High-stability fireproof compression-resistant artificial stone and preparation method thereof

Abstract

The invention relates to the technical field of building materials, in particular to a high-stability fireproof compression-resistant artificial stone and a preparation method thereof.The high-stability fireproof compression-resistant artificial stone is characterized in that a tight and stable structure is formed in the artificial stone through the mutual promotion synergistic effect of a gelling system, a reinforcing material and an auxiliary agent and the synergistic effect of the gelling system, the reinforcing material and the auxiliary agent. The gelling system provides basic adhesion and stability, the reinforcing material further strengthens the stability of the structure, and the auxiliary agent ensures the smooth proceeding of the whole preparation process and the stability of the final performance. Due to the comprehensive action, the artificial stone can keep the structural integrity in the long-term use process, is not prone to deformation, cracking and the like, can meet the requirements for the mechanical property of materials in the fields of building decoration, furniture manufacturing and the like, and solves the problems that in the prior art, the flame retardance and the mechanical property are difficult to consider, and the raw material compatibility is poor; wide application prospects are realized.

Description

Technical Field

[0001] The invention relates to the technical field of building materials, and in particular to a high-stability fireproof and pressure-resistant artificial stone and a preparation method thereof. Background Art

[0002] Artificial stone, as the name implies, is a stone similar to natural stone produced through artificial processing. It is a new type of composite material made of thermosetting resins such as polyester and other additives such as fillers and pigments, injected into metal molds and heated and cured. As an important substitute for natural stone, artificial stone is widely used in architectural decoration, furniture manufacturing and other fields. However, traditional artificial stone has many defects: although organic resin artificial stone has good mechanical properties, it has insufficient flame retardant properties, and organic resin is easy to decompose at high temperature and release harmful gases; although inorganic artificial stone is resistant to high temperature, it has low compressive strength and high brittleness, which makes it difficult to meet high-end application requirements. In the existing technology, the performance can be improved by adding inorganic flame retardants, such as brucite, or using polymer gelling materials, but the following problems still exist:

[0003] 1. The compatibility between fillers and cementitious materials is poor, resulting in weak interface bonding and unstable mechanical properties;

[0004] 2. The effect of a single flame retardant system is limited, and the improvement of fire resistance performance is not significant;

[0005] 3. The aggregate grading is unreasonable and the material density is insufficient, which affects the compressive strength and durability.

[0006] Therefore, according to the above-mentioned related technologies, it is urgent to develop a high-stability fire-resistant and pressure-resistant artificial stone and a preparation method thereof. Summary of the invention

[0007] In view of this, the purpose of the present invention is to propose a high-stability fire-resistant and pressure-resistant artificial stone and a preparation method thereof, so as to provide an artificial stone and a preparation method thereof with high stability, excellent fire resistance and high strength, so as to solve the problems in the prior art that it is difficult to balance flame retardancy and mechanical properties, and poor compatibility of raw materials.

[0008] Based on the above objectives, the present invention provides a high-stability fire-resistant and pressure-resistant artificial stone and a preparation method thereof.

[0009] A high-stability fireproof and pressure-resistant artificial stone comprises the following raw materials in parts by weight: 115-190 parts of a gelling system, 42-66 parts of a reinforcing filler, and 18.5-36.5 parts of an additive;

[0010] The gelling system comprises the following raw materials: unsaturated polyester, modified water magnesium powder and modified tungsten tailings;

[0011] The reinforcing filler comprises the following raw materials: modified magnesium sulfate and modified tungsten tailings.

[0012] Preferably, the unsaturated polyester in the gelling system is vinyl unsaturated polyester, the modified brucite powder in the gelling system is organosilicon-modified brucite powder, and the modified tungsten tailings are silane-modified tungsten tailings. Vinyl unsaturated polyester is the basis of the gelling system, having good adhesion and film-forming properties. The vinyl groups on the surface of the organosilicon-modified brucite powder can copolymerize with the double bonds in the vinyl unsaturated polyester to form a chemical cross-linking network. This cross-linking not only enhances the bonding force between the two, enabling the brucite powder to be better dispersed in the resin matrix, but also improves the stability and strength of the gelling system. At the same time, the brucite powder decomposes endothermically at high temperatures, releasing crystal water, which plays a flame-retardant role and protects the resin matrix from high-temperature damage. The silane coupling agent on the surface of the silane-modified tungsten tailings can chemically react with groups such as hydroxyl groups in the vinyl unsaturated polyester to form chemical bond connections. This enhances the interfacial bonding force between the tungsten tailings and the resin, reducing the interfacial defects. As a filling material, the tungsten tailings fill the voids in the resin, increasing the density of the gelling system, reducing the shrinkage rate of the resin, and further enhancing the stability and mechanical properties of the system. The organosilicon-modified brucite powder and the silane-modified tungsten tailings act together in the gelling system. The flame-retardant characteristics of the brucite powder can protect the tungsten tailings and the resin matrix at high temperatures. The presence of the tungsten tailings provides a supporting structure for the dispersion of the brucite powder, preventing the brucite powder from agglomerating and enabling it to play a more uniform flame-retardant role. In addition, they also have a synergistic effect in improving the density of the system, jointly enhancing the overall performance of the gelling system;

