Modified rock wool fiber base material fireproof thermal insulation composite board and preparation method thereof

Abstract

The invention discloses a modified rock wool fiber base material fireproof thermal insulation composite board and a preparation method thereof, and belongs to the field of rock wool boards. The modified rock wool fiber base material fireproof thermal insulation composite board comprises the following components in parts by weight: 60-70 parts of basalt, 3-7 parts of diabase, 15-20 parts of blast furnace slag, 3-5 parts of dolomite, 0.5-1.5 parts of borax, 1-3 parts of silica fume, 8-12 parts of a modified emulsion and 4-7 parts of a binder. Through the chemical design of the modified emulsion and the collaborative optimization of the components of the composite board, the technical problems of low strength, high brittleness and high moisture absorption of a traditional rock wool composite board are solved, the comprehensive improvement of mechanical properties, water resistance and heat insulation performance is realized, and a high-performance integrated solution is provided for a building fireproof heat insulation material.

Description

Technical Field

[0001] This invention belongs to the field of rock wool board technology, specifically referring to a modified rock wool fiber-based fireproof and heat-insulating composite board and its preparation method. Background Technology

[0002] Traditional rock wool is widely used in building exterior wall insulation systems due to its wide availability of raw materials (basalt, industrial slag), low cost, low thermal conductivity, and non-combustibility. However, its practical application reveals three major defects: insufficient mechanical properties: the fibers are only bonded by van der Waals forces, resulting in a tensile strength of only 7-10 kPa, making it susceptible to fiber detachment and hollow insulation layers due to external impacts; poor weather resistance: the hydroxyl groups (-OH) on the fiber surface are highly hydrophilic, with a water absorption rate of 5%-10%, making it prone to freeze-thaw damage in humid environments, and long-term ultraviolet radiation can cause fiber pulverization; and limited construction adaptability: the fiber diameter is large (5-15 μm), brittle, and generates a large amount of dust during cutting, which is highly irritating to the human respiratory tract. In addition, the board has low hardness, making it difficult to use directly in irregularly shaped structures.

[0003] Traditional rock wool fiber substrates can no longer meet market demands, making modification and the preparation of high-performance composite panels a hot research topic in the industry. Currently, domestic and international modification technologies for rock wool fibers mainly focus on three aspects: hydrophobic modification, interface modification, and reinforcement modification. Hydrophobic modification often uses hydrophobic reagents such as organosilanes and fluorocarbons to treat the surface of rock wool fibers, constructing a hydrophobic layer on the fiber surface through chemical bonding or physical adsorption, thereby reducing the material's water absorption rate. Interface modification introduces coupling agents to improve the interfacial bonding between rock wool fibers and the organic matrix, enhancing the compatibility and mechanical properties of the composite system. Reinforcement modification typically involves adding nanofillers and fiber reinforcements to compensate for the high brittleness of rock wool fibers, improving the material's flexural strength and toughness. In terms of composite panel preparation, single modified rock wool fiber substrates still suffer from limited functionality, failing to simultaneously meet multiple requirements such as fire resistance, thermal insulation, waterproofing, and sound insulation. Summary of the Invention

[0004] In order to overcome the shortcomings of the prior art, this invention provides a modified rock wool fiber-based fireproof and thermal insulation composite board and its preparation method. Through the chemical design of the modified emulsion and the synergistic optimization of the composite board components, this invention breaks through the technical problems of low strength, high brittleness and high moisture absorption of traditional rock wool composite boards, and achieves a comprehensive improvement in mechanical properties, water resistance and thermal insulation performance, providing a high-performance integrated solution for building fireproof and thermal insulation materials.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The present invention proposes a modified rock wool fiber-based fireproof and heat-insulating composite board, wherein the modified rock wool fiber-based fireproof and heat-insulating composite board comprises the following components in parts by weight: 60-70 parts basalt, 3-7 parts diabase, 15-20 parts blast furnace slag, 3-5 parts dolomite, 0.5-1.5 parts borax, 1-3 parts silica fume, 8-12 parts modified emulsion, and 4-7 parts binder;

[0006] Preferably, the raw materials for preparing the modified emulsion include the following components in parts by weight: 10-12 parts KH550, 7.0-15.6 parts tetraethyl orthosilicate, 5-7.5 parts maleic anhydride, 8-11 parts diallyl bisphenol A, and 6-7 parts polyetheramine;

[0007] Preferably, the solid content of the modified emulsion is 5%-10%;

[0008] Preferably, the method for preparing the modified emulsion specifically includes the following steps:

[0009] S1. Dissolve KH550 and tetraethyl orthosilicate in anhydrous ethanol, add deionized water, mix well, raise the reaction temperature to carry out polycondensation reaction, after the reaction is completed, cool, and distill under reduced pressure to obtain amino-modified branched polysiloxane.

[0010] Preferably, in step S1, the volume ratio between deionized water and tetraethyl orthosilicate is 11:4.5-7.5;

[0011] Preferably, in step S1, the reaction temperature of the polycondensation reaction is 50-80°C, and the reaction time of the polycondensation reaction is 4-8 hours.

[0012] S2. Dissolve the amino-modified branched polysiloxane prepared in step S1 in DMAc, dissolve maleic anhydride in DMAc, and add it dropwise to the reaction system. After stirring evenly, add toluene and carry out the ring-opening reaction at room temperature. After the reaction is completed, add p-toluenesulfonic acid, raise the reaction temperature and carry out the reflux reaction. After the reaction is completed, cool, add saturated sodium bicarbonate aqueous solution to neutralize the reaction system, add ethyl acetate for extraction, allow to stand and separate into layers, collect the organic phase, wash, dry and obtain maleimide-modified polysiloxane.

