A long-lasting heat-insulating composite rock wool board and its preparation method

Abstract

The present invention discloses a long-acting heat-insulating composite rock wool board and a preparation method thereof. The composite rock wool board is composed of a modified rock wool board, an alkali-resistant fiberglass mesh cloth, a modified waterproof mortar and an interfacial agent. The modified rock wool board uses tetraethyl orthosilicate as a silicon source, and then adds trimethylchlorosilane for modification to obtain SiO2 aerogel, which is formulated into a solution, and the rock wool board is modified by an infiltration method. The modified waterproof mortar uses a phosphorus-containing hyperbranched flame retardant, polyether polyol and diphenylmethane diisocyanate as raw materials to prepare a phosphorus-containing hyperbranched flame retardant polyurethane material, and then adds filler sand and cement to prepare the modified waterproof mortar. The present invention not only greatly improves the hydrophobicity and heat-insulating performance of the rock wool board, but also improves the fireproof and flame-retardant performance, enhances the strength and elastic performance, prolongs its service life, and achieves a long-acting heat-insulating effect.

Description

Technical Field

[0001] The present invention relates to the technical field of rock wool boards, and particularly to a long - acting heat - insulating composite rock wool board and a preparation method thereof. Background Technique

[0002] Rock wool products are the main energy - saving materials in the internationally recognized "fifth conventional energy" due to their excellent fire - proof and heat - insulating properties. For every 1 ton of rock wool products used for heat insulation in buildings, at least 1 ton of oil - equivalent energy can be saved annually, which conforms to the trends of low - carbon, energy - saving, and emission reduction. However, rock wool materials are water - absorbent, and their durability is poor after being affected by moisture. This not only affects their service life and structural stability but also further affects the fire - proof and heat - insulating properties of the material, restricting its popularization and development in the field of building heat - insulating materials. Therefore, we propose a long - acting heat - insulating composite rock wool board and a preparation method thereof. Summary of the Invention

[0003] The purpose of the present invention is to provide a long - acting heat - insulating composite rock wool board and a preparation method thereof to solve the problems raised in the above - mentioned background technique.

[0004] To solve the above - mentioned technical problems, the present invention provides the following technical solution: A preparation method of a long - acting heat - insulating composite rock wool board, comprising the following steps:

[0005] (1) Making a modified rock wool board: modifying the rock wool board with SiO2 aerogel;

[0006] (2) Making a modified waterproof mortar: uniformly composed of a phosphorus - containing hyperbranched flame - retardant polyurethane material, sand, and cement;

[0007] (3) Making a composite rock wool board: laying a layer of alkali - resistant fiberglass mesh cloth flat on the upper surface of the modified rock wool board, successively coating an interface agent and the modified waterproof mortar, and drying; turning the lower surface of the modified rock wool board over, laying a layer of alkali - resistant fiberglass mesh cloth flat, successively coating an interface agent and the modified waterproof mortar, and after drying, obtaining a board, and pressing the board into shape by a laminator. The lamination pressure is 0 - 16 MPa, the hot - press pressure is 12 grades, the cold - press pressure is 5 grades. The pressure accuracy is ±0.05 MPa; the lamination temperature is 128 - 180 °C, the temperature accuracy is ±3 °C; the lamination hot - press time is 20 - 30 min, and the lamination cold - press time is 12 - 16 min.

[0008] Further, the modified rock wool board is obtained by the following process:

[0009] (1) Add tetraethyl orthosilicate to deionized water. After stirring evenly, slowly add 0.1 M HCl solution drop by drop to obtain a sol; then add 0.5 M ammonia water and continuously stir to obtain a gel; place the gel in a water bath at 50 - 60 °C for water bath aging for 24 - 48 h, then wash with deionized water and ethanol for 12 - 24 h, and then centrifuge to obtain a wet gel; soak the wet gel in a mixed solution of trimethylchlorosilane and n - hexane (volume ratio 1:5) for 12 - 24 h, then wash with n - hexane three times, and finally dry in an oven at 60 - 70 °C for 24 - 48 h to obtain SiO₂ aerogel;

[0010] (2) Prepare a solution by mixing SiO₂ aerogel and ethanol (the proportion of aerogel is 5 - 10%) as a modifier, and modify rock wool by the infiltration method. Take it out after 3 - 5 min and place it at room temperature to dry for 24 - 48 h to obtain a modified rock wool board.