[0013] Preferably, the modified magnesium sulfate in the reinforcing filler is basic magnesium sulfate whisker, and the modified tungsten tailings in the reinforcing filler are silane-modified tungsten tailings aggregate. The basic magnesium sulfate whisker has the characteristics of high strength and high modulus. Its fine fibrous structure can fill the voids in the silane-modified tungsten tailings aggregate to form a "nano-micron" multi-level reinforcement structure. When the material is subjected to external forces, the whiskers can play a bridging role to prevent the propagation of cracks and improve the impact resistance of the material. The silane-modified tungsten tailings aggregate provides a stable supporting framework for the whiskers, enabling the whiskers to better play the reinforcement role. At the same time, the grading relationship between the two can optimize the packing density of the material and further improve the compressive strength of the material.

[0014] Preferably, the auxiliary agent comprises the following raw materials: hardener, initiator, accelerator, masterbatch, and deionized water. The hardener, initiator, and accelerator act synergistically to control the crosslinking and curing process of vinyl unsaturated polyester. The hardener provides the active groups required for the crosslinking reaction, the initiator initiates the start of the crosslinking reaction, and the accelerator regulates the reaction rate to enable the reaction to proceed at an appropriate time and temperature. This can ensure that all components in the gelling system react fully to form a stable three-dimensional network structure, improving the strength and stability of the material. Masterbatch: The masterbatch is used to provide uniform color for artificial stone. It can be evenly dispersed during the stirring process of the gelling system, cooperate with other components, and does not affect the performance of the gelling system while meeting the aesthetic requirements of the product. Deionized water: Deionized water can adjust the viscosity of the gelling system, enabling better mixing of all components. During the stirring process, it helps to disperse organosilicon-modified brucite powder and silane-modified tungsten tailings, ensuring the uniformity and stability of the gelling system. During the process of mixing the reinforcing material with the gelling system, the crosslinking reaction controlled by the hardener, initiator, and accelerator also affects the interfacial bonding between the reinforcing material and the gelling system. A suitable crosslinking reaction can enable basic magnesium sulfate whiskers and silane-modified tungsten tailings aggregates to better combine with the gelling system, giving full play to the reinforcing effect. Deionized water can also improve the dispersibility of the reinforcing material in the system. For basic magnesium sulfate whiskers, it can prevent whisker agglomeration and make them evenly distributed in the system; for silane-modified tungsten tailings aggregates, it helps the silane coupling agent on the aggregate surface to hydrolyze fully, enhancing the bonding force with other components.

[0015] Preferably, the hardener is 1,1,3,3-tetramethylbutyl-2-ethylhexanoate peroxide, the initiator is cyclohexanone peroxide, and the accelerator is cobalt naphthenate.

[0016] Preferably, the mass ratio of the unsaturated polyester, modified brucite powder, and modified tungsten tailings in the gelling system is 100:50 - 70:10 - 20.

[0017] Preferably, the mass ratio of the modified magnesium sulfate and modified tungsten tailings in the reinforcing filler is 2 - 6:40 - 60.

[0018] Preferably, the mass ratio of the hardener, initiator, accelerator, masterbatch, and deionized water in the auxiliary agent is 2 - 4:1 - 3:0.5 - 1.5:5 - 8:10 - 20.

[0019] Preferably, the preparation process of the organosilicon-modified brucite powder is as follows:

[0020] Step A1. Add 2,4,6,8 - tetramethylcyclotetrasiloxane, chloroplatinic acid and toluene into a reaction flask equipped with a reflux condenser, a dropping funnel and a thermometer. After stirring evenly, add propyl methacrylate and react at 45 - 60 °C for 40 - 60 min. Then add vinyltrimethoxysilane and 2,6 - di - tert - butyl - p - cresol and react at 90 - 105 °C for 2 - 5 h. Cool to room temperature and concentrate under reduced pressure to obtain an alkenyl cyclic organosilicon cross - linker.

[0021] Step A2. Add antigorite powder and ethanol into the reaction flask. After stirring evenly at a rotation speed of 400 - 600 r / min, add the alkenyl cyclic organosilicon cross - linker and stir for reaction. After the reaction ends, filter, wash with deionized water, dry and grind to obtain organosilicon - modified antigorite powder.