[0013] Preferably, in step S2, the mass of p-toluenesulfonic acid added is 1%-3% of the mass of maleic anhydride;

[0014] Preferably, in step S2, the reaction time for the ring-opening reaction is 3-4 hours;

[0015] Preferably, in step S2, the reflux reaction temperature is 110-120℃, and the reflux reaction time is 4-6h;

[0016] S3. Dissolve the maleimide-modified polysiloxane and diallyl bisphenol A prepared in step S2 in DMAc, mix them evenly, raise the reaction temperature to carry out the prepolymerization reaction, after the reaction is completed, cool, add polyetheramine, mix them evenly, raise the reaction temperature to carry out the addition reaction, after the reaction is completed, cool, add DMAc to adjust the solid content to 5%-10%, and obtain the modified emulsion.

[0017] Preferably, in step S3, the polyetheramine includes at least one of polyetheramine D230 and polyetheramine D400;

[0018] Preferably, in step S3, the reaction temperature of the prepolymerization reaction is 150-160℃, and the reaction time of the prepolymerization reaction is 0.5-1.0h;

[0019] Preferably, in step S3, the reaction temperature of the addition reaction is 80-100℃, and the reaction time of the addition reaction is 1-2 hours;

[0020] This invention also provides a method for preparing a modified rock wool fiber-based fireproof and heat-insulating composite board, specifically including the following steps:

[0021] ① After crushing and grinding basalt, diabase, blast furnace slag, dolomite, borax and silica fume, they are put into a melting furnace according to the weight proportions. The temperature is raised and maintained to melt the raw materials. After melting, the raw materials are spun into fibers by a four-roll centrifuge. After cooling, the fibers are collected and air-classified to obtain high-adhesion rock wool fibers.

[0022] Preferably, in step ①, the melting temperature is 1450-1500℃ and the melting time is 30-40 min;

[0023] ② Take the high-adhesion rock wool fiber prepared in step ① and put it into the impregnation tank. Add the modified emulsion, turn on the stirring, and perform vacuum treatment. After impregnation for 20-30 minutes, perform drying treatment and pre-crosslinking treatment to obtain modified rock wool fiber.

[0024] Preferably, in step ②, the drying temperature is 50-60℃ and the drying time is 1-2 hours;

[0025] Preferably, in step ②, the temperature of the pre-crosslinking treatment is 70-80℃, and the time of the pre-crosslinking treatment is 0.5-1.5h;

[0026] ③ Put the modified rock wool fiber prepared in step ② into the kneader, start the stirring and spray the binder, so that the rock wool fiber is kneaded into flocs and then poured into the pendulum felting machine to spread it into fiber felt.

[0027] ④ After stacking the fiber felt prepared in step ③, adjust the hot pressing parameters, hot press to form, cool naturally, demold, cut, and polish to obtain the modified rock wool fiber substrate fireproof and heat-insulating composite board.

[0028] The beneficial effects achieved by this invention are as follows:

[0029] This invention provides a modified rock wool fiber-based fireproof and thermal insulation composite board and its preparation method. By chemically designing the modified emulsion and synergistically optimizing the components of the composite board, this invention overcomes the technical problems of low strength, high brittleness, and high moisture absorption of traditional rock wool composite boards, achieving a comprehensive improvement in mechanical properties, water resistance, and thermal insulation performance, and providing a high-performance integrated solution for building fireproof and thermal insulation materials. In this invention, KH550 (γ-aminopropyltriethoxysilane) undergoes polycondensation with tetraethyl orthosilicate to form an amino-modified branched polysiloxane, providing active sites for subsequent reactions. The amino-modified polysiloxane undergoes a ring-opening reaction with maleic anhydride, followed by reflux dehydration to generate maleimide-modified polysiloxane. The maleimide groups are copolymerized with diallyl bisphenol A free radicals, while polyetheramines D230 / D400 are introduced to form a three-dimensional cross-linked network. The siloxane bonds of KH550 condense with Si-OH on the surface of rock wool fibers to construct fiber-emulsion-resin covalent bonds, enhancing interfacial bonding. Diallyl bisphenol A forms a rigid cross-linked network to ensure strength, while polyetheramine introduces flexible segments to alleviate stress concentration, solving the problem of traditional rock wool being brittle and easily broken. After KH550 condensation, a hydrophobic layer (terminal methyl groups facing outwards) is formed on the fiber surface. The hydrophobic groups of the benzene ring of diallyl bisphenol A are exposed on the surface through a cross-linking network. The ether bonds of polyetheramine moderately retain hydrophilicity to balance stress, synergistically reducing moisture absorption. In this invention, basalt and diabase provide a high-melting-point silicate framework, blast furnace slag refines the grains, dolomite adjusts the melt viscosity, borax decomposes at high temperature to generate a B2O3 glassy protective layer, silica fume fills the pores and inhibits heat conduction. The basalt / diabase matrix, the borax glassy layer, and the phenolic resin high-temperature carbonized carbon layer form a triple fire barrier, improving fire resistance. Attached Figure Description

[0030] Figure 1 The mechanical properties of the composite plates prepared in Examples 1-3 and Comparative Examples 1-3 of this invention are shown in the figure.