[0011] Further, in step (1), the mass ratio of tetraethyl orthosilicate, isopropanol to water is 1:(1.15 - 1.2):(0.35 - 0.52).

[0012] Further, in step (1), the dosage of trimethylchlorosilane is 0.7 - 0.9 times the volume of tetraethyl orthosilicate.

[0013] Further, in step (2), the dosage of SiO₂ aerogel is 0.05 - 0.1 times the volume of ethanol.

[0014] Further, in step (2), the rock wool is cut into rock wool specimens with a size of 300 * 300 mm and a thickness of 30 mm.

[0015] Further, the preparation process of the modified waterproof mortar is as follows:

[0016] (1) Add polyether polyol (heated to 120 °C for vacuum dehydration for 2 h), phosphorus - containing hyperbranched flame retardant and N,N - dimethylacetamide (DMAc) to a completely dry four - necked flask equipped with an electric stirrer, a condenser and nitrogen protection. Mix evenly, turn on the condenser, introduce nitrogen, and heat to 70 - 80 °C; then dropwise add diphenylmethane diisocyanate (MDI) dissolved in DMAc, and finish dropping within 2 - 3 h. React at 60 - 80 °C for 2 - 3 h, then add 1,4 - butanediol, and then dropwise add MDI dissolved in DMAC, and finish dropping within 2 - 3 h; add malic acid thickener, stir at room temperature for 1 - 2 h, and cool and discharge to obtain a phosphorus - containing hyperbranched flame - retardant polyurethane material;

[0017] (2) Mix the filler sand and cement (sand∶cement = 2:1) that have passed through a 60 - mesh sieve, add the flame - retardant polyurethane material and m - phenylenediamine curing agent, and stir evenly at room temperature to obtain the modified waterproof mortar.

[0018] Further, in the step (1), the mass ratio of the polyether polyol to the diphenylmethane diisocyanate is (5.6:1) to (6.3:1).

[0019] Further, in the step (2), the content of the hyperbranched flame-retardant polyurethane material is 9-15% of the fillers (sand, cement).

[0020] Further, the preparation process of the phosphorus-containing hyperbranched flame retardant is as follows:

[0021] (1) Add water and ethanol (volume ratio 2:3) into a beaker according to the proportion, stir evenly at room temperature, then add tetrapropylammonium hydroxide (25%), diethylaminomethyltriethoxysilane and anilinomethyltrimethoxysilane, react for 10-12 h, filter by suction, and dry under vacuum to obtain the amino-containing organosilicon.

[0022] (2) First, add dimethylformamide (DMF) to 3-hydroxyphthalic anhydride and dissolve it fully; then add diisopropanolamine to a four-necked flask, stir evenly, dropwise add the fully dissolved 3-hydroxyphthalic anhydride, and react at room temperature for 3-4 h; then add the amino-containing organosilicon and p-toluenesulfonic acid, start heating, heat to 120-130 °C, carry out condensation reflux, keep warm for 6-8 h, and carry out vacuum distillation to obtain the hyperbranched polymer; add the obtained hyperbranched polymer to a four-necked flask equipped with a thermometer and a stirrer, raise the temperature to 50-60 °C, add the polyphosphoric acid reagent and p-toluenesulfonic acid, mix evenly and then raise the temperature to 70-80 °C, keep warm and react for 5-6 h, hydrolyze for 2-3 h, and carry out vacuum distillation to prepare the phosphorus-containing hyperbranched flame retardant.

[0023] Further, in the step (1), the mass ratio of the diethylaminomethyltriethoxysilane to the anilinomethyltrimethoxysilane is (1:2.5) to (1:3.0).

[0024] Further, in the step (2), the mass ratio of the 3-hydroxyphthalic anhydride to the diisopropanolamine is (1:1) to (1:1.5).

[0025] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0026] (1) By modifying the rock wool board with SiO2 aerogel, the present invention greatly improves the service life and heat preservation performance of the rock wool board. SiO2 aerogel is a superhydrophobic material with a hydrophobic angle of up to 150°, belonging to a water-repellent material. It not only has excellent thermal insulation performance, but also has good hydrophobicity, sound insulation and light transmittance. After modification, the thermal conductivity of the rock wool board decreases and the hydrophobicity improves.