[0022] A preparation method of a highly stable fire - resistant and compressive artificial stone, comprising the following steps:

[0023] Step S1. Aggregate pretreatment: Screen tungsten tailings into four particle sizes of 0.2 - 0.3 mm, 0.3 - 0.5 mm, 0.5 - 1.0 mm, and 1.0 - 2.0 mm, and mix them according to the fractal grading formula: Mix and control the fractal dimension F = 2.4 - 2.6 to obtain modified tungsten tailings.

[0024] Step S2. Mix the modified tungsten tailings and modified magnesium sulfate to obtain a reinforcing filler.

[0025] Step S3. Premixing process: Stir unsaturated polyester, organosilicon - modified antigorite powder and modified tungsten tailings for 8 - 13 min to obtain a gelling system.

[0026] Step S4. Mix the hardener, initiator, accelerator, color masterbatch and deionized water evenly to obtain an additive.

[0027] Step S5. Add the gelling system, reinforcing filler and additive into a powerful mixer and stir at 35 - 50 °C for 25 - 45 min to obtain a mixture.

[0028] Step S6. Molding process: Transfer the mixture to a mold, vibrate to remove bubbles, place it on a hot press, and cure and form at a pressure of 5 - 10 MPa and a temperature of 50 - 70 °C for 2 - 5 h. After cooling, grinding and polishing, a highly stable fire - resistant and compressive artificial stone is obtained.

[0029] The beneficial effects of the present invention:

[0030] The present invention provides a highly stable fireproof and compression-resistant artificial stone and a preparation method thereof. Through the mutual promotion and synergistic effect among the gelling system, reinforcing material, and additives, a tight and stable structure is formed inside the artificial stone. The gelling system provides basic adhesion and stability, the reinforcing material further strengthens the structural stability, and the additives ensure the smooth progress of the entire preparation process and the stability of the final performance. This comprehensive effect enables the artificial stone to maintain the structural integrity during long-term use and is not prone to problems such as deformation and cracking;

[0031] Organosilicon-modified brucite powder is the main flame retardant component. It can decompose endothermically at high temperatures, release crystal water, dilute the oxygen concentration, and simultaneously form a magnesium oxide heat-insulating layer. The silane-modified tungsten tailings aggregate can also play a role in heat insulation and oxygen barrier to a certain extent. The synergistic effect of the gelling system and the reinforcing material enables the flame retardant components to be more evenly distributed in the material, improving the fireproof effect. The use of additives ensures the molding quality of the material and avoids the decline in fireproof performance caused by molding defects.

[0032] The reinforcing effect of basic magnesium sulfate whiskers and silane-modified tungsten tailings aggregate cooperates with the bonding effect of the gelling system, making the artificial stone have high compressive strength and impact strength. The curing process controlled by additives makes the internal structure of the material more dense, further improving the strength. This high strength enables the artificial stone to meet the requirements of the mechanical properties of materials in fields such as building decoration and furniture manufacturing, solves the problems in the prior art that it is difficult to balance flame retardancy and mechanical properties and the poor compatibility of raw materials, and has broad application prospects. Specific embodiments

[0033] To make the purpose, technical solution, and advantages of the present invention clearer, the following further details the present invention in conjunction with specific embodiments.

[0034] Example 1: A preparation method of a highly stable fireproof and compression-resistant artificial stone, including the following steps:

[0035] S1. Add 100 g of 2,4,6,8-tetramethylcyclotetrasiloxane, 0.5 g of chloroplatinic acid, and 400 g of toluene to a reaction flask equipped with a reflux condenser, dropping funnel, and thermometer. After stirring evenly, add 100 g of propyl methacrylate and react at 45 °C for 40 min. Then add 180 g of vinyltrimethoxysilane and 1 g of 2,6-di-tert-butyl-p-cresol, and react at 90 °C for 2 - 3 - 4 - 5 h. Cool to room temperature and concentrate under reduced pressure to obtain an alkenyl cyclic organosilicon crosslinking agent;

[0036] S2. Add 100 g of brucite powder and 400 mL of ethanol to a reaction flask. After stirring evenly at a rotation speed of 400 r / min, add 8 g of vinyl cyclic organosilicon crosslinking agent, stir and react. After the reaction is completed, filter, wash with deionized water, dry and grind to obtain organosilicon-modified brucite powder;

[0037] S3. Aggregate pretreatment: Screen tungsten tailings into four particle sizes of 0.2 - 0.3 mm, 0.3 - 0.5 mm, 0.5 - 1.0 mm, and 1.0 - 2.0 mm, and mix according to the fractal grading formula: Mix and control the fractal dimension F = 2.4 - 2.6 to obtain modified tungsten tailings;

[0038] S4. Mix 40 g of modified tungsten tailings and 2 g of basic magnesium sulfate whiskers to obtain reinforcing filler;