[0031] Figure 2 The graph shows the water resistance results of the composite panels prepared in Examples 1-3 and Comparative Examples 1-3 of this invention.

[0032] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the embodiments of the invention to explain the invention and do not constitute a limitation thereof. Detailed Implementation

[0033] The specific embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort fall within the protection scope of the present invention.

[0034] In this invention, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The preferred embodiments and materials described in this invention are merely illustrative and not intended to limit the invention; any methods or materials identical or equivalent to those described herein may be applied.

[0035] Unless otherwise specified, the experimental methods described in the following embodiments of the present invention are all conventional experimental methods in the relevant field; the reagents and materials used are all commercially available products.

[0036] Example 1

[0037] This embodiment provides a modified rock wool fiber-based fireproof and heat-insulating composite board, which comprises the following components in parts by weight: 70 parts basalt, 5 parts diabase, 20 parts blast furnace slag, 3 parts dolomite, 1 part borax, 2 parts silica fume, 12 parts modified emulsion, and 5 parts phenolic resin binder.

[0038] The raw materials for preparing the modified emulsion include the following components in parts by weight: 11 parts KH550, 7.0-15.6 parts tetraethyl orthosilicate, 5 parts maleic anhydride, 8 parts diallyl bisphenol A, and 6 parts polyetheramine;

[0039] The preparation method of the modified emulsion specifically includes the following steps:

[0040] S1. Accurately weigh 11g of KH550 and 7.0g of tetraethyl orthosilicate into a flask, add 50mL of anhydrous ethanol, stir at 300rpm until the reactants are completely dissolved, add 7.5mL of deionized water, mix well, raise the reaction temperature to 60℃ to carry out polycondensation reaction, react for 6h, after the reaction is completed, wait for the reaction system to cool to room temperature, and then distill under reduced pressure to obtain amino-modified branched polysiloxane;

[0041] S2. Accurately weigh the amino-modified branched polysiloxane prepared in step S1 into a flask, add 50 mL of DMAc, and stir until the amino-modified branched polysiloxane is fully dissolved. Then, take 5.0 g of maleic anhydride and place it in a 20 mL flask. In DMAc, maleic anhydride was stirred at 40°C until completely dissolved. Then, it was added dropwise to the reaction system at a rate of 1 mL / min. After stirring at 300 rpm until the reaction system was homogeneous, 20 mL of toluene was added. The ring-opening reaction was carried out under continuous stirring at room temperature for 3 hours. After the reaction was completed, 0.15 g of p-toluenesulfonic acid was added to the reaction system. A reflux apparatus was installed, and the reaction temperature was raised to 115°C. The reaction was carried out under reflux with continuous stirring for 6 hours. After the reaction was completed, the reaction system was allowed to cool naturally to room temperature. Saturated sodium bicarbonate solution was added to the reaction system and thoroughly mixed to adjust the reaction system to neutral. Ethyl acetate was added and extracted three times. The organic phase was collected, washed twice with distilled water, dried with anhydrous sodium sulfate, filtered, and the filtrate was collected. The filtrate was then distilled under reduced pressure and dried under vacuum at 60°C for 12 hours to obtain maleimide-modified polysiloxane.

[0042] S3. Accurately weigh 8.0 g of maleimide-modified polysiloxane and diallyl bisphenol A prepared in step S2 into a flask, add 20 mL of DMAc, stir at 300 rpm to fully disperse the reactants, raise the reaction temperature to 150°C, maintain the constant temperature for prepolymerization reaction for 0.5 h. After the reaction is completed, wait for the reaction system to cool to 80°C, add 6.0 g of polyetheramine D230 to the reaction system, maintain the reaction temperature at 80°C for addition reaction for 2 h. After the reaction is completed, wait for the reaction system to cool naturally to 40°C, add DMAc to adjust the solid content to 10%, continue stirring, mix to form a homogeneous system, and obtain the modified emulsion.

[0043] This invention also provides a method for preparing a modified rock wool fiber-based fireproof and heat-insulating composite board, specifically including the following steps:

[0044] ① Take basalt and crush it to 5cm, diabase and crush it to 3cm, and ball mill silica fume to D50=1μm. Grind dolomite and borax and pass them through a 200-mesh sieve. Take basalt, diabase, blast furnace slag, dolomite, borax and silica fume according to the weight proportions and put them into a melting furnace. Raise the temperature to 1450℃ and keep the temperature for 40min. After melting the raw materials, pass them through a four-roll centrifuge at 2800rpm to spin them into fibers. After cooling, collect the fibers and obtain high-adhesion rock wool fibers after air classification.

[0045] ② Take the high-adhesion rock wool fiber prepared in step ① and put it into the impregnation tank. Add the modified emulsion, turn on the stirring, stir at 100 rpm and vacuum treatment. After impregnation for 20 min, dry it. After vacuum drying at 60℃ for 1 h, perform pre-crosslinking treatment in a nitrogen atmosphere and keep it at 70℃ for 1.5 h to obtain modified rock wool fiber.

[0046] ③ Put the modified rock wool fiber prepared in step ② into the kneader, start the stirring, stir at 60 rpm, dilute the phenolic resin with water to make a 10% binder solution and spray the binder, so that the rock wool fiber is kneaded into flocs and then poured into the pendulum felting machine to lay the fiber felt.

