High-strength light-weight artificial stone plate and preparation method thereof

Abstract

This invention relates to the field of building materials technology, and in particular to a high-strength lightweight artificial stone slab and its preparation method. The high-strength lightweight artificial stone slab is made from the following raw materials in the indicated weight percentages: 8-16 wt% modified unsaturated resin binder, 0.2-0.8 wt% compound curing agent, 0.05-0.2 wt% defoamer, 0.5-2.0 wt% coupling agent compound, 15-30 wt% inorganic mineral powder, 15-25 wt% hollow glass microspheres, and 35-50 wt% inorganic mineral sand; the hollow glass microspheres have a particle size of 5-100 μm and a true density of 0.14-1.3 g / cm³. 3 The artificial stone slab of this invention has technical advantages such as being lightweight, high-strength, sound and heat insulated, having a low coefficient of thermal expansion, and good dimensional stability, thus expanding the application range of artificial stone slabs.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, and in particular to a high-strength lightweight artificial stone slab and its preparation method. Background Technology

[0002] Artificial synthetic stone is an artificial composite material that has gradually emerged in recent years. It is synthesized from natural mineral powder and resin, has no radioactive hazards, meets green building material standards, and has excellent processing performance. It is easy to cut and polish, and can achieve complex shapes such as curved surfaces and irregular shapes. Its impact resistance is better than traditional building materials such as ceramics, making it a viable alternative to natural stone and widely used in the field of building materials.

[0003] Existing artificial stone slabs use unsaturated polyester resin as a binder, mineral powder as fine aggregate, and mineral sand as coarse aggregate. After adding pigments, curing agents, and coupling agents, they are made into artificial decorative surface materials through processes such as stirring, pressing, curing, cutting, and polishing.

[0004] Chinese Patent CN111620601B discloses a method for preparing artificial stone slabs, comprising: (1) mixing artificial stone slab raw materials evenly to obtain a mixture; (2) spreading the mixture into a mold to form a loose blank; (3) vibrating and pressing the loose blank to obtain a compact blank; (4) heating and curing the compact blank to obtain a slab blank; (5) polishing the slab blank to obtain a finished artificial stone slab; the artificial stone slab is mainly made of the following raw materials in weight percentage: 50-65% first aggregate, 25-40% second aggregate, 7-11% unsaturated polyester resin, 1.5-3% silicone oil, 0.1-2% coupling agent, 0.1-2% curing agent, and 0.1-2% additives; the coupling agent is γ-methacryloyloxypropyltrimethoxysilane. The unsaturated polyester resin is a linear polymer compound with ester bonds and unsaturated double bonds, which is formed by the condensation polymerization of unsaturated dicarboxylic acid diol or saturated dicarboxylic acid unsaturated diol. The additives include pigments, which can be one or both of inorganic and organic pigments.

[0005] Although the aforementioned artificial stone slabs achieved good flexural strength and compressive strength, their coefficient of thermal expansion (2.57-2.68*10) was low. -5 The coefficient of thermal expansion ( / ℃) is relatively high, which is within the average range for domestic artificial stone slabs (coefficient of thermal expansion 1.8-3.3*10). -5 The coefficient of thermal expansion ( / ℃) does not meet the European export standard (coefficient of thermal expansion 1.2-1.6*10). -5 / ℃). The main reason for its relatively high coefficient of thermal expansion is the use of linear polymer compounds as binders. Furthermore, the density of the aforementioned artificial stone slabs, converted from raw material density, is between 2.25 and 2.40 g / cm³. 3While these artificial stone slabs are much lighter than natural stone, their density is still relatively high, failing to meet consumers' demand for lightweight artificial stone slabs. Therefore, the inventors have provided a lightweight, high-strength artificial stone slab with good dimensional stability, along with its preparation method. Summary of the Invention

[0006] To address the issues of dimensional instability and high density in existing artificial stone slabs, which fail to meet lightweight requirements, this invention provides a high-strength lightweight artificial stone slab and its preparation method.

[0007] The high-strength, lightweight artificial stone slab provided by this invention is achieved through the following technical solution:

[0008] A high-strength, lightweight artificial stone slab is made from the following raw materials in weight percentages: 8-16 wt% modified unsaturated resin binder, 0.2-0.8 wt% compound curing agent, 0.05-0.2 wt% defoamer, 0.5-2.0 wt% coupling agent compound, 15-30 wt% inorganic mineral powder, 15-25 wt% hollow glass microspheres, and 35-50 wt% inorganic mineral sand; the hollow glass microspheres have a particle size of 5-100 μm and a true density of 0.14-1.3 g / cm³. 3 .

