protection, add 200 g of DMSO and 50 g of 1,3-bis(2-isocyanato-2-propyl)benzene to the reactor in sequence, stir and dissolve, heat up to 90 °C, then slowly dropwise add 80 g of polytetrahydrofuran ether diol (PTMG-1000) over 20 min. After dropping, add 2 g of the catalyst dibutyltin dilaurate, and react for 8 h to obtain a polyurethane prepolymer; S2: Add 100 g of octamethylcyclotetrasiloxane and 30 g of dodecyl(methyl)dimethoxysilane to the reactor, stir and heat up to 90 °C, then add 4 g of tetramethylammonium hydroxide, react for 3 h, add 40 g of fluorinated organosiloxane (prepared in Example 4), continue to heat up to 120 °C, react for 2 h, heat up to 140 °C to decompose tetramethylammonium hydroxide for 20 min to obtain a long-chain fluorinated organosiloxane; S3: Under nitrogen protection, add 350 g of DMSO, 180 g of the polyurethane prepolymer, and 10 g of 4,4'-dithiobisbenzeneamine to the reactor, stir, heat up to 90 °C, slowly add 2 g of dibutyltin dilaurate, and react for 3 h to obtain a polyurethane emulsion; then cool down to 60 °C, add 45 g of the long-chain fluorinated organosiloxane, continue to react for 1.5 h. After the reaction is completed, remove the solvent by reduced pressure evaporation, add 1020 g of acetone to adjust the viscosity, pour it into an emulsifying tank, slowly add 40 g of triethylamine to neutralize for 10 min under high-speed stirring (3000 r / min), and then add 200 g of deionized water to shear and emulsify for 20 min to obtain the modified waterproof agent.

[0043] Comparative Example 10 An anti-aging, heat-insulating and sound-insulating composite material, the raw material composition and process are basically the same as those in Example 9, the difference is that the modified waterproof agent is replaced with a modified waterproof agent prepared by the following method with the same weight: S1: Under nitrogen protection, add 200 g of DMSO and 50 g of 1,3-bis(2-isocyanato-2-propyl)benzene to the reactor in sequence, stir and dissolve, heat up to 90 °C, then slowly dropwise add 80 g of polytetrahydrofuran ether diol (PTMG-1000) over 20 min. After dropping, add 2 g of the catalyst dibutyltin dilaurate, and react for 8 h to obtain a polyurethane prepolymer; S2: Add 100 g of octamethylcyclotetrasiloxane and 30 g of dodecyl(methyl)dimethoxysilane to the reactor, stir and heat up to 90 °C, then add 4 g of tetramethylammonium hydroxide, react for 3 h, add 40 g of fluorinated organosiloxane (prepared in Example 4), continue to heat up to 120 °C, react for 2 h, heat up to 140 °C to decompose tetramethylammonium hydroxide for 20 min to obtain a long-chain fluorinated organosiloxane; S3: Under nitrogen protection, add 350 g of DMSO, 180 g of polyurethane prepolymer, and 45 g of long-chain fluorinated organosiloxane into the reactor. Heat up to 90 °C, slowly add 2 g of dibutyltin dilaurate, and react for 3 h. After the reaction is completed, remove the solvent by reduced distillation, add 120 g of acetone to adjust the viscosity, pour it into the emulsifying tank, slowly add 40 g of triethylamine under high-speed stirring (3000 r / min) to neutralize for 10 min, and then add 200 g of deionized water for shear emulsification for 20 min to obtain the modified waterproof agent.