[0047] ④ After stacking the fiber felt prepared in step ③, adjust the hot pressing parameters: pressure 5MPa, temperature 150℃, heating rate 5℃ / min, holding time 10min. After hot pressing and molding, allow it to cool naturally, demold, cut, and polish to obtain the modified rock wool fiber substrate fireproof and heat-insulating composite board.

[0048] Example 2

[0049] This embodiment provides a modified rock wool fiber-based fireproof and heat-insulating composite board, which comprises the following components in parts by weight: 65 parts basalt, 3 parts diabase, 17 parts blast furnace slag, 4 parts dolomite, 0.5 parts borax, 1 part silica fume, 10 parts modified emulsion, and 4 parts phenolic resin binder.

[0050] The raw materials for preparing the modified emulsion include the following components in parts by weight: 10 parts KH550, 10.5 parts tetraethyl orthosilicate, 6 parts maleic anhydride, 11 parts diallyl bisphenol A, and 7 parts polyetheramine.

[0051] The preparation method of the modified emulsion specifically includes the following steps:

[0052] S1. Accurately weigh 10g of KH550 and 10.5g of tetraethyl orthosilicate into a flask, add 50mL of anhydrous ethanol, stir at 300rpm until the reactants are completely dissolved, add 6.0mL of deionized water, mix well, raise the reaction temperature to 50℃ to carry out polycondensation reaction, react for 8h, after the reaction is completed, wait for the reaction system to cool to room temperature, and then distill under reduced pressure to obtain amino-modified branched polysiloxane;

[0053] S2. Accurately weigh the amino-modified branched polysiloxane prepared in step S1 into a flask, add 50 mL of DMAc, and stir until the amino-modified branched polysiloxane is fully dissolved. Then, take 6.0 g of maleic anhydride and place it in a 20 mL flask. In DMAc, maleic anhydride was stirred at 40°C until completely dissolved. Then, it was added dropwise to the reaction system at a rate of 1 mL / min. After stirring at 300 rpm until the reaction system was homogeneous, 20 mL of toluene was added. The ring-opening reaction was carried out under continuous stirring at room temperature for 3.5 h. After the reaction was completed, 0.12 g of p-toluenesulfonic acid was added to the reaction system. A reflux apparatus was installed, and the reaction temperature was raised to 120°C. The reaction was carried out under reflux with continuous stirring for 4 h. After the reaction was completed, the reaction system was allowed to cool naturally to room temperature. Saturated sodium bicarbonate solution was added to the reaction system and thoroughly mixed to adjust the reaction system to neutral. Ethyl acetate was added and extracted three times. The organic phase was collected, washed twice with distilled water, dried with anhydrous sodium sulfate, filtered, and the filtrate was collected. The filtrate was then distilled under reduced pressure and dried under vacuum at 60°C for 12 h to obtain maleimide-modified polysiloxane.

[0054] S3. Accurately weigh 11g of maleimide-modified polysiloxane and diallyl bisphenol A prepared in step S2 into a flask, add 20mL of DMAc, stir at 300rpm to fully disperse the reactants, raise the reaction temperature to 160℃, maintain the constant temperature for prepolymerization reaction for 0.5h. After the reaction is completed, wait for the reaction system to cool to 90℃, add 7.0g of polyetheramine D400 to the reaction system, maintain the reaction temperature at 80℃ for addition reaction for 1.5h. After the reaction is completed, wait for the reaction system to cool naturally to 40℃, add DMAc to adjust the solid content to 5%, continue stirring, mix to form a homogeneous system, and obtain the modified emulsion.

[0055] This invention also provides a method for preparing a modified rock wool fiber-based fireproof and heat-insulating composite board, specifically including the following steps:

[0056] ① Take basalt and crush it to 5cm, diabase and crush it to 3cm, and ball mill silica fume to D50=1μm. Grind dolomite and borax and pass them through a 200-mesh sieve. Take basalt, diabase, blast furnace slag, dolomite, borax and silica fume according to the weight proportions and put them into a melting furnace. Raise the temperature to 1500℃ and keep the temperature for 30min. After melting the raw materials, pass them through a four-roll centrifuge at 2800rpm to spin them into fibers. After cooling, collect the fibers and obtain high-adhesion rock wool fibers after air classification.

[0057] ② Take the high-adhesion rock wool fiber prepared in step ① and put it into the impregnation tank. Add the modified emulsion, turn on the stirring, stir at 100 rpm and vacuum treatment. After impregnation for 30 min, dry it. After vacuum drying at 50℃ for 1.5 h, perform pre-crosslinking treatment in nitrogen atmosphere and keep it at 75℃ for 1 h to obtain modified rock wool fiber.

[0058] ③ Put the modified rock wool fiber prepared in step ② into the kneader, start the stirring, stir at 60 rpm, dilute the phenolic resin with water to make a 10% binder solution and spray the binder, so that the rock wool fiber is kneaded into flocs and then poured into the pendulum felting machine to lay the fiber felt.

[0059] ④ After stacking the fiber felt prepared in step ③, adjust the hot pressing parameters: pressure 5MPa, temperature 150℃, heating rate 5℃ / min, holding time 10min. After hot pressing and molding, allow it to cool naturally, demold, cut, and polish to obtain the modified rock wool fiber substrate fireproof and heat-insulating composite board.

[0060] Example 3

[0061] This embodiment provides a modified rock wool fiber-based fireproof and heat-insulating composite board, which comprises the following components in parts by weight: 60 parts basalt, 7 parts diabase, 15 parts blast furnace slag, 5 parts dolomite, 1.5 parts borax, 3 parts silica fume, 8 parts modified emulsion, and 7 parts phenolic resin binder.