[0039] S5. Premixing process: Mix 100 g of vinyl unsaturated polyester, 50 g of organosilicon-modified brucite powder and 10 g of modified tungsten tailings, and stir for 8 min to obtain a gelling system;

[0040] S6. Mix 2 g of 1,1,3,3-tetramethylbutyl-2-ethylhexanoate peroxide, 1 g of cyclohexanone peroxide, 0.5 g of cobalt naphthenate, 5 g of color masterbatch and 10 g of deionized water evenly to obtain an additive;

[0041] S7. Add 115 g of the gelling system, 42 g of the reinforcing filler and 18.5 g of the additive to a powerful mixer, and stir at 35 °C for 25 min to obtain a mixture;

[0042] S8. Molding process: Transfer the mixture to a mold, vibrate to remove bubbles, place it on a hot press, cure and mold at a pressure of 5 MPa and a temperature of 50 °C for 2 h, and obtain a high-stability fireproof and compressive artificial stone after cooling, grinding and polishing.

[0043] Example 2: A method for preparing a high-stability fireproof and compressive artificial stone, comprising the following steps:

[0044] S1. Add 100 g of 2,4,6,8-tetramethylcyclotetrasiloxane, 0.7 g of chloroplatinic acid and 430 g of toluene to a reaction flask equipped with a reflux condenser, a dropping funnel and a thermometer. After stirring evenly, add 120 g of propyl methacrylate, react at 50 °C for 45 min, add 185 g of vinyltrimethoxysilane and 1.3 g of 2,6-di-tert-butyl-p-cresol, react at 95 °C for 3 h, cool to room temperature, and concentrate under reduced pressure to obtain a vinyl cyclic organosilicon crosslinking agent;

[0045] S2. Add 100 g of antigorite powder and 430 mL of ethanol to a reaction flask. After stirring evenly at a rotation speed of 450 r / min, add 8.5 g of alkenyl cyclic organosilicon crosslinking agent, stir and react. After the reaction is completed, filter, wash with deionized water, dry and grind to obtain organosilicon-modified antigorite powder;

[0046] S3. Aggregate pretreatment: Screen tungsten tailings into four particle sizes of 0.2 - 0.3 mm, 0.3 - 0.5 mm, 0.5 - 1.0 mm, and 1.0 - 2.0 mm, and mix according to the fractal grading formula: Mix and control the fractal dimension F = 2.4 - 2.6 to obtain modified tungsten tailings;

[0047] S4. Mix 45 g of modified tungsten tailings and 3 g of basic magnesium sulfate whiskers to obtain reinforcing filler;

[0048] S5. Premixing process: Stir 100 g of vinyl unsaturated polyester, 55 g of organosilicon-modified antigorite powder, and 13 g of modified tungsten tailings for 10 min to obtain a gelling system;

[0049] S6. Mix 2.5 g of 1,1,3,3-tetramethylbutyl-2-ethylhexanoate peroxide, 2 g of cyclohexanone peroxide, 0.7 g of cobalt naphthenate, 6 g of color masterbatch, and 13 g of deionized water evenly to obtain an additive;

[0050] S7. Add 140 g of the gelling system, 50 g of the reinforcing filler, and 22 g of the additive to a powerful mixer and stir at 40 °C for 30 min to obtain a mixture;

[0051] S8. Molding process: Transfer the mixture to a mold, vibrate to remove bubbles, place it on a hot press, and cure and mold at a pressure of 7 MPa and a temperature of 55 °C for 3 h. After cooling, grinding, and polishing, a high-stability fireproof and compressive artificial stone is obtained.

[0052] Example 3: A preparation method of a high-stability fireproof and compressive artificial stone, comprising the following steps:

[0053] S1. Add 100 g of 2,4,6,8-tetramethylcyclotetrasiloxane, 0.9 g of chloroplatinic acid, and 460 g of toluene to a reaction flask equipped with a reflux condenser, a dropping funnel, and a thermometer. After stirring evenly, add 140 g of propyl methacrylate, react at 55 °C for 50 min, add 190 g of vinyltrimethoxysilane and 1.6 g of 2,6-di-tert-butyl-p-cresol, react at 100 °C for 4 h, cool to room temperature, and concentrate under reduced pressure to obtain an alkenyl cyclic organosilicon crosslinking agent;

[0054] S2. Add 100 g of brucite powder and 460 mL of ethanol to the reaction flask. After stirring evenly at a rotation speed of 500 r / min, add 9 g of alkenyl cyclic organosilicon crosslinking agent, stir and react. After the reaction is completed, filter, wash with deionized water, dry and grind to obtain organosilicon-modified brucite powder;