[0044] Comparative Example 11 S1: Under nitrogen protection, add 200 g of DMSO and 50 g of 1,3-bis(2-isocyanato-2-propyl)benzene into the reactor in sequence, stir to dissolve, heat up to 90 °C, and then slowly dropwise add 80 g of polytetrahydrofuran ether glycol (PTMG-1000) dropwise for 20 min. After dropping, add 2 g of the catalyst dibutyltin dilaurate and react for 8 h to obtain a polyurethane prepolymer; S2: Add 100 g of octamethylcyclotetrasiloxane and 30 g of dodecyl(methyl)dimethoxysilane into the reactor, stir and heat up to 90 °C, then add 4 g of tetramethylammonium hydroxide and react for 3 h. Add 40 g of perfluorodecyltrimethoxysilane, continue to heat up to 120 °C and react for 2 h, and heat up to 140 °C to decompose tetramethylammonium hydroxide for 20 min to obtain a long-chain fluorinated organosiloxane; S3: Under nitrogen protection, add 350 g of DMSO, 180 g of polyurethane prepolymer, and 10 g of bis(2-amino-3-methylphenyl) disulfide into the reactor, stir, heat up to 90 °C, slowly add 2 g of dibutyltin dilaurate, and react for 3 h to obtain a polyurethane emulsion; then cool down to 60 °C, add 45 g of long-chain fluorinated organosiloxane, and continue to react for 1.5 h. After the reaction is completed, remove the solvent by reduced distillation, add 120 g of acetone to adjust the viscosity, pour it into the emulsifying tank, slowly add 40 g of triethylamine under high-speed stirring (3000 r / min) to neutralize for 10 min, and then add 200 g of deionized water for shear emulsification for 20 min to obtain the modified waterproof agent.

[0045] Comparative Example 12 An anti-aging heat-insulating and sound-insulating composite material has the same raw material composition and process as in Example 9, except that the modified waterproof agent is replaced with a modified waterproof agent prepared by the following method with the same weight: (1) 3 kg of non-ionic diol Ymer-N120 was vacuum dried at 100 °C for 3 h. Under nitrogen protection, 0.1 kg of dibutyltin dilaurate was added, and the mixture was stirred at 90 °C for 15 min. Under stirring, 2 kg of hexamethylene diisocyanate, 2 kg of isophorone diisocyanate, and 2 kg of 2-hydroxyethyl methacrylate were added in sequence. The temperature was lowered to 70 °C, and stirring was continued for 2 h. After precipitation with ether, it was vacuum dried at 50 °C for 20 h to obtain a prefabricated polyurethane dispersion; (2) 10 kg of dimethyldiethoxysilane, 5 kg of 1,3-bis(aminopropyl)tetramethyldisiloxane, and 6 kg of octamethylcyclotetrasiloxane were mixed evenly. 0.18 kg of tetramethylammonium hydroxide was added, and the reaction was carried out at 100 °C for 10 h. The temperature was lowered to 40 °C, 60 kg of acetone was added and stirred evenly. 2 kg of triethylamine was added. Under nitrogen protection, the prefabricated polyurethane dispersion was added during stirring, and the reaction was carried out for 4 h. The temperature was lowered to room temperature, and 40 kg of water was added dropwise and stirred evenly to obtain a waterproof agent.

[0046] Comparative Example 13 An environmentally friendly building energy-saving sound insulation material prepared by using the raw material composition, ratio, and method of Example 4 of the Chinese invention patent with the publication number CN119285887A.

[0047] In Examples 8-10 and Comparative Examples 1-12 of this application, the diatom mud model is B717, purchased from Changbai Korean Autonomous County Beijiang Diatomite New Material Technology Co., Ltd.; the ceramic hollow microsphere model is E-SPHERES, purchased from Dalian Yibang Technology Co., Ltd.; the ceramic fiber model is 1050 type, purchased from Shandong Luyang Energy Saving Materials Co., Ltd.; the environmentally friendly sound-absorbing cotton model is ME64-30T, specification: 1200×600×30 mm, purchased from Shengboshi (Beijing) Acoustic Technology Co., Ltd. When weighing the environmentally friendly sound-absorbing cotton, the cut thickness is 8 mm and the width is 350 mm, and the length changes according to the weighed weight. The water mentioned in this application is all deionized water.

[0048] The water absorption rate of the anti-aging heat-insulating and sound-insulating composite materials prepared in Examples 8-10 and Comparative Examples 1-13 was tested, and the experimental method was carried out according to ASTM D570-98.

[0049] The vertical burning (UL-94) and smoldering time tests of the anti-aging heat-insulating and sound-insulating composite materials prepared in Examples 8-10 and Comparative Examples 1-13 were carried out. The vertical burning level was tested by a horizontal and vertical burning tester according to the ASTM-D3801:2010 standard. The sample size was 127 mm×13 mm×10 mm, and the test results are shown in Table 1.

[0050] Table 1

[0051] As can be seen from Examples 8, 9, and 10 in Table 1, the water absorption rates of the anti-aging, heat-insulating, and sound-insulating composite materials prepared by the present invention are all lower than 1.35%, and the flame retardant grade is V-0, indicating good flame retardant and waterproof properties.