[0062] The raw materials for preparing the modified emulsion include the following components in parts by weight: 12 parts KH550, 15.6 parts tetraethyl orthosilicate, 7.5 parts maleic anhydride, 9.5 parts diallyl bisphenol A, and 6.5 parts polyetheramine;

[0063] The preparation method of the modified emulsion specifically includes the following steps:

[0064] S1. Accurately weigh 12g of KH550 and 15.6g of tetraethyl orthosilicate into a flask, add 50mL of anhydrous ethanol, stir at 300rpm until the reactants are completely dissolved, add 4.5mL of deionized water, mix well, raise the reaction temperature to 80℃ to carry out polycondensation reaction, react for 4h, after the reaction is completed, wait for the reaction system to cool to room temperature, and then distill under reduced pressure to obtain amino-modified branched polysiloxane;

[0065] S2. Accurately weigh the amino-modified branched polysiloxane prepared in step S1 into a flask, add 50 mL of DMAc, and stir until the amino-modified branched polysiloxane is fully dissolved. Then, take 7.5 g of maleic anhydride and place it in a 20 mL flask. In DMAc, maleic anhydride was stirred at 40°C until completely dissolved. Then, it was added dropwise to the reaction system at a rate of 1 mL / min. After stirring at 300 rpm until the reaction system was homogeneous, 20 mL of toluene was added. The ring-opening reaction was carried out under continuous stirring at room temperature for 4 hours. After the reaction was completed, 0.075 g of p-toluenesulfonic acid was added to the reaction system. A reflux apparatus was installed, and the reaction temperature was raised to 115°C. The reaction was carried out under reflux with continuous stirring for 5 hours. After the reaction was completed, the reaction system was allowed to cool naturally to room temperature. Saturated sodium bicarbonate solution was added to the reaction system and thoroughly mixed to adjust the reaction system to neutral. Ethyl acetate was added and extracted three times. The organic phase was collected, washed twice with distilled water, dried with anhydrous sodium sulfate, filtered, and the filtrate was collected. The filtrate was then distilled under reduced pressure and dried under vacuum at 60°C for 12 hours to obtain maleimide-modified polysiloxane.

[0066] S3. Accurately weigh 9.5g of maleimide-modified polysiloxane and diallyl bisphenol A prepared in step S2 into a flask, add 20mL of DMAc, stir at 300rpm to fully disperse the reactants, raise the reaction temperature to 150℃, maintain the constant temperature for prepolymerization reaction for 1h. After the reaction is completed, wait for the reaction system to cool to 100℃, add 3.5g of polyetheramine D230 and 3.0g of polyetheramine D400 to the reaction system, maintain the reaction temperature at 80℃ for addition reaction for 1h. After the reaction is completed, wait for the reaction system to cool naturally to 40℃, add DMAc to adjust the solid content to 7.5%, continue stirring, mix to form a homogeneous system, and obtain the modified emulsion.

[0067] This invention also provides a method for preparing a modified rock wool fiber-based fireproof and heat-insulating composite board, specifically including the following steps:

[0068] ① Take basalt and crush it to 5cm, diabase and crush it to 3cm, and ball mill silica fume to D50=1μm. Grind dolomite and borax and pass them through a 200-mesh sieve. Take basalt, diabase, blast furnace slag, dolomite, borax and silica fume according to the weight proportions and put them into a melting furnace. Raise the temperature to 1500℃ and keep the temperature for 40min. After melting the raw materials, pass them through a four-roll centrifuge at 2800rpm to spin them into fibers. After cooling, collect the fibers and obtain high-adhesion rock wool fibers after air classification.

[0069] ② Take the high-adhesion rock wool fiber prepared in step ① and put it into the impregnation tank. Add the modified emulsion, turn on the stirring, stir at 100 rpm and vacuum treatment. After impregnation for 25 min, dry it. After vacuum drying at 55℃ for 2 h, perform pre-crosslinking treatment in a nitrogen atmosphere and keep it at 80℃ for 0.5 h to obtain modified rock wool fiber.

[0070] ③ Put the modified rock wool fiber prepared in step ② into the kneader, start the stirring, stir at 60 rpm, dilute the phenolic resin with water to make a 10% binder solution and spray the binder, so that the rock wool fiber is kneaded into flocs and then poured into the pendulum felting machine to lay the fiber felt.

[0071] ④ After stacking the fiber felt prepared in step ③, adjust the hot pressing parameters: pressure 5MPa, temperature 150℃, heating rate 5℃ / min, holding time 10min. After hot pressing and molding, allow it to cool naturally, demold, cut, and polish to obtain the modified rock wool fiber substrate fireproof and heat-insulating composite board.

[0072] Comparative Example 1

[0073] This comparative example provides a composite plate and its preparation method. The only difference between this example and Example 1 is that the raw materials for preparing the modified emulsion do not include polyetheramine, while the remaining components and their contents are the same as in Example 1.

[0074] Comparative Example 2

[0075] This comparative example provides a composite plate and its preparation method. The only difference between this example and Example 1 is that the raw materials for preparing the modified emulsion do not include diallyl bisphenol A, while the other components and their contents are the same as in Example 1.

[0076] Comparative Example 3

[0077] This comparative example provides a composite board and its preparation method. The only difference between this example and Example 1 is that the raw materials for preparing the composite board do not include modified emulsion, while the other components and their contents are the same as in Example 1.