[0055] S3. Aggregate pretreatment: Screen the tungsten tailings into four particle sizes of 0.2 - 0.3 mm, 0.3 - 0.5 mm, 0.5 - 1.0 mm, and 1.0 - 2.0 mm, and mix them according to the fractal grading formula: Mix and control the fractal dimension F = 2.4 - 2.6 to obtain modified tungsten tailings;

[0056] S4. Mix 50 g of modified tungsten tailings and 4 g of basic magnesium sulfate whiskers to obtain reinforcing filler;

[0057] S5. Premixing process: Stir 100 g of vinyl unsaturated polyester, 60 g of organosilicon-modified brucite powder, and 16 g of modified tungsten tailings for 12 min to obtain a gelling system;

[0058] S6. Mix 3 g of 1,1,3,3-tetramethylbutyl-2-ethylhexanoate peroxide, 2.5 g of cyclohexanone peroxide, 1.2 g of cobalt naphthenate, 7 g of color masterbatch, and 16 g of deionized water evenly to obtain an additive;

[0059] S7. Add 170 g of the gelling system, 60 g of the reinforcing filler, and 30 g of the additive to a high-strength mixer and stir at 45 °C for 35 min to obtain a mixture;

[0060] S8. Molding process: Transfer the mixture to a mold, vibrate to remove bubbles, place it on a hot press, and cure and mold at a pressure of 9 MPa and a temperature of 60 °C for 4 h. After cooling, grinding, and polishing, a high-stability fireproof and compressive artificial stone is obtained.

[0061] Example 4: A method for preparing a high-stability fireproof and compressive artificial stone, comprising the following steps:

[0062] S1. Add 100 g of 2,4,6,8-tetramethylcyclotetrasiloxane, 1 g of chloroplatinic acid, and 500 g of toluene to a reaction flask equipped with a reflux condenser, a dropping funnel, and a thermometer. After stirring evenly, add 150 g of propyl methacrylate, react at 60 °C for 60 min, add 200 g of vinyltrimethoxysilane and 2 g of 2,6-di-tert-butyl-p-cresol, react at 105 °C for 5 h, cool to room temperature, and concentrate under reduced pressure to obtain an alkenyl cyclic organosilicon crosslinking agent;

[0063] S2. Add 100 g of antigorite powder and 500 mL of ethanol to the reaction flask. After stirring evenly at a rotation speed of 600 r / min, add 10 g of vinyl cyclic organosilicon crosslinking agent, stir and react. After the reaction is completed, filter, wash with deionized water, dry and grind to obtain organosilicon-modified antigorite powder;

[0064] S3. Aggregate pretreatment: Screen the tungsten tailings into four particle sizes of 0.2 - 0.3 mm, 0.3 - 0.5 mm, 0.5 - 1.0 mm, and 1.0 - 2.0 mm, and mix according to the fractal grading formula: Mix and control the fractal dimension F = 2.4 - 2.6 to obtain modified tungsten tailings;

[0065] S4. Mix 60 g of modified tungsten tailings and 6 g of basic magnesium sulfate whiskers to obtain reinforcing filler;

[0066] S5. Premixing process: Stir 100 g of vinyl unsaturated polyester, 70 g of organosilicon-modified antigorite powder, and 20 g of modified tungsten tailings for 13 min to obtain a gelling system;

[0067] S6. Mix 4 g of 1,1,3,3-tetramethylbutyl-2-ethylhexanoate peroxide, 3 g of cyclohexanone peroxide, 1.5 g of cobalt naphthenate, 8 g of masterbatch, and 20 g of deionized water evenly to obtain an additive;

[0068] S7. Add 190 g of the gelling system, 66 g of the reinforcing filler, and 36.5 g of the additive to a powerful mixer and stir at 50 °C for 45 min to obtain a mixture;

[0069] S8. Molding process: Transfer the mixture to a mold, vibrate to remove bubbles, place it on a hot press, and cure and mold at a pressure of 10 MPa and a temperature of 70 °C for 5 h. After cooling, grinding, and polishing, obtain a high-stability fireproof and compressive artificial stone.

[0070] Comparative Example 1:

[0071] Compared with Example 1, this comparative example did not add modified tungsten tailings during the preparation process of the gelling system, and the remaining steps and parameters were the same. This comparative example will not be repeated here, and finally an artificial stone was obtained.

[0072] Comparative Example 2:

[0073] Compared with Example 1, this comparative example only replaced "organosilicon-modified antigorite powder" with "commercially available ordinary antigorite powder", and the remaining steps and parameters were the same. This comparative example will not be repeated here, and finally an artificial stone was obtained.