[0027] (2) In the present invention, a phosphorus-containing hyperbranched flame-retardant polyurethane material is added to the mortar to improve the flame retardancy and flexibility of the composite rock wool board. The hyperbranched polymer itself has many branches and a low viscosity, which enables the hyperbranched polymer to have good compatibility with the material, reducing adverse effects on the material. At the same time, the ends of the hyperbranched polymer contain a large number of active functional groups, and its ends can be modified to introduce flame-retardant elements into the macromolecules of the hyperbranched polymer, making it a flame retardant for more materials.

[0028] (3) During the combustion process of the phosphorus-containing hyperbranched polyurethane, a dense, complete, and fluffy carbon layer will form on the surface. This carbon layer has the functions of oxygen isolation, heat insulation, and flame transmission blockage. In addition, the prominent advantage of this added phosphorus-containing flame-retardant system is that a large amount of low-toxic and harmless gases, such as N2, are released during combustion, and no secondary hazards will be formed. They will diffuse and then reduce the oxygen concentration in the air around the combustible material, thus playing a role in reducing the ignition point of the material. Under the synergistic effect of the three flame-retardant elements of nitrogen, phosphorus, and silicon, the material simultaneously has the abilities of carbonization, foaming, oxygen isolation and heat insulation, and inhibition of material degradation, etc., exerting a synergistic effect. With a high Si content, the mechanical properties such as the impact resistance and tensile properties of the substrate are significantly improved. Detailed implementation manners

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0030] In this embodiment, tetraethyl orthosilicate has a silicon content of 28% and is purchased from Shanghai Zhuorui Chemical Co., Ltd.; trimethylchlorosilane is purchased from Shandong Lilbang New Materials Co., Ltd.; ammonia water has a purity of 28% and is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; absolute ethanol is purchased from Xi'an Sanpu Chemical Reagent Co., Ltd.; n-hexane is purchased from Jilin Beihua Fine Chemical Co., Ltd.; polyether polyol has a weight-average molecular weight MW: 2000 - 3000 and is purchased from Hubei Jusheng Technology Co., Ltd.; N,N-dimethylacetamide is purchased from Shandong Jinyuanyuan New Materials Co., Ltd.; diphenylmethane diisocyanate is purchased from Shanghai Macklin Biochemical Co., Ltd.; 1,4-butanediol is purchased from Nantong Runfeng Petrochemical Co., Ltd.; malic acid is purchased from Shaanxi Fujuyuan Biotechnology Co., Ltd.; m-phenylenediamine is purchased from Jinan Century Tongda Chemical Industry Co., Ltd.; tetrapropylammonium hydroxide is purchased from Wuhan Penglei Biotechnology Co., Ltd.; diethylaminomethyltriethoxysilane is purchased from Hubei Kefule Materials Technology Co., Ltd.; anilinomethyltrimethoxysilane is purchased from Shanghai Xianghui Pharmaceutical Technology Co., Ltd.; 3-hydroxyphthalic anhydride is purchased from Shandong Xuanhong Biopharmaceutical Co., Ltd.; dimethylformamide is purchased from Shanghai Merck Chemical Technology Co., Ltd.; diisopropanolamine is purchased from Shanghai Macklin Biochemical Co., Ltd.; p-toluenesulfonic acid is purchased from Shanghai Aladdin Chemistry Co., Ltd.; polyphosphoric acid has a P2O5 content of ≥85% and is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; the alkali-resistant fiberglass mesh has a thickness of 1 mm and is purchased from Henglian Wire Mesh Products (Dalian) Co., Ltd.; interface agent: EL1230 flexible type, with a thickness of 1.5 - 3 mm, is purchased from Beijing Wotu Building Materials Co., Ltd.; the rock wool board has a thickness between 30 - 200 mm and the rock wool board is purchased from Lanning Rock Wool Sandwich Panel Factory; the modified waterproof mortar has a thickness of 6 - 8 mm.

[0031] Example 1: A preparation method of a long-acting heat-insulating composite rock wool board, comprising the following processes:

[0032] 1. The preparation process of the modified rock wool board is as follows:

[0033] (1) Take 13 g of tetraethyl orthosilicate and 15 g of isopropanol and add them to 5 ml of deionized water. After stirring evenly, gradually add 0.1 M HCl solution. When the pH value is adjusted to 3, stop adding to obtain a sol; then add 0.5 M ammonia water, continue stirring, and stop adding when the pH value is adjusted to 8 to obtain a gel; place the gel in a 50 °C water bath for water bath aging for 48 h, then wash with deionized water and ethanol for 24 h, and then centrifuge to obtain a wet gel; soak the wet gel in a mixed solution of trimethylchlorosilane and n-hexane (volume ratio 1:5) for 24 h, then wash three times with n-hexane, and finally place it in an oven at 60 °C for drying for 48 h to obtain SiO2 aerogel;

[0034] (2) Mix 10 g of SiO2 aerogel and 200 g of ethanol to prepare a solution (the proportion of aerogel is 5%) as a modifier, and modify a 300*300 mm rock wool sample by the infiltration method. Take it out after 5 minutes and dry it at room temperature for 48 hours to obtain a modified rock wool board.