[0078] Experimental Example 1

[0079] This experiment tests the mechanical properties of the composite plates prepared in Examples 1-3 and Comparative Examples 1-3:

[0080] 1. Compressive Strength Test: 100mm × 100mm × 50mm cubic specimens were cut from the composite plates prepared in Examples 1-3 and Comparative Examples 1-3, with at least 5 parallel specimens prepared for each group. The specimen surface must be flat, free of cracks and missing corners. The edges were sanded to an error ≤ 0.5mm. An electronic universal testing machine equipped with compressive strength fixtures was used. The specimen was placed in the center of the bearing surface of the testing machine, ensuring uniform load distribution. The loading rate was set to 2mm / min. The testing machine was started and loaded at a uniform speed. The maximum load F at specimen failure was recorded. max (Unit: N), calculate the compressive strength using the following formula:

[0081] ;

[0082] Where, σ c S is the compressive strength (unit: MPa), and S is the area of ​​the specimen subjected to pressure (unit: mm). 2 );

[0083] 2. Flexural Strength Test: 200mm × 50mm × 50mm rectangular specimens were cut from the composite plates prepared in Examples 1-3 and Comparative Examples 1-3, with at least 5 parallel specimens per group. The specimen surface must be flat, free of cracks and missing corners. The edges were sanded to an error ≤ 0.5mm. An electronic universal testing machine equipped with a three-point bending fixture was used, with a support span of 150mm. The specimen was placed on the support, and the load was applied to the midpoint of the specimen. The loading rate was set to 1mm / min, and the load was applied uniformly until the specimen fractured. The maximum load F at fracture was recorded. b (Unit: N), calculate the flexural strength using the following formula:

[0084] ;

[0085] Where σ b 1. Flexural strength (MPa); L. Support span (mm); b. Specimen width (mm); h. Specimen height (mm).

[0086] 3. Impact toughness test: 120mm × 15mm × 10mm cuboid specimens were cut from the composite plates prepared in Examples 1-3 and Comparative Examples 1-3, with at least 5 parallel specimens per group. The specimen surface must be flat, free of cracks and missing corners. The edges were sanded to an error ≤0.5mm. A pendulum impact testing machine was used. The specimen was placed on a simply supported beam support of the testing machine with a span of 70mm. The pendulum was raised to a predetermined height, and then released to impact the midpoint of the specimen. The impact absorption energy A displayed by the testing machine was recorded. k (Unit: kJ), calculate the impact toughness using the following formula:

[0087] ;

[0088] Where, α k Impact toughness (unit: kJ / m) 2 S is the impact area of ​​the specimen (unit: m²). 2 );

[0089] Figure 1 The figures show the mechanical properties of the composite boards prepared in Examples 1-3 and Comparative Examples 1-3 of this invention. As shown, Example 2 is the best, while Example 3 is slightly worse. Comparative Example 1 lacks polyetheramine (flexible segments), which undergoes an addition reaction with maleimide-modified polysiloxane and diallyl bisphenol A in step S3 of the modified emulsion, thus alleviating stress concentration. Comparative Example 2 lacks diallyl bisphenol A (crosslinking monomer), which copolymerizes with maleimide groups in step S3 to construct a three-dimensional crosslinking network. After its absence, the crosslinking density is significantly reduced, and internal defects increase. Comparative Example 3 did not add modified emulsion, and the surface of the rock wool fiber was not chemically modified. It only relied on physical bonding with the phenolic resin, and there were a large number of microcracks and weak bonding areas at the interface. The modified emulsion enhances performance through the synergistic effect of multiple components. The siloxane bonds of KH550 strengthen the chemical bonding of the fiber-resin interface, tetraethyl orthosilicate improves heat resistance, maleic anhydride / maleimide constructs reactive sites, diallyl bisphenol A forms a three-dimensional cross-linked network to ensure rigidity, and polyetheramine introduces flexible segments to alleviate stress concentration, ultimately achieving a balance between strength and toughness.

[0090] Experiment Example 2

[0091] The thermal insulation performance of the composite panels prepared in Examples 1-3 and Comparative Examples 1-3 was tested. Thermal insulation performance is characterized by thermal conductivity, which is a core indicator of thermal insulation materials. The steady-state heat flow method was used for testing. Samples measuring 300mm × 300mm × 20mm were cut from the composite panels prepared in Examples 1-3 and Comparative Examples 1-3, with at least two parallel samples per group. The sample surfaces were flat and free of pores. Before testing, the samples were pretreated for 24 hours at 23℃±2℃ and 50%±5% relative humidity. Using a thermal conductivity meter, the samples were placed between the hot and cold plates of the heat flow meter. The temperature difference between the hot and cold plates was set to 20℃ (hot plate temperature 35℃, cold plate temperature 15℃). The equipment was started, and the heat flow density q (unit: W / m³) was recorded after the heat flow density and temperature reached a stable state (heat flow fluctuation ≤1%). 2 Calculate the thermal conductivity λ using the following formula;

[0092] ;

[0093] Where λ is the thermal conductivity (unit: W / (m·K)), d is the sample thickness (unit: m); ΔT is the temperature difference between the hot and cold plates (unit: K).