[0052] Comparative Example 1 is a comparative example without adding a modified flame retardant. From the data in Table 1, it can be seen that its water absorption rate is 1.26%, and the combustion grade (UL-94) is V-2. When the modified flame retardant is not added, the flame retardant performance of the prepared anti-aging, heat-insulating, and sound-insulating composite material is poor.

[0053] 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 of the preparation process of the modified flame retardant is replaced by phenylphosphoryl dichloride. From the data in Table 1, it can be seen that its water absorption rate is 1.30%, and the combustion grade (UL-94) is V-1. This is because the spirocyclic phosphate molecule contains two phosphorus heterocycles, which can form a dense and continuous carbon layer during combustion. At the same time, these functional groups can act synergistically to release non-combustible gases, further diluting the concentration of combustible gases, thereby suppressing combustion. The carbon layer formed by phenylphosphoryl dichloride is relatively less dense, so the flame retardant effect is relatively poor.

[0054] 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. From the data in Table 1, it can be seen that its water absorption rate is 1.27%, and the combustion grade (UL-94) is V-1. This is because the intermediate 2 prepared in step S2 contains a 4-hydroxyphenyl group, and the hydroxyl group can dehydrate to form a stable aromatic ring structure at high temperature, enhancing the stability of the carbon layer and improving the flame retardant ability.

[0055] Comparative Example 4 is a comparative example different from Example 9. The difference is that 4,4'-diaminodiphenyl ether in step S1 of the modified flame retardant is replaced by 4,4'-diaminodiphenylmethane. It can be seen from the data in Table 1 that its water absorption rate is 1.33% and the combustion rating (UL-94) is V-1 grade, and its flame retardant performance is relatively poor. The difference between 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylmethane lies in the ether bond and methylene group between the benzene rings. Although both the ether bond and the methylene group can increase the flexibility of the polymer chain, the ether bond has better flexibility due to its higher rotational freedom and smaller internal rotation barrier; while the methylene group, through its simple structure and flexible rotation, in the polymer chain, the repeated occurrence of methylene units can increase the flexibility of the molecular chain, making the whole molecular chain easier to bend and deform, providing flexibility for the polymer chain, and its flexibility is slightly worse than that of the ether bond. Therefore, the introduction of the ether bond can significantly improve the flexibility and solubility of the molecular chain, and further improve the flame retardant performance of the modified flame retardant.

[0056] 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. It can be seen from the data in Table 1 that its water absorption rate is 1.25% and the combustion rating (UL-94) is V-1 grade, and its flame retardant performance is not as good as the composite material prepared in Example 9.

[0057] Comparative Example 6 is a comparative example different from Example 9. The difference is that the modified waterproof agent is replaced by a commercially available waterproof agent UNIDYNE XF-5007. It can be seen from the data in Table 1 that its water absorption rate is 4.28% and the combustion rating (UL-94) is V-0 grade, indicating that the waterproof effect of this waterproof agent is average.

[0058] Comparative Example 7 is a comparative example different from Example 9. The difference is that the long-chain fluorinated organosiloxane added in step S3 of the preparation process of the modified waterproof agent is replaced by a fluorinated organosiloxane (prepared in Example 4). It can be seen from the data in Table 1 that its water absorption rate is 2.76% and the combustion rating (UL-94) is V-0 grade.

[0059] Comparative Example 8 is a comparative example different from Example 9. The difference is that the long-chain fluorinated organosiloxane added in step S2 of the preparation process of the modified waterproof agent is different. It can be seen from the data in Table 1 that its water absorption rate is 5.74% and the combustion rating (UL-94) is V-0 grade, and the waterproof effect is average. This is because the molecular structure of the fluorosilane has high stability and chemical inertness, making it not easily affected by external factors during use. This stability makes the waterproof performance of the fluorosilane have good durability.

[0060] Comparative Example 9 is a comparative example different from Example 9. The difference is that bis(2-amino-3-methylphenyl) disulfide in step S3 of the preparation process of the modified waterproofing agent is replaced by 4,4'-dithiobis(aniline). It can be seen from the data in Table 1 that its water absorption rate is 1.31% and the combustion rating (UL-94) is V-0 grade.

[0061] Comparative Example 10 is a comparative example different from Example 9. The difference is that bis(2-amino-3-methylphenyl) disulfide is not added in step S3 of the preparation process of the modified waterproofing agent. It can be seen from the data in Table 1 that its water absorption rate is 1.48% and the combustion rating (UL-94) is V-0 grade.