[0035] 2. The preparation process of the phosphorus-containing hyperbranched flame retardant is as follows:

[0036] (1) Add 40 ml of water and 60 ml of ethanol (volume ratio 2:3) to a beaker according to the proportion, stir evenly at room temperature, then add 0.5 ml of tetrapropylammonium hydroxide (25%), 10 g of diethylaminomethyltriethoxysilane and 27 g of anilinomethyltrimethoxysilane, react for 12 h, filter by suction, and dry in vacuum to obtain an amino-containing organosilicon.

[0037] (2) First, add 10 g of dimethylformamide (DMF) to 12 g of 3-hydroxyphthalic anhydride and dissolve it fully; then add 9.7 g of diisopropanolamine to a four-necked flask, stir evenly, and dropwise add the fully dissolved 3-hydroxyphthalic anhydride, and react at room temperature for 3 h; then add 1.5 g of amino-containing organosilicon and 0.2 g of p-toluenesulfonic acid, start heating, heat to 125 °C, carry out condensation reflux, keep warm for 6 h, and carry out vacuum distillation to obtain a hyperbranched polymer; add the obtained hyperbranched polymer to a four-necked flask equipped with a thermometer and a stirrer, heat up to 50 °C, add 0.5 g of polyphosphoric acid reagent and 0.2 g of p-toluenesulfonic acid in three portions, mix evenly and then heat up to 80 °C, keep warm and react for 5 h, hydrolyze for 3 h, and carry out vacuum distillation to prepare a phosphorus-containing hyperbranched flame retardant.

[0038] 3. The preparation process of the modified waterproof mortar is as follows:

[0039] (1) Add 24 g of polyether polyol (heated to 120 °C and vacuum dehydrated for 2 h) to a completely dry four-necked flask equipped with an electric stirrer, a condenser and nitrogen protection, add 4 g of phosphorus-containing hyperbranched flame retardant and 10 g of N,N-dimethylacetamide (DMAc), mix evenly, open the condenser, introduce nitrogen, and heat up to 70 °C; then dropwise add 4 g of diphenylmethane diisocyanate (MDI) dissolved in 10 g of DMAc, add it within 2 h, react at 60 °C for 3 h, then add 3 g of 1,4-butanediol, and then dropwise add 35 g of MDI dissolved in DMAC, add it within 2 h; add 0.2 g of malic acid thickener, stir at room temperature for 1 h, cool and discharge to obtain a phosphorus-containing hyperbranched flame retardant polyurethane material.

[0040] (2) Mix 40 g of sand sieved through a 60-mesh sieve and 20 g of cement (sand∶cement = 2∶1), add 12 g of flame retardant polyurethane material and 10 g of m-xylylenediamine curing agent, and stir evenly at room temperature to obtain a modified waterproof mortar.

[0041] 4. Manufacturing the composite rock wool board: Lay a layer of alkali-resistant fiberglass mesh cloth flat on the upper surface of the modified rock wool board, coat the interface agent and modified waterproof mortar in sequence, and dry; Turn the lower surface of the modified rock wool board over, lay a layer of alkali-resistant fiberglass mesh cloth flat, coat the interface agent and modified waterproof mortar in sequence, and after drying, obtain a board, and press and form the board through a laminator. The lamination pressure is 0 - 16 MPa, the hot press pressure is grade 12, and the cold press pressure is grade 5. The pressure accuracy is ±0.05 MPa; The lamination temperature is 128 - 180 °C, and the temperature accuracy is ±3 °C; The lamination hot press time is 20 - 30 min, and the lamination cold press time is 12 - 16 min.