[0009] Preferably, the modified unsaturated resin adhesive is composed of unsaturated polyester resin and polyurethane resin containing active double bonds.

[0010] Preferably, the compound curing agent is composed of a peroxide initiator and triallyl isocyanate.

[0011] Preferably, the peroxide initiator is any one of methyl ethyl ketone peroxide, cyclohexanone peroxide, and benzoyl peroxide.

[0012] Preferably, the coupling agent compound is composed of methacryloxysilane and mercaptosilane, or the compound curing agent is composed of methacryloxysilane, mercaptosilane and chelated titanate coupling agent.

[0013] This invention reduces the density of artificial stone slabs by using hollow glass microspheres, giving them excellent sound and heat insulation properties as well as lightweight properties. By using modified unsaturated resin binders and compound curing agents to form a three-dimensional cross-linked network structure containing polyurethane elastic segments, it not only improves the compressive strength, flexural strength, and dimensional stability of artificial stone slabs, but also improves their toughness and impact resistance, expanding the application range of artificial stone slabs and enhancing their market competitiveness.

[0014] Preferably, the chelating titanate coupling agent includes at least one of KR138S, KR212, and KR238S.

[0015] Preferably, the high-strength lightweight artificial stone slab is made from the following raw materials in weight percentages: 10-12 wt% modified unsaturated resin binder, 0.5-0.8 wt% compound curing agent, 0.3-0.5 wt% defoamer, 0.8-1.2 wt% coupling agent compound, 24-30 wt% inorganic mineral powder, 18-24 wt% hollow glass microspheres, and 40-45 wt% inorganic mineral sand.

[0016] In the formulation of high-strength lightweight artificial stone slabs, the modified unsaturated resin binder has the largest coefficient of thermal expansion. By optimizing the ratio of inorganic mineral powder, hollow glass microspheres, and inorganic mineral sand, the amount of modified unsaturated resin binder used is reduced. This ensures the mechanical properties of the artificial stone slab, further improves the coefficient of thermal expansion, enhances the dimensional stability of the artificial stone slab, and reduces the production cost of artificial stone.

[0017] Preferably, the inorganic ore powder consists of 26-32 wt% median diameter D. 50 It is an inorganic mineral powder with a diameter of 8-10 μm and a median diameter of 8-12 wt%. 50 It consists of inorganic mineral powder with a particle size of 3-5 μm and the balance being the median diameter D. 50 It consists of inorganic mineral powder with a particle size of 15-20 μm.

[0018] More preferably, the inorganic ore powder is composed of 30±0.5wt% median diameter D 50 It is an inorganic mineral powder with a particle size of 8-10 μm and a median diameter D of 10 ± 0.5 wt%. 50 It consists of inorganic mineral powder with a particle size of 3-5 μm and the balance being the median diameter D. 50 It consists of inorganic mineral powder with a particle size of 15-20 μm.

[0019] Optimizing the gradation of inorganic mineral powder can improve the density of artificial stone slabs, which is beneficial to improving the mechanical properties and impact strength of artificial stone slabs. It can also reduce the amount of modified unsaturated resin binder, which is beneficial to improving the dimensional stability of artificial stone slabs and reducing the production cost of artificial stone.

[0020] Preferably, the inorganic ore sand is composed of 20-35 wt% median diameter D. 50 It consists of inorganic mineral sand with a diameter of 90-100 μm and a median diameter of 10-20 wt%. 50 It consists of inorganic mineral sand with a diameter of 45-55 μm and the balance being the median diameter D. 50 It consists of inorganic mineral sand with a particle size of 160-180 μm.

[0021] More preferably, the inorganic ore sand is composed of 30±0.5wt% median diameter D 50 It is an inorganic mineral sand with a diameter of 90-100 μm and a median diameter of 15 ± 0.5 wt%. 50 It consists of inorganic mineral sand with a diameter of 45-55 μm and the balance being the median diameter D. 50 It consists of inorganic mineral sand with a particle size of 160-180 μm.