[0062] Comparative Example 11 is a comparative example different from Example 9. The difference is that the fluorinated organosiloxane in step S2 of the preparation process of the modified waterproofing agent is replaced by perfluorodecyltrimethoxysilane. It can be seen from the data in Table 1 that its water absorption rate is 2.86% and the combustion rating (UL-94) is V-0 grade. The main reason why the waterproof performance of perfluorodecyltrimethoxysilane (APTS) is inferior to that of the fluorinated organosiloxane prepared in this application lies in the differences in its molecular structure and surface energy. The APTS molecule contains only one perfluoroalkyl chain, which can provide certain hydrophobicity, but the waterproof layer formed by it is thinner and the surface energy is relatively high. In contrast, the fluorinated organosiloxane of this application contains two alkyl chains and is connected by a malonamide structure. This structure makes the waterproof layer formed on the surface thicker, denser, and has a lower surface energy, and can more effectively repel water molecules, thus providing better waterproof performance.

[0063] Comparative Example 12 is a comparative example different from Example 9. The difference is that the preparation method of the modified waterproofing agent is different. It can be seen from the data in Table 1 that its water absorption rate is 4.92% and the combustion rating (UL-94) is V-0 grade. The waterproof effect is inferior to that of the modified waterproofing agent prepared in this application. This is because the electronegativity of fluorine atoms is extremely strong and can form a strong hydrogen bond repulsion with the hydrogen atoms in water molecules. This effect makes it impossible for water droplets to form effective adhesion when contacting the material surface, thereby improving the waterproof effect.

[0064] Comparative Example 13 is an environmentally friendly building energy-saving sound insulation material prepared by using the raw materials of Example 4 of the Chinese invention patent with the publication number CN119285887A and the process of this application. It can be seen from the data in Table 1 that its water absorption rate is 10.36% and the combustion rating (UL-94) is V-0 grade. The waterproof effect is inferior to that of this application.

[0065] The tensile properties of the anti-aging heat-insulating and sound-insulating composite material before and after damage were tested according to the ASTM D2343 standard. The experimental results are shown in Table 2.

[0066] The specific method of the destruction test is as follows: Use a square iron block of 1.5 cm * 0.5 cm to impact the composite material evenly (impact once every 8 cm 2 at one point), the impact pressure each time is 0.35 MPa. After the impact, conduct the tensile property test after placing it for 24 h.

[0067] Table 2

[0068] It can be seen from Table 2 that the tensile property of the anti-aging heat-insulating and sound-insulating composite material prepared in Examples 8 - 10 of this application is greater than 12.5 MPa, and its tensile property after the destruction test is still greater than 10.2 MPa, indicating that the anti-aging heat-insulating and sound-insulating composite material prepared in this application has excellent tensile properties and excellent self-healing properties. Bis(2-amino-3-methylphenyl) disulfide (APDS) shows stronger self-healing ability than 4,4'-dithiobis(aniline) (DTDA). The main reason is that the structure of APDS not only contains dynamic disulfide bonds but also has amino and methyl substituents. These groups can form additional hydrogen bonds or other interactions with other components in the polyurethane, thereby enhancing the intermolecular synergy and improving the repair efficiency. In addition, the disulfide bonds of APDS can undergo dynamic exchange reactions under mild conditions (such as lower temperatures), and the activity of this reaction is relatively high, which can quickly repair the broken chemical bonds. In contrast, although DTDA also contains disulfide bonds, its structure is relatively simple and mainly relies on the dynamic exchange of disulfide bonds to achieve self-healing, lacking additional synergy, so it performs slightly worse in terms of self-healing efficiency and improvement of mechanical properties.