[0074] Comparative Example 3:

[0075] In this comparative example, compared with Example 1, magnesium oxysulfate whiskers were not added during the preparation of the reinforcing filler. At the same time, the amount of modified tungsten tailings in the reinforcing filler was increased to 42 g to ensure that the total amount of the reinforcing filler remained constant. The remaining steps and parameters were the same. This comparative example will not be repeated here, and finally artificial stone was obtained.

[0076] Comparative Example 4:

[0077] In this comparative example, compared with Example 1, only the amount of the hardener 1,1,3,3-tetramethylbutyl-2-ethylhexanoate peroxide was increased to 8 g, and the remaining steps and parameters were the same. This comparative example will not be repeated here, and finally artificial stone was obtained.

[0078] Comparative Example 5:

[0079] In this comparative example, compared with Example 1, only "modified tungsten tailings" was replaced with "unscreened tungsten tailings with a particle size of 0.5 - 2 mm", and the remaining steps and parameters were the same. This comparative example will not be repeated here, and finally artificial stone was obtained.

[0080] Performance test: The following performance tests were carried out on the artificial stones prepared in Examples 1 - 4 and Comparative Examples 1 - 5:

[0081] 1. Stability test: The artificial stone samples were placed in an environmental chamber at a temperature of 60 °C and a relative humidity of 90% for 30 days, and whether the samples showed deformation, cracking, etc. was observed, and the dimensional change rate was recorded.

[0082] 2. Fire resistance test: Using an oxygen index tester, the oxygen index of the artificial stone was tested according to the standard of GB / T 2406.2 - 2009. The higher the oxygen index, the better the fire resistance.

[0083] 3. Compressive strength test: Using a pressure testing machine, the compressive strength of the artificial stone samples was tested according to the standard of GB / T 9966.1 - 2020, and the maximum failure load was recorded and the compressive strength was calculated.

[0084] 4. Impact resistance test: Using a falling weight impact testing machine, the impact resistance of the artificial stone samples was tested according to the standard of GB / T 14152 - 2001, and the impact failure situation and impact strength were recorded; the results are shown in Table 1 below.

[0085] Table 1 Summary of experimental results of Examples 1 - 4 and Comparative Examples 1 - 5

[0086] Project Stability Fire resistance Compressive strength Impact strength Example 1 ≤0.1％ 35 80 18 Example 2 ≤0.08％ 37 95 16 Example 3 ≤0.06％ 38 90 17 Example 4 ≤0.05％ 36 85 15 Comparative example 1 0.3％ 30 60 10 Comparative example 2 0.25％ 28 55 9 Comparative example 3 0.2％ 32 65 11 Comparative example 4 0.22％ 31 62 10 Comparative example 5 0.28％ 30 63 10

[0087] Data analysis:

[0088] As can be seen from Table 1, the artificial stones prepared in Examples 1-4 have higher stability, better fire resistance, higher compressive strength and impact strength;

[0089] The high-stability fire-resistant and compressive artificial stone prepared by the present invention achieves a significant improvement in effects through the mutual promotion and synergistic effect among the gelling system, reinforcing materials and additives, specifically as follows:

[0090] Laying the foundation for the gelling system: The gelling system consists of vinyl unsaturated polyester, organosilicon-modified brucite powder and silane-modified tungsten tailings. Among them, vinyl unsaturated polyester serves as the matrix, providing basic bonding properties and a mechanical support framework. The organosilicon-modified brucite powder not only has good flame retardant properties, but its alkenyl cyclic organosilicon structure can also undergo a certain degree of chemical cross-linking with vinyl unsaturated polyester, enhancing the internal binding force of the gelling system and making the whole system more stable. On the one hand, the silane-modified tungsten tailings can fill the voids in the gelling system, improving the density of the system; on the other hand, the silane groups on its surface can interact with vinyl unsaturated polyester and organosilicon-modified brucite powder, further enhancing the interfacial binding force, thereby improving the overall stability and strength of the gelling system.

[0091] Strengthening the performance of the reinforcing materials: The reinforcing materials include basic magnesium sulfate whiskers and silane-modified tungsten tailings aggregates. The basic magnesium sulfate whiskers have excellent mechanical properties, and their fine fibrous structure can play a bridging and strengthening role in the gelling system, effectively preventing the propagation of cracks and significantly improving the compressive and impact strength of the artificial stone. The silane-modified tungsten tailings aggregates form a closely packed structure through a reasonable particle size fractal grading (controlling the fractal dimension F = 2.4 - 2.6), further improving the density of the material. At the same time, it cooperates with the components in the gelling system to synergistically enhance the stability and strength of the material. For example, when subjected to external forces, the basic magnesium sulfate whiskers and silane-modified tungsten tailings aggregates jointly bear the stress, enabling the material to better resist damage.