[0022] Optimizing the gradation of inorganic mineral sand can improve the density of artificial stone slabs, which is beneficial to improving the mechanical properties and impact strength of artificial stone slabs. It can also reduce the amount of modified unsaturated resin binder, which is beneficial to improving the dimensional stability of artificial stone slabs and reducing the production cost of artificial stone.

[0023] Preferably, the hollow glass microspheres are composed of 25-35 wt% median diameter D. 50 Hollow glass microspheres with a diameter of 28-35 μm and a median diameter of 10-15 wt% D 50 Hollow glass microspheres of 10-20 μm, with the balance being the median diameter D. 50 It consists of hollow glass microspheres of 50-55 μm.

[0024] Preferably, the hollow glass microspheres are composed of 30±0.5wt% median diameter D. 50 Hollow glass microspheres of 28-35 μm, with a median diameter D of 10 ± 0.5 wt%. 50 Hollow glass microspheres of 10-20 μm, with the balance being the median diameter D. 50 It consists of hollow glass microspheres of 50-55 μm.

[0025] Optimizing the gradation of hollow glass microspheres can improve the density of artificial stone slabs, which is beneficial to improving the mechanical properties and impact strength of artificial stone slabs. It can also reduce the amount of modified unsaturated resin binder, which is beneficial to improving the dimensional stability of artificial stone slabs and reducing the production cost of artificial stone.

[0026] The present invention provides a method for preparing high-strength lightweight artificial stone slabs, which is achieved through the following technical solution:

[0027] A method for preparing high-strength lightweight artificial stone slabs includes the following steps:

[0028] Step 1: Mix the coupling agent compound, inorganic ore powder, hollow glass microspheres, and inorganic ore sand evenly to obtain a modified mixture of coupling agent compound.

[0029] Step 2: Under nitrogen protection and at a temperature of 0-10℃, mix the accurately measured coupling agent compound modified mixture with the modified unsaturated resin binder, compound curing agent, and defoamer evenly. Then, vacuum defoaming treatment is performed for 15-30 minutes, and low-temperature nitrogen is introduced to restore the temperature to room temperature to obtain the injection molding slurry.

[0030] Step 3: Place the injection slurry into the molding mold, and after pressing and medium-temperature curing, obtain the semi-finished artificial stone. The semi-finished artificial stone can be cut and polished to obtain the finished artificial stone.

[0031] Preferably, the inorganic mineral powder is any one of granite powder, quartz powder, basalt powder, and volcanic rock powder.

[0032] Preferably, the inorganic mineral sand is any one of granite sand, quartz sand, basalt sand, and volcanic rock sand.

[0033] In summary, the present invention has the following advantages:

[0034] 1. The artificial stone slab of the present invention has the technical advantages of being lightweight, high-strength, sound and heat insulated, having a low coefficient of thermal expansion, and good dimensional stability, thus expanding the application range of artificial stone slabs.

[0035] 2. This invention improves the overall density by optimizing the gradation of inorganic mineral powder, inorganic mineral sand, and hollow glass microspheres, which is beneficial to improving the mechanical properties and impact strength of artificial stone slabs, and can reduce the amount of modified unsaturated resin binder, which is beneficial to improving the dimensional stability of artificial stone slabs and reducing the overall production cost.

[0036] 3. The preparation method of the present invention is relatively simple and easy to operate. The production equipment is conventional artificial stone production equipment. The professional requirements for operators are not high, which is conducive to realizing industrialized mass production. The production cost of artificial stone slabs is reduced through large-scale production, and the market competitiveness of the product is further enhanced. Detailed Implementation

[0037] To further understand the inventiveness and technical advancements of this invention, the preferred embodiments of this invention will be discussed in detail below with reference to examples and comparative examples.

[0038] Example: A high-strength lightweight artificial stone slab is made from the following raw materials in weight percentages: 8-16 wt% modified unsaturated resin binder, 0.2-0.8 wt% compound curing agent, 0.05-0.2 wt% defoamer, 0.5-2.0 wt% coupling agent compound, 15-30 wt% inorganic mineral powder, 15-25 wt% hollow glass microspheres, and 35-50 wt% inorganic mineral sand.

[0039] The inorganic mineral powder can be any one of granite powder, quartz powder, basalt powder, or volcanic rock powder.

[0040] Inorganic mineral sand can be any one of granite sand, quartz sand, basalt sand, or volcanic rock sand.