[0042] Example 2: A preparation method of a long-lasting heat-insulating composite rock wool board, including the following processes:

[0043] 1. The specific steps of the modified rock wool board are as follows:

[0044] (1) Take 17.3 g of tetraethyl orthosilicate and 20 g of isopropanol, add them to 6 ml of deionized water, stir evenly, and then dropwise add 0.1 M HCl solution. Stop dropping when the pH value is adjusted to 3 to obtain a sol; Then add 0.5 M ammonia water, continuously stir, and stop adding when the pH value is adjusted to 8 to obtain a gel; Put the gel into a water bath at 55 °C for water bath aging for 48 h, then wash with deionized water and ethanol for 24 h, and then centrifuge to obtain a wet gel; Immerse the wet gel in a mixed solution of trimethylchlorosilane and n-hexane (volume ratio 1:5) for 24 h, then wash with n-hexane three times, and finally dry in an oven at 60 °C for 48 h to obtain SiO2 aerogel;

[0045] (2) Mix 15 g of SiO2 aerogel and 200 g of ethanol to prepare a solution (the proportion of aerogel is 7.5%) as a modifier, and modify a 300*300 mm rock wool sample by the infiltration method. Take it out after 5 min and place it at room temperature to dry for 48 h to obtain a modified rock wool board.

[0046] 2. The preparation process of the phosphorus-containing hyperbranched flame retardant is as follows:

[0047] (1) Add 40 ml of water and 60 ml of ethanol (volume ratio 2:3) to a beaker according to the proportion, stir evenly at room temperature, then add 0.5 ml of tetrapropylammonium hydroxide (25%), 12 g of diethylaminomethyltriethoxysilane and 32.4 g of anilinomethyltrimethoxysilane, react for 12 h, filter by suction, and dry in vacuum to obtain an amino-containing silicone.

[0048] (2) First, add 10 g of dimethylformamide (DMF) to 15 g of 3-hydroxyphthalic anhydride and dissolve it thoroughly. Then, add 12.2 g of diisopropanolamine to a four-necked flask, stir evenly, and dropwise add the thoroughly dissolved 3-hydroxyphthalic anhydride, and react at room temperature for 3 h. Then, add 1.6 g of amino-containing silicone and 0.3 g of p-toluenesulfonic acid, start heating, heat to 125 °C, carry out condensation reflux, keep warm for 6 h, and perform vacuum distillation to obtain a hyperbranched polymer. Add the obtained hyperbranched polymer to a four-necked flask equipped with a thermometer and a stirrer, raise the temperature to 55 °C, add 0.6 g of polyphosphoric acid reagent and 0.3 g of p-toluenesulfonic acid in three portions, mix evenly, then raise the temperature to 80 °C, keep warm and react for 5 h, hydrolyze for 3 h, and perform vacuum distillation to prepare a phosphorus-containing hyperbranched flame retardant.

[0049] 3. The preparation process of the modified waterproof mortar is as follows:

[0050] (1) Add 30 g of polyether polyol (heated to 120 °C and vacuum dehydrated for 2 h) to a completely dry four-necked flask equipped with an electric stirrer, a condenser and nitrogen protection, add 5 g of phosphorus-containing hyperbranched flame retardant and 10 g of N,N-dimethylacetamide (DMAc), mix evenly, turn on the condenser, introduce nitrogen, and raise the temperature to 70 °C. Then, dropwise add 5 g of diphenylmethane diisocyanate (MDI) dissolved in 10 g of DMAc, add it within 2 h, react at 70 °C for 3 h, then add 3 g of 1,4-butanediol, and then dropwise add 35 g of MDI dissolved in DMAC, add it within 2 h. Add 0.2 g of malic acid thickener, stir at room temperature for 1 h, cool and discharge to obtain a phosphorus-containing hyperbranched flame retardant polyurethane material;

[0051] (2) Mix 40 g of sand passed through a 60-mesh sieve and 20 g of cement (sand∶cement = 2∶1), add 15 g of flame retardant polyurethane material and 11 g of m-xylylenediamine curing agent, and stir evenly at room temperature to obtain the modified waterproof mortar.

[0052] Other processes are the same as those in Example 1.

[0053] Example 3: A preparation method of a long-acting heat-insulating composite rock wool board, including the following processes:

[0054] 1. The specific steps of the modified rock wool board are as follows:

[0055] (1) 17.3 g of tetraethyl orthosilicate and 20 g of isopropyl alcohol were added to 6 ml of deionized water. After stirring evenly, 0.1 M HCl solution was added dropwise. When the pH value was adjusted to 3, the dropping was stopped to obtain a sol; then 0.5 M ammonia water was added and stirring was continued. When the pH value was adjusted to 8, the addition was stopped to obtain a gel; the gel was placed in a water bath at 60 °C for water bath aging for 48 h, then washed with deionized water and ethanol for 24 h, and then centrifuged to obtain a wet gel; the wet gel was immersed in a mixed solution of trimethylchlorosilane and n-hexane (volume ratio 1:5) for 24 h, then washed three times with n-hexane, and finally dried in an oven at 60 °C for 48 h to obtain SiO2 aerogel;

[0056] (2) 20 g of SiO2 aerogel and 200 g of ethanol were mixed to prepare a solution (the proportion of aerogel was 10%) as a modifier. The 300*300 mm rock wool sample was modified by the infiltration method for 5 min and then taken out. After being dried at room temperature for 48 h, a modified rock wool board was obtained.