[0094] The thermal conductivity of the composite plates prepared in Examples 1-3 and Comparative Examples 1-3 is shown in the table below:

[0095]

[0096] Thermal conductivity is a core indicator of thermal insulation materials, depending on the material's porosity, pore size distribution, fiber-resin interface bonding state, and the content of low thermal conductivity phases. Rock wool itself has a porous fiber structure (air thermal conductivity ≈ 0.026 W / (m·K)). Modification treatment indirectly controls the overall thermal insulation performance by changing the fiber surface properties, binder dosage, and crosslinking density. In Examples 1-3, the thermal conductivity remained below 0.04 W / (m·K), meeting the requirements of Class A thermal insulation materials in the national standard. The modified emulsion enhanced the chemical bonding of the fiber-resin interface through KH550 siloxane bonds, appropriately increasing the bulk density (reducing ineffective pores) while retaining the micropores between fibers (air phase dominates thermal insulation), thus stabilizing the thermal conductivity within a reasonable range. Comparative Example 1 lacks polymer... The presence of ether amine (flexible segments) in the modified emulsion prevents the introduction of flexible segments in step S3, resulting in a harder film-forming emulsion, increased rigidity of the fiber surface coating, tighter inter-fiber bonding, increased bulk density, and a reduced proportion of air phase. Comparative Example 2, lacking diallyl bisphenol A (crosslinking monomer), results in a lower crosslinking density in the modified emulsion (free radical copolymerization is hindered in step S3), a looser fiber surface coating network, weaker inter-fiber bonding, lower bulk density, slightly increased porosity, and slightly lower thermal conductivity. Comparative Example 3 exhibits the lowest thermal conductivity. Without the addition of modified emulsion, the rock wool fibers are only physically impregnated (phenolic resin bonding), without chemical surface modification. This leads to weak inter-fiber bonding, low bulk density, increased porosity, and more air trapped between fibers, resulting in a significant decrease in thermal conductivity.

[0097] Experimental Example 3

[0098] This experiment tests the water resistance of the composite boards prepared in Examples 1-3 and Comparative Examples 1-3. Moisture absorption is characterized by water absorption rate and moisture absorption percentage, reflecting the composite board's ability to absorb water in a humid environment, directly affecting the stability of its thermal insulation performance. Samples of 100mm × 100mm × 20mm were cut from the composite boards prepared in Examples 1-3 and Comparative Examples 1-3, with at least three parallel samples per group. The samples were dried to constant weight (drying in a 105℃ oven for 24 hours, then weighed after cooling, recorded as m0). The samples were completely immersed in deionized water, with the water level 20mm above the sample, for 24 hours. The samples were then removed, the surface water was wiped off with a damp cloth, and the samples were immediately weighed, recorded as m1. Another identical sample was placed in a constant temperature and humidity chamber at a temperature of 23℃ ± 2℃ and a relative humidity of 75% ± 5%, and left to stand for 72 hours. The samples were then removed and quickly weighed, recorded as m2. The water absorption rate (W) was calculated according to the following formula. a ,%) and moisture absorption rate (W h ,%):

[0099] ;

[0100] ;

[0101] Figure 2 The figures show the water resistance results of the composite boards prepared in Examples 1-3 and Comparative Examples 1-3 of this invention. As shown in the figures, the water absorption rate and moisture absorption rate of Examples 1-3 are both at a low level. The modified emulsion constructs a dense hydrophobic crosslinked film on the surface of rock wool fibers. In Example 2, polyetheramine is replaced with long-chain D400, which has a stronger hydrophobic effect of polyether segments. The amount of diallyl bisphenol A is increased, and the density of the crosslinked network is higher. The barrier performance of the hydrophobic film is better than that of Example 1. In Example 3, the amount of tetraethyl orthosilicate is the highest, the branching degree of amino-modified branched polysiloxane is the largest, the density of maleimide groups introduced after the reaction with maleic anhydride is the highest, and the crosslinked network formed in the prepolymerization stage is the densest. In Comparative Example 1, the modified emulsion prepolymerized only formed linear maleimide-modified polysiloxane, which could not construct a three-dimensional cross-linked network. It exhibited poor film-forming properties and the film layer contained numerous micropores. The interfacial bonding with rock wool fibers relied solely on hydrogen bonding, making the film layer prone to detachment. Moisture could penetrate through the micropores and fiber fissures. In Comparative Example 2, the prepolymerization stage lacked free radical copolymerization between allyl double bonds and maleimide double bonds. The modified emulsion lacked a cross-linked network and remained only a linear polymer, unable to form a continuous hydrophobic film on the fiber surface. The interfacial bonding force between the polymer and the fiber is extremely weak. After hot pressing, it is easy to peel off from the fiber surface, and the micropores on the fiber surface are completely exposed, allowing water to penetrate freely. In Comparative Example 3, phenolic resin is directly bonded to rock wool fiber. Although phenolic resin has a certain degree of hydrophobicity, its interfacial compatibility with inorganic fibers is poor, and it cannot effectively wet the fiber surface. It can only fill some of the large pores and cannot seal the nanoscale micropores on the fiber surface. After hot pressing, there are a large number of gaps at the interface between fibers, and water can quickly penetrate through capillary action.

[0102] Although the present invention has been shown and described through specific embodiments, those skilled in the art should understand that various changes, adjustments, substitutions and improvements can be made to the embodiments without departing from the technical concept and protection spirit of the present invention.

[0103] The descriptions and accompanying drawings in this specification are not intended to limit the scope of this invention, and the actual applications and implementations of this invention are diverse. Any technical solutions that are substantially the same as those of this invention, obtained by those skilled in the art based on the technical teachings of this invention without any inventive effort, should be included within the protection scope of this invention.