[0041] The compound curing agent consists of a peroxide initiator and triallyl isocyanurate. The peroxide initiator is any one of methyl ethyl ketone peroxide, cyclohexanone peroxide, or benzoyl peroxide.

[0042] The modified unsaturated resin adhesive consists of conventional unsaturated polyester resin and polyurethane resin with active double bonds in the main chain, which provides toughening and reinforcing effects. The polyurethane resin with active double bonds in the main chain is a customized product; specifically, maleic anhydride-modified polyester polyol is used as a raw material in the production of this polyurethane resin. The maleic anhydride-modified polyester polyol is prepared from maleic anhydride, adipic acid, and 3-methyl-1,5-pentanediol.

[0043] Linear polyurethane resin has a relatively high coefficient of thermal expansion. To improve the dimensional stability of artificial stone, it needs to undergo free radical polymerization with triallyl isocyanate and the active double bonds in unsaturated polyester resin to form a three-dimensional network cross-linked structure, thereby improving the dimensional stability and mechanical properties of artificial stone. However, excessive cross-linking density can lead to a significant decrease in the impact strength of artificial stone. Therefore, it is necessary to control the content of triallyl isocyanate in the compound curing agent and the content of maleic anhydride in the maleic anhydride-modified polyester.

[0044] Furthermore, the polyurethane resin is end-capped with either bisphenol A epoxy resin or hydroxyethyl methacrylate. The coupling agent compound consists of methacryloxysilane and mercaptosilane.

[0045] If the polyurethane resin is end-capped with bisphenol A epoxy resin, it will undergo a dehydration condensation reaction with the mixed fillers (quartz powder, quartz sand, hollow glass microspheres) to form active thiol groups on the polysiloxane. Under the action of a thermal field, these groups will click chemically, improving the overall crosslinking density of the artificial stone and thus improving its overall dimensional stability and mechanical properties. To avoid excessive crosslinking density in the artificial stone, the amount of coupling agent compound needs to be controlled.

[0046] If the polyurethane resin is end-capped with hydroxyethyl methacrylate, it will react with the mixed fillers (inorganic mineral powder, inorganic mineral sand, hollow glass microspheres) through dehydration condensation to form active double bonds on the polysiloxane, active double bonds in the unsaturated polyester resin, and active double bonds in the triallyl isocyanate. Under the action of a peroxide initiator, these react with free radicals, improving the overall crosslinking density and thus enhancing the overall dimensional stability and mechanical properties. To avoid excessive crosslinking density in artificial stone, it is necessary to control the amount of coupling agent compound used. Another invention can reduce the amount of triallyl isocyanate used, thereby reducing the raw material cost of artificial stone.

[0047] Alternatively, the coupling agent compound may consist of methacryloxysilane, mercaptosilane, and chelated titanate coupling agents. The chelated titanate coupling agents can undergo transesterification with unsaturated polyester resins. This transesterification reaction optimizes the stress distribution of polymer chain segments, which helps reduce overall internal stress and improves the mechanical properties, heat resistance, and dimensional temperature characteristics of artificial stone.

[0048] The preferred formulation for high-strength lightweight artificial stone slabs is as follows: 10-12 wt% modified unsaturated resin binder, 0.5-0.8 wt% compound curing agent, 0.3-0.5 wt% defoamer, 0.8-1.2 wt% coupling agent compound, 24-30 wt% inorganic mineral powder, 18-24 wt% hollow glass microspheres, and 40-45 wt% inorganic mineral sand.

[0049] Optimizing the gradation of inorganic mineral powder, inorganic mineral sand, and hollow glass microspheres can improve the overall density, which is beneficial to improving the mechanical properties and impact strength of artificial stone slabs. It can also reduce the amount of modified unsaturated resin binder, which is beneficial to improving the dimensional stability of artificial stone slabs and reducing the overall production cost.

[0050] The optimized allocation scheme for inorganic ore powder is as follows: the inorganic ore powder consists of 26-32 wt% median diameter D 50 It is an inorganic mineral powder with a diameter of 8-10 μm and a median diameter of 8-12 wt%. 50 It consists of inorganic mineral powder with a particle size of 3-5 μm and the balance being the median diameter D. 50 It consists of inorganic mineral powder with a particle size of 15-20 μm.