[0057] 2. The preparation process of the phosphorus-containing hyperbranched flame retardant is as follows:

[0058] (1) 40 ml of water and 60 ml of ethanol (volume ratio 2:3) were added in proportion to a beaker and stirred evenly at room temperature. Then 0.5 ml of tetrapropylammonium hydroxide (25%), 15 g of diethylaminomethyltriethoxysilane and 40.5 g of anilinomethyltrimethoxysilane were added and reacted for 12 h. After filtration and vacuum drying, an amino-containing organosilicon was obtained.

[0059] (2) First, 15 g of dimethylformamide (DMF) was added to 18 g of 3-hydroxyphthalic anhydride and dissolved completely; then 14.8 g of diisopropanolamine was added to a four-necked flask and stirred evenly. The fully dissolved 3-hydroxyphthalic anhydride was added dropwise and reacted at room temperature for 3 h; then 1.8 g of amino-containing organosilicon and 0.4 g of p-toluenesulfonic acid were added, and heating was started. When heated to 125 °C, condensation reflux was carried out and kept warm for 6 h. After reduced pressure distillation, a hyperbranched polymer was obtained; the obtained hyperbranched polymer was added to a four-necked flask equipped with a thermometer and a stirrer, the temperature was raised to 60 °C, 0.7 g of polyphosphoric acid reagent and 0.4 g of p-toluenesulfonic acid were added in three portions, after mixing evenly, the temperature was raised to 80 °C, kept warm and reacted for 5 h, hydrolyzed for 3 h, and reduced pressure distillation was carried out to prepare a phosphorus-containing hyperbranched flame retardant.

[0060] 3. The preparation process of the modified waterproof mortar is as follows:

[0061] (1) Add 30 g of polyether polyol to a completely dry four-necked flask equipped with an electric stirrer, a condenser, and nitrogen protection. After heating to 120 °C and vacuum dehydrating for 2 h, add 5 g of a phosphorus-containing hyperbranched flame retardant and 10 g of N,N-dimethylacetamide (DMAc), mix evenly, turn on the condenser, introduce nitrogen, and raise the temperature to 70 °C; then dropwise add 5 g of diphenylmethane diisocyanate (MDI) dissolved in 10 g of DMAc, add it all within 2 h, react at 80 °C for 3 h, then add 3 g of 1,4-butanediol, and then dropwise add 35 g of MDI dissolved in DMAC, add it all within 2 h; add 0.02 g of malic acid thickener, stir at room temperature for 1 h, cool and discharge to obtain a phosphorus-containing hyperbranched flame-retardant polyurethane material;

[0062] (2) Mix 40 g of sand passed through a 60-mesh sieve and 20 g of cement (sand∶cement = 2∶1), add 20 g of the flame-retardant polyurethane material and 12 g of m-xylylenediamine curing agent, stir evenly at room temperature to obtain a modified waterproof mortar.

[0063] Other processes are the same as those in Example 1.

[0064] Comparative Example 1: A preparation method of a long-lasting heat-insulating composite rock wool board,

[0065] Compared with Example 2, in Comparative Example 1, a conventional rock wool board of the same specification is selected without SiO2 aerogel modification; other steps are the same as those in Example 2 to obtain a long-lasting heat-insulating composite rock wool board.

[0066] Comparative Example 2: A preparation method of a long-lasting heat-insulating composite rock wool board,

[0067] Compared with Example 2, in Comparative Example 2, a common mortar of the same specification is selected without adding a phosphorus-containing hyperbranched flame-retardant polyurethane material; other steps are the same as those in Example 2 to obtain a long-lasting heat-insulating composite rock wool board.