[0092] Ensuring molding and performance with additives: The additives include hardeners, initiators, accelerators, masterbatch and deionized water. The hardeners, initiators and accelerators act synergistically to precisely control the cross-linking and curing process of vinyl unsaturated polyester, ensuring that the material can form a stable three-dimensional network structure at the appropriate time and conditions, thereby guaranteeing the strength and stability of the artificial stone. The masterbatch is used to provide the artificial stone with an attractive color, meeting different application requirements. The deionized water plays a role in adjusting the fluidity of the slurry, enabling the components to be evenly mixed, facilitating the subsequent molding process, and ensuring the uniformity of the material properties.

[0093] The comprehensive effects brought by the synergistic effect of the three:

[0094] High stability: The synergistic effect of the gelling system, reinforcing materials, and additives forms a tight and stable structure within the artificial stone. The gelling system provides the basic bonding and stability, the reinforcing materials further enhance the structural stability, and the additives ensure the smooth progress of the entire preparation process and the stability of the final properties. This comprehensive effect enables the artificial stone to maintain the integrity of its structure during long-term use and is not prone to problems such as deformation and cracking.

[0095] Good fire resistance: Organosilicon-modified brucite powder is the main flame retardant component. It can decompose endothermically at high temperatures, release crystal water, dilute the oxygen concentration, and simultaneously form a magnesium oxide heat-insulating layer. The silane-modified tungsten tailings aggregate can also play a role in heat insulation and oxygen barrier to a certain extent. The synergistic effect of the gelling system and the reinforcing materials enables the flame retardant components to be more evenly distributed in the material, improving the fire prevention effect. The use of additives ensures the molding quality of the material and avoids the decline in fire resistance caused by molding defects.

[0096] High strength: The reinforcing effect of basic magnesium sulfate whiskers and silane-modified tungsten tailings aggregate cooperates with the bonding effect of the gelling system, making the artificial stone have high compressive strength and impact strength. The curing process controlled by additives makes the internal structure of the material more dense, further improving the strength. This high strength enables the artificial stone to meet the requirements for the mechanical properties of materials in fields such as building decoration and furniture manufacturing.

[0097] In addition, using a small amount of modified tungsten tailings in the gelling system first and then compounding it with the reinforcing filler containing a large amount of modified tungsten tailings has the following effects:

[0098] Optimization effect on the gelling system: Enhancing the interfacial bonding force: The silane coupling agent on the surface of the modified tungsten tailings can react with groups such as hydroxyl groups in vinyl unsaturated polyester to form chemical bond connections. Adding a small amount of modified tungsten tailings to the gelling system first can make it evenly disperse between vinyl unsaturated polyester and organosilicon-modified brucite powder, enhancing the interfacial bonding force of each component and making the gelling system more stable; Improving the density: A small amount of modified tungsten tailings can fill the voids in the gelling system, increase the density of the system, reduce the shrinkage rate of the resin, and thus improve the stability and mechanical properties of the gelling system; Promoting the cross-linking reaction: The modified tungsten tailings can promote the cross-linking reaction between organosilicon-modified brucite powder and vinyl unsaturated polyester, making the chemical cross-linking network more perfect and further enhancing the strength of the gelling system.

[0099] Synergistic effect when compounded with reinforcing fillers: Optimize the grading structure: The modified tungsten tailings in the reinforcing fillers are fractionally graded and have different particle sizes. Adding a small amount of modified tungsten tailings to the cementitious system first and then compounding with the reinforcing fillers can further optimize the overall grading structure, resulting in a higher bulk density of the material and improving its compressive strength; Enhance the synergistic effect: The modified tungsten tailings in the cementitious system cooperate with a large amount of tungsten tailings in the reinforcing fillers and act together with magnesium sulfate hydroxide whiskers to form a "nano-micron" multi-level reinforcement structure. When the material is subjected to external forces, they can jointly bear the stress, better prevent crack propagation, and improve the impact resistance of the material; Uniformly disperse the reinforcing materials: The uniformly dispersed modified tungsten tailings in the cementitious system can provide a better dispersion environment for the magnesium sulfate hydroxide whiskers and a large amount of tungsten tailings in the reinforcing fillers, prevent whisker agglomeration, and enable the reinforcing materials to play a reinforcing role more uniformly.

[0100] Effect of improving the overall performance: Improve stability: By optimizing the structure and interaction of the cementitious system and the reinforcing fillers, a more compact and stable structure is formed inside the artificial stone, and problems such as deformation and cracking are less likely to occur during long-term use; Enhance fire resistance: The modified tungsten tailings and organosilicon-modified brucite powder act synergistically in the cementitious system and the reinforcing fillers, enabling the flame retardant components to be more evenly distributed in the material and improving the fire protection effect; Improve mechanical properties: Considering the above various effects, the mechanical properties of the artificial stone, such as compressive strength and impact strength, are significantly improved, and it can better meet the requirements for the mechanical properties of materials in fields such as building decoration and furniture manufacturing.