[0051] The optimized allocation scheme for inorganic ore sand is as follows: the inorganic ore sand consists of 20-35 wt% median diameter D 50 It consists of inorganic mineral sand with a diameter of 90-100 μm and a median diameter of 10-20 wt%. 50 It consists of inorganic mineral sand with a diameter of 45-55 μm and the balance being the median diameter D. 50 It consists of inorganic mineral sand with a particle size of 160-180 μm.

[0052] The optimized packing scheme for hollow glass microspheres is as follows: the hollow glass microspheres are composed of 25-35 wt% median diameter D 50 Hollow glass microspheres with a diameter of 28-35 μm and a median diameter of 10-15 wt% D 50 Hollow glass microspheres of 10-20 μm, with the balance being the median diameter D. 50 It consists of hollow glass microspheres of 50-55 μm.

[0053] Example 1-A: A high-strength, lightweight artificial stone slab is made from the following raw materials in weight percentages: 10 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A (Jiangyin Rongshun Chemicals Co., Ltd.), 0.4 wt% of triallyl isocyanurate (CAS: 1025-15-6), and 0.05 wt% of BASF Efka PB. 2770 silicone-free defoamer, 0.5wt% coupling agent KH-570 (CAS:2530-85-0), 0.5wt% coupling agent KH-591 (CAS:4420-74-0), 0.4wt% bis(dioctylpyrophosphonooxy)ethylene titanate (CAS:65467-75-6), 27wt% quartz powder, 20wt% hollow glass microspheres, and 40wt% quartz sand.

[0054] The preparation method of polyurethane resin A containing active double bonds is as follows: S1. First, prepare maleic anhydride modified polyester diol: Add 140g of maleic anhydride, 1460g of adipic acid, 1420g of neopentyl glycol, and 0.5g of antioxidant 1010 to a reaction vessel, heat to 135℃ and hold for 3 hours, then uniformly heat to 230℃ and hold for 3 hours over 4 hours, controlling the temperature at the top of the distillation column at 102±0.5℃. As the reaction proceeds, take samples to measure the acid value. When the acid value reaches the range of 20-30mgKOH / g, add 0.2g of tetrabutyl titanate and evacuate the vacuum. Over 4 hours, gradually evacuate the pressure inside the vessel from atmospheric pressure to a relative vacuum of approximately -0.098MPa, take samples for testing, and when the hydroxyl value of the product in the vessel reaches... If the KOH concentration is 56.0 mg / g, the product is qualified. The reactor is then restored to normal pressure using nitrogen to break the vacuum and cooled to 110°C. The product is then unloaded and packaged to obtain maleic anhydride modified polyester glycol with a molecular weight of 2000. S2. Subsequently, 100 g of maleic anhydride modified polyester glycol, 175.6 g of toluene, 10.52 g of 1,4-butanediol, 50.06 g of Wanhua MDI-50, and 0.04 g of dibutyltin dilaurate T12 are weighed and added to the reactor. The mixture is heated to 75°C and reacted for 100 minutes. Then, the temperature is lowered to 60°C and 15 g of Phoenix brand epoxy resin E44 is added for end-capping reaction for 30 minutes. The mixture is then cooled to 25°C in a water bath, and the product is discharged to obtain polyurethane resin A containing active double bonds with a solid content of 50 wt%.

[0055] Quartz powder is composed of 30 wt% median diameter D 50 It consists of 8.5 μm quartz powder (800 mesh quartz powder) and 10 wt% median diameter D. 50 The quartz powder is 3.9 μm (1200 mesh), with the balance being the median diameter D. 50 It consists of 19.1μm quartz powder (325 mesh quartz powder). The 325 mesh quartz powder, 800 mesh quartz powder, and 1200 mesh quartz powder were provided by Shijiazhuang Xu'ang Mineral Products Processing Co., Ltd.

[0056] Quartz sand is composed of 30wt% median diameter D 50 It is 92.8μm quartz sand (70 mesh quartz sand) with a median diameter of 15wt%. 50 The silica sand is 52.8 μm (120 mesh silica sand), with the balance being the median diameter D. 50 It consists of 168.5μm silica sand (40 mesh silica sand). The 40 mesh silica powder, 70 mesh silica powder, and 120 mesh silica powder were provided by Shijiazhuang Xu'ang Mineral Products Processing Co., Ltd.