[0068] Comparative Example 3: A preparation method of a long-lasting heat-insulating composite rock wool board,

[0069] Compared with Example 2, in Comparative Example 3, in the preparation process of the modified waterproof mortar, a phosphorus-containing hyperbranched flame retardant is not added, a conventional polyurethane material of the same quality is made, and the preparation process of the phosphorus-containing hyperbranched flame retardant is deleted, and the remaining steps are the same as those in Example 2 to obtain a long-lasting heat-insulating composite rock wool board.

[0070] Experiment

[0071] Take the phosphorus-containing hyperbranched flame-retardant polyurethane materials in Examples 1-3, the phosphorus-containing hyperbranched flame-retardant polyurethane material in Comparative Example 1, and the conventional polyurethane material in Comparative Example 3, respectively prepare specimens, detect their properties and record the test results:

[0072] The combustion performance was determined according to GB / T 2408-2021 "Determination of the burning behavior of plastics (horizontal and vertical methods)". Experimental steps: Coat the prepared polyurethane material on a polytetrafluoroethylene plate to form a film, dry it overnight at 60 °C in a vacuum drying oven, cut it into square specimens of 3 cm × 3 cm after drying, install the specimens, light a Bunsen burner, align the Bunsen burner flame with the center of the lower end face of the specimen, light the specimen and conduct the determination, observe the phenomenon after the specimen burns vertically, and record the data.

[0073] Carbon layer formation UL94-V rating Example 1 Many, thick, and dense V-2 Example 2 Many, thick, and dense V-2 Example 3 Many, thick, and dense V-2 Comparative Example 1 Many and thick Insufficient rating Comparative Example 3 There is, but not in flakes Insufficient rating

[0074] Take the composite rock wool boards obtained in Examples 1-3 and Comparative Examples 1-3, prepare specimens, and detect their properties respectively and record the test results:

[0075] The hygroscopicity was determined according to GB / T 10299-2011 "Test method for water repellency of thermal insulating materials". Experimental steps: The size of the composite rock wool board specimen is 300*300 mm and the thickness is 30 mm. Under the conditions of 40 °C and a relative humidity of 90%, put the specimen into the water repellency test, and the test time is 96 hours. Measure the mass of the specimen before and after the experiment respectively.

[0076] The thermal conductivity was determined according to GB / T 10294-2008 "Determination of steady-state thermal resistance and related properties of thermal insulating materials (guarded hot plate method)". Experimental steps: The size of the specimen is 300*300 mm and the thickness is 30 mm. Weigh the specimen and calculate the density of the specimen; turn on the power supply, install the specimen according to the diagram, set the clamping force within the range of (9-18) kg, measure the thickness of the specimen; set the hot plate temperature and cold plate temperature. Set the power to the automatic function, start recording data automatically, and preliminarily estimate the power after the cold plate and hot plate temperatures are stable.

[0077] The tensile strength was determined according to GB / T 30804-2014 "Determination of tensile strength perpendicular to the surface of building thermal insulation products". Experimental steps: The size of the specimen is 300*300 mm and the thickness is 30 mm. Cure the specimens for 3 days and 28 days respectively, bond them to two rigid plates or rigid blocks, and then install them on a testing machine to conduct a tensile test at a constant speed until failure.

[0078] Record the maximum tensile load and calculate the tensile strength of the specimen.

[0079]

[0080]

[0081] According to the data in the above table, the following conclusions can be clearly obtained:

[0082] 1. Compared with Comparative Example 1, the composite rock wool boards obtained in Experimental Examples 1-3 are completely hydrophobic after being modified with SiO2 aerogel, greatly improving the hydrophobic performance of the composite rock wool boards.

[0083] 2. Compared with Examples 1-3, the combustion performance of the products obtained in Comparative Example 1 and Comparative Example 3 decreased. It can be seen that the phosphorus-containing hyperbranched flame-retardant polyurethane material in the present invention can improve the fire resistance and flame retardancy of the composite rock wool board and reduce the thermal conductivity to achieve the effect of heat preservation.

[0084] 3. Compared with Comparative Example 2, the tensile strength of Examples 1-3 increased. It can be seen that the modified waterproof mortar can increase the strength and elastic properties of the composite rock wool board and extend the service life.

[0085] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "including", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device.