[0069] As mentioned above, the above are only the preferred embodiments of the present invention and are not used to limit the present invention; however, for those of ordinary skill in the art, without departing from the scope of the technical solution of the present invention, any equivalent changes such as slight modifications, evolutions made by using the technical content disclosed above are all equivalent embodiments of the present invention; at the same time, any equivalent changes, modifications, and evolutions made to the above embodiments based on the essence of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. An anti-aging, heat-insulating and sound-insulating composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 10-20 parts of seaweed mud, 10-15 parts of ceramic hollow microspheres, 6-10 parts of ceramic fibers, 10-15 parts of environmentally friendly sound-absorbing cotton, 2-4 parts of antioxidant, 4-6 parts of modified flame retardant, 60-80 parts of modified waterproofing agent, 150-200 parts of DMF; The modified flame retardant is prepared by the following method: S1: 2-benzyloxy-5-hydroxybenzaldehyde reacts with 4,4'-diaminodiphenyl ether in the presence of glacial acetic acid as a catalyst 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 and 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide are reacted under the action of triethylamine for 16-20 hours, and then intermediate 2 is added as a capping agent to continue the reaction for 4-6 hours, and the modified flame retardant is obtained by post-treatment.

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

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

4. The anti-aging, heat-insulating and sound-insulating composite material according to claim 1, characterized in that: In step S3, the feed 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).

5. The anti-aging, heat-insulating and sound-insulating composite material according to claim 1, characterized in that: The antioxidant is one of N-isopropyl-N'-phenyl-p-phenylenediamine, N-N'-diphenyl-p-phenylenediamine and 4,4'-bis(α,α-dimethylbenzyl)diphenylamine.

6. The anti-aging, heat-insulating and sound-insulating composite material according to claim 1, characterized in that: The modified waterproofing agent is prepared by the following method: S1: Under nitrogen protection, 1,3-bis(2-isocyano-2-propyl)benzene and polytetrahydrofuran ether diol react under the action of a catalyst, dibutyltin dilaurate, to obtain a polyurethane prepolymer; S2: add octamethylcyclotetrasiloxane and dodecyl(methyl)dimethoxysilane to the reactor, stir and heat to 80-100°C, then add tetramethylammonium hydroxide, react for 2-4h, add fluorinated organosiloxane, continue to heat to 110-120°C, react for 1-3h, and obtain long-chain fluorinated organosiloxane; S3: Under nitrogen protection, polyurethane prepolymer and bis(2-amino-3-methylphenyl) disulfide undergo chain extension reaction under the action of dibutyltin dilaurate as a catalyst to obtain a polyurethane emulsion; then long-chain fluorinated organic siloxane is added for post-chain extension reaction, triethylamine is added for neutralization, and then deionized water is added for emulsification to obtain a modified waterproofing agent.

7. The anti-aging, heat-insulating and sound-insulating composite material according to claim 6, characterized in that: In step S1, the mass ratio of 1,3-bis(2-isocyanato-2-propyl)benzene and polytetrahydrofuran ether diol is (4-6):(6-10); In step S2, the mass ratio of octamethylcyclotetrasiloxane, dodecyl(methyl)dimethoxysilane and fluorine-containing organosiloxane is 10:(1-5):(2-6); In step S3, the mass ratio of the polyurethane prepolymer, bis(2-amino-3-methylphenyl) disulfide, and long-chain fluorinated organic siloxane is (15-20):1:(3-6).

8. The anti-aging, heat-insulating and sound-insulating composite material according to claim 6, characterized in that: The preparation process of the fluorinated organosiloxane is as follows: Diethyl malonate reacts with 1-iodo-1H,1H,2H,2H-perfluorooctane to generate diethyl malonate substituted with a fluorine-containing group, which is then hydrolyzed and reacted with thionyl chloride to generate an acyl chloride product, and finally the acyl chloride product is reacted with 3-aminopropyltriethoxysilane to generate a fluorine-containing organosiloxane.

9. A method for preparing the anti-aging, heat-insulating and sound-insulating composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Weigh by weight: 10-20 parts of seaweed mud, 10-15 parts of ceramic hollow microspheres, 6-10 parts of ceramic fibers, 10-15 parts of environmentally friendly sound-absorbing cotton, 2-4 parts of antioxidant, 4-6 parts of modified flame retardant, 60-80 parts of modified waterproofing agent, and 150-200 parts of DMF; (2) grinding seaweed mud and ceramic fiber, adding ceramic hollow microspheres to the grinding and stirring to obtain a mixture A; stirring and mixing an antioxidant, a modified flame retardant, a modified waterproofing agent and DMF to obtain a mixture B; and subjecting the mixtures A and B to ultrasonic mixing treatment to obtain a mixture C; (3) The mixture C is evenly applied on both sides of the surface of the environmentally friendly sound-absorbing cotton, and after drying, an anti-aging heat-insulating and sound-insulating composite material is obtained.

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