Claims

1. A modified rock wool fiber-based fireproof and heat-insulating composite board, characterized in that: The modified rock wool fiber-based fireproof and heat-insulating composite board comprises the following components in parts by weight: 60-70 parts basalt, 3-7 parts diabase, 15-20 parts blast furnace slag, 3-5 parts dolomite, 0.5-1.5 parts borax, 1-3 parts silica fume, 8-12 parts modified emulsion, and 4-7 parts binder; the raw materials for preparing the modified emulsion comprise the following components in parts by weight: 10-12 parts KH550, 7.0-15.6 parts tetraethyl orthosilicate, 5-7.5 parts maleic anhydride, 8-11 parts diallyl bisphenol A, and 6-7 parts polyetheramine; the solid content of the modified emulsion is 5%-10%.

2. The modified rock wool fiber-based fireproof and heat-insulating composite board according to claim 1, characterized in that: The preparation method of the modified emulsion specifically includes the following steps: S1. Dissolve KH550 and tetraethyl orthosilicate in anhydrous ethanol, add deionized water, mix well, raise the reaction temperature to carry out polycondensation reaction, after the reaction is completed, cool, and distill under reduced pressure to obtain amino-modified branched polysiloxane. S2. Dissolve the amino-modified branched polysiloxane prepared in step S1 in DMAc, dissolve maleic anhydride in DMAc, and add it dropwise to the reaction system. After stirring evenly, add toluene and carry out the ring-opening reaction at room temperature. After the reaction is completed, add p-toluenesulfonic acid, raise the reaction temperature and carry out the reflux reaction. After the reaction is completed, cool, add saturated sodium bicarbonate aqueous solution to neutralize the reaction system, add ethyl acetate for extraction, allow to stand and separate into layers, collect the organic phase, wash, dry and obtain maleimide-modified polysiloxane. S3. Dissolve the maleimide-modified polysiloxane and diallyl bisphenol A prepared in step S2 in DMAc. After mixing evenly, raise the reaction temperature to carry out a prepolymerization reaction. After the reaction is completed, cool, add polyetheramine, mix evenly, raise the reaction temperature to carry out an addition reaction. After the reaction is completed, cool, add DMAc to adjust the solid content to 5%-10%, and obtain the modified emulsion.

3. The modified rock wool fiber-based fireproof and heat-insulating composite board according to claim 2, characterized in that: In step S1, the volume ratio between deionized water and tetraethyl orthosilicate is 11:4.5-7.5; the reaction temperature of the polycondensation reaction is 50-80℃, and the reaction time of the polycondensation reaction is 4-8h.

4. The modified rock wool fiber-based fireproof and heat-insulating composite board according to claim 3, characterized in that: In step S2, the mass of p-toluenesulfonic acid added is 1%-3% of the mass of maleic anhydride; the reaction time of the ring-opening reaction is 3-4 hours; the reaction temperature of the reflux reaction is 110-120°C, and the reaction time of the reflux reaction is 4-6 hours.

5. The modified rock wool fiber-based fireproof and heat-insulating composite board according to claim 4, characterized in that: In step S3, the polyetheramine includes at least one of polyetheramine D230 and polyetheramine D400; the reaction temperature of the prepolymerization reaction is 150-160℃, and the reaction time of the prepolymerization reaction is 0.5-1.0h; the reaction temperature of the addition reaction is 80-100℃, and the reaction time of the addition reaction is 1-2h.

6. A method for preparing a modified rock wool fiber-based fireproof and heat-insulating composite board according to any one of claims 1-5, characterized in that: Specifically, the steps include the following: ① After crushing and grinding basalt, diabase, blast furnace slag, dolomite, borax and silica fume, they are put into a melting furnace according to the weight proportions. The temperature is raised and maintained to melt the raw materials. After melting, the raw materials are spun into fibers by a four-roll centrifuge. After cooling, the fibers are collected and air-classified to obtain high-adhesion rock wool fibers. ② Take the high-adhesion rock wool fiber prepared in step ① and put it into the impregnation tank. Add the modified emulsion, turn on the stirring, and perform vacuum treatment. After impregnation for 20-30 minutes, perform drying treatment and pre-crosslinking treatment to obtain modified rock wool fiber. ③ Put the modified rock wool fiber prepared in step ② into the kneader, start the stirring and spray the binder, so that the rock wool fiber is kneaded into flocs and then poured into the pendulum felting machine to spread it into fiber felt. ④ After stacking the fiber felt prepared in step ③, adjust the hot pressing parameters, hot press to form, cool naturally, demold, cut, and polish to obtain the modified rock wool fiber substrate fireproof and heat-insulating composite board.

7. The method for preparing a modified rock wool fiber-based fireproof and heat-insulating composite board according to claim 6, characterized in that: In step ①, the melting temperature is 1450-1500℃ and the melting time is 30-40min.

8. The method for preparing a modified rock wool fiber-based fireproof and heat-insulating composite board according to claim 7, characterized in that: In step ②, the drying temperature is 50-60℃ and the drying time is 1-2 hours.

9. The method for preparing a modified rock wool fiber-based fireproof and heat-insulating composite board according to claim 8, characterized in that: In step ②, the temperature of the pre-crosslinking treatment is 70-80℃, and the time of the pre-crosslinking treatment is 0.5-1.5h.

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