[0086] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a long-acting heat-insulating composite rock wool board, characterized in that: It includes the following steps: (1) Fabricate a modified rock wool board: Modify the rock wool board with SiO2 aerogel; (2) Fabricate a modified waterproof mortar: It is composed of a phosphorus-containing hyperbranched flame-retardant polyurethane material, sand, and cement mixed evenly; (3) Fabricate a composite rock wool board: Lay a layer of alkali-resistant fiberglass mesh cloth flat on the upper surface of the modified rock wool board, coat the interface agent and the modified waterproof mortar in sequence, and dry; Turn the lower surface of the modified rock wool board over, lay a layer of alkali-resistant fiberglass mesh cloth flat, coat the interface agent and the modified waterproof mortar in sequence, and after drying, obtain a board, and press and form the board through a laminator; The preparation process of the modified waterproof mortar is as follows: (1) Mix polyether polyol, phosphorus-containing hyperbranched flame retardant, and N,N-dimethylacetamide evenly, and under a nitrogen atmosphere, heat up to 70 - 80 °C; Then dropwise add diphenylmethane diisocyanate dissolved in N,N-dimethylacetamide, and finish adding it within 2 - 3 h, react at 60 - 80 °C for 2 - 3 h, then add 1,4-butanediol, dropwise add diphenylmethane diisocyanate dissolved in N,N-dimethylacetamide, and finish adding it within 2 - 3 h, cool and discharge to obtain a phosphorus-containing hyperbranched flame-retardant polyurethane material; (2) Mix the filler sand and cement, add the phosphorus-containing hyperbranched flame-retardant polyurethane material, and stir evenly to obtain the modified waterproof mortar; The preparation process of the phosphorus-containing hyperbranched flame retardant is as follows: (1) Mix water and absolute ethanol evenly, add tetrapropylammonium hydroxide, diethylaminomethyltriethoxysilane, and anilinomethyltrimethoxysilane, react for 10 - 12 h, filter by suction, and dry in vacuum to obtain an amino-containing organosilicon; (2) Dropwise add a dimethylformamide solution of 3-hydroxyphthalic anhydride to diisopropanolamine, and react at room temperature for 2 - 3 h; Then add the amino-containing organosilicon and p-toluenesulfonic acid, heat to 120 - 130 °C, keep warm for 6 - 8 h, and distill under reduced pressure to obtain a hyperbranched polymer; (3) Add the hyperbranched polymer, heat up to 50 - 60 °C, then add a polyphosphoric acid reagent and p-toluenesulfonic acid, mix evenly and then heat up to 70 - 80 °C, keep warm and react for 3 - 5 h, hydrolyze for 2 - 3 h, and distill under reduced pressure to prepare a phosphorus-containing hyperbranched flame retardant.

2. The preparation method of a long-acting heat-insulating composite rock wool board according to claim 1, characterized in that: The preparation process of the modified rock wool board is as follows: (1) Take tetraethyl orthosilicate and isopropanol and add them to deionized water, stir evenly, and then gradually add HCl solution to obtain a sol; Then add ammonia water and continuously stir to obtain a gel; Put the gel into a water bath at 50 - 60 °C for water bath aging for 24 - 48 h, then wash with deionized water and ethanol for 12 - 24 h, and then centrifuge to obtain a wet gel; Immerse the wet gel in a mixed solution of trimethylchlorosilane and n-hexane for 12 - 24 h, then wash with n-hexane three times, and finally dry in an oven at 60 - 70 °C for 24 - 48 h to obtain SiO2 aerogel; (2) Mix SiO2 aerogel and ethanol to prepare a solution as a modifier, modify the rock wool by the infiltration method, take it out after 3 - 5 min, and place it at room temperature to dry for 24 - 48 h to obtain a modified rock wool board.

3. The preparation method of a long-acting heat-insulating composite rock wool board according to claim 2, characterized in that: The mass ratio of the tetraethyl orthosilicate, isopropanol and water is 1:(1.15 - 1.2):(0.35 - 0.52).

4. The preparation method of a long-acting heat-insulating composite rock wool board according to claim 1, characterized in that: The mass ratio of the polyether polyol and diphenylmethane diisocyanate is (5.6:1) - (6.3:1).

5. The preparation method of a long-acting heat-insulating composite rock wool board according to claim 1, characterized in that: The modified waterproof mortar comprises the following mass components: 12 - 20 parts of flame-retardant polyurethane material, 40 parts of sand, and 20 parts of cement.

6. The preparation method of a long-lasting heat-insulating composite rock wool board according to claim 1, characterized in that: The mass ratio of the 3-hydroxyphthalic anhydride and diisopropanolamine is (1:1) - (1:1.5).

7. A long-acting heat-insulating composite rock wool board prepared by the preparation method according to any one of claims 1 - 6.

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