[0101] This invention is intended to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this invention shall be included within the protection scope of this invention.

Claims

1. A highly stable fireproof and compressive artificial stone, characterized in that, It includes the following raw materials in parts by mass: 115 - 190 parts of a gelling system, 42 - 66 parts of a reinforcing filler, and 18.5 - 36.5 parts of an auxiliary agent; The gelling system includes the following raw materials: unsaturated polyester, modified brucite powder, and modified tungsten tailings; The reinforcing filler includes the following raw materials: modified magnesium sulfate and modified tungsten tailings.

2. The high-stability fireproof and compression-resistant artificial stone according to claim 1, wherein In the gelling system, the unsaturated polyester is vinyl unsaturated polyester, and the modified brucite powder in the gelling system is organosilicon - modified brucite powder.

3. The high-stability fireproof and compression-resistant artificial stone according to claim 1, characterized in that, In the reinforcing filler, the modified magnesium sulfate is basic magnesium sulfate whisker, and the modified tungsten tailings in the reinforcing filler are silane - modified tungsten tailings aggregate.

4. The highly stable fireproof and compressive artificial stone according to claim 1, characterized in that, The auxiliary agent includes the following raw materials: hardener, initiator, accelerator, masterbatch, and deionized water.

5. The high-stability fireproof and compression-resistant artificial stone according to claim 4, characterized in that, The hardener is 1,1,3,3 - tetramethylbutyl - 2 - ethylhexanoate peroxide, the initiator is cyclohexanone peroxide, and the accelerator is cobalt naphthenate.

6. The highly stable fireproof and compression-resistant artificial stone according to claim 1, characterized in that, In the gelling system, the mass ratio of unsaturated polyester, modified brucite powder, and modified tungsten tailings is 100:50 - 70:10 - 20.

7. The high-stability fireproof and compression-resistant artificial stone according to claim 1, characterized in that, In the reinforcing filler, the mass ratio of the modified magnesium sulfate and modified tungsten tailings is 2 - 6:40 - 60.

8. The high-stability fireproof and compression-resistant artificial stone according to claim 1, wherein In the auxiliary agent, the mass ratio of hardener, initiator, accelerator, masterbatch, and deionized water is 2 - 4:1 - 3:0.5 - 1.5:5 - 8:10 - 20.

9. The high-stability fireproof and compression-resistant artificial stone according to claim 1, characterized in that The preparation process of the modified brucite powder is as follows: Step A1. Add 2,4,6,8 - tetramethylcyclotetrasiloxane, chloroplatinic acid, and toluene into a reaction flask equipped with a reflux condenser, dropping funnel, and thermometer. After stirring evenly, add propyl methacrylate, react at 45 - 60 °C for 40 - 60 min, add vinyltrimethoxysilane and 2,6 - di - tert - butyl - p - cresol, react at 90 - 105 °C for 2 - 5 h, cool to room temperature, and concentrate under reduced pressure to obtain an alkenyl - cyclic organosilicon cross - linker; Step A2. Add brucite powder and ethanol into the reaction flask. After stirring evenly at a rotation speed of 400 - 600 r / min, add the alkenyl - cyclic organosilicon cross - linker, stir and react. After the reaction is completed, filter, wash with deionized water, and dry and grind to obtain the modified brucite powder.

10. A preparation method of a highly stable fireproof and compressive artificial stone, characterized in that, It includes the following steps: Step S1. Aggregate pretreatment: Screen tungsten tailings into four particle sizes of 0.2 - 0.3 mm, 0.3 - 0.5 mm, 0.5 - 1.0 mm, and 1.0 - 2.0 mm, and mix them according to the fractal grading formula: Mix them and control the fractal dimension F = 2.4 - 2.6 to obtain modified tungsten tailings; Step S2. Mix the modified tungsten tailings and modified magnesium sulfate to obtain a reinforcing filler; Step S3. Premixing process: Stir the unsaturated polyester, modified brucite powder, and modified tungsten tailings for 8 - 13 min to obtain a gelling system; Step S4. Mix the hardener, initiator, accelerator, masterbatch, and deionized water evenly to obtain an auxiliary agent; Step S5. Add the gelling system, reinforcing filler, and auxiliary agent into a powerful mixer and stir at 35 - 50 °C for 25 - 45 min to obtain a mixture; Step S6. Molding treatment: Transfer the mixture to a mold, vibrate to remove bubbles, place it on a hot press, and cure and form at a pressure of 5 - 10 MPa and a temperature of 50 - 70 °C for 2 - 5 h. After cooling, grinding, and polishing, a high - stability fire - resistant and compressive artificial stone is obtained.

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