[0057] Hollow glass microspheres are composed of 30 wt% median diameter D 50 Hollow glass microspheres of 35 μm diameter (D10000, true density 0.6 ± 0.03 g / cm³), with a median diameter of 10 wt% D...50 Hollow glass microspheres of 15 μm (C100, true density 1.1 ± 0.2 g / cm³), with the balance being the median diameter D. 50 It consists of 50μm hollow glass microspheres C35 (true density 0.37±0.02g / cm3). Hollow glass microspheres D10000, C100, and C35 were provided by Zhongke Huaxing New Materials Co., Ltd.

[0058] A method for preparing high-strength lightweight artificial stone slabs includes the following steps:

[0059] Step 1: Prepare a modified aqueous solution of 43.4 parts by weight by mixing 0.5 parts by weight of coupling agent KH-570, 0.5 parts by weight of coupling agent KH-591, 0.4 parts by weight of bis(dioctylpyrophosphoryloxy)ethylene titanate, 14 parts by weight of deionized water, and 28 parts by weight of ethanol. Take 43.4 parts by weight of the modified aqueous solution and 8.1 parts by weight of median diameter D... 50 Quartz powder with a diameter of 8.5 μm and a median diameter D of 2.7 parts by weight. 50 Quartz powder with a diameter of 3.9 μm and a median diameter D of 16.2 parts by weight. 50 Quartz powder with a diameter of 19.1 μm and a median diameter D of 6 parts by weight 50 Hollow glass microspheres of 35 μm (D10000) and 2 parts by weight of median diameter D 50 Hollow glass microspheres of 15 μm C100, with a median diameter D of 12 parts by weight. 50 Hollow glass microspheres with a diameter of 50 μm (C35), 12 parts by weight, with a median diameter D 50 It is 92.8μm quartz sand (70 mesh quartz sand), 6 parts by weight of median diameter D 50 It consists of 52.8 μm quartz sand (120 mesh quartz sand) and 22 parts by weight of median diameter D. 50 Quartz sand with a diameter of 168.5 μm (40 mesh quartz sand) was put into a kneader and kneaded and mixed for half an hour. After vacuum drying for 6 hours to remove moisture and ethanol, the modified mixture of coupling agent compound was obtained.

[0060] Step 2: Under nitrogen protection and at a temperature of 4°C, the modified mixture of coupling agent compound prepared in Step 1 is mixed evenly with 10 parts by weight of 8033 unsaturated polyester resin, 1 part by weight of polyurethane resin A containing active double bonds, 0.1 parts by weight of methyl ethyl ketone peroxide, 0.05 parts by weight of colorless accelerator T-8A, 0.4 parts by weight of triallyl isocyanurate, and 0.05 parts by weight of BASF Efka PB 2770 silicone-free defoamer. Then, the mixture is vacuum defoamed for 30 minutes, and then low-temperature nitrogen is introduced to restore normal pressure. The resulting material is the injection molding slurry.

[0061] Step 3: Place the injection slurry into the molding mold, and then press and cure it at a medium temperature: cure it at 85℃ for 2 hours, and then cure it at 50℃ for 22 hours to obtain semi-finished artificial stone. The semi-finished artificial stone can be cut and polished to obtain finished artificial stone.

[0062] The difference between Example 1-B and Example 1-A is that: a high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 10 wt% of 8033 unsaturated polyester resin, 1 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% of coupling agent KH-570, 0.5 wt% of coupling agent KH-591, 0.4 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of granite powder, 20 wt% of hollow glass microspheres, and 40 wt% of granite sand.

[0063] Granite powder is composed of 30wt% median diameter D 50 It is 8.7 μm granite powder (800 mesh granite powder) with a median diameter of 10 wt%. 50 The material is 3.8 μm granite powder (1200 mesh granite powder), with the balance being the median diameter D. 50 It is composed of 19.3μm granite powder (325 mesh granite powder).

[0064] 325 mesh granite powder is produced by a 3R3016 Raymond mill. Granite crushed stone is fed into the 3R3016 Raymond mill for crushing, and then sieved through a 325 mesh screen. The sieved material is 325 mesh granite powder with a median diameter D. 50 It is 19.3 μm.

[0065] 800-mesh granite powder is produced using a 3R3016 Raymond mill. Granite crushed stone is fed into the 3R3016 Raymond mill for crushing, and then sieved through an 800-mesh screen. The sieved material is the 800-mesh granite powder, with a median diameter D. 50 It is 8.7μm.

[0066] 1200 mesh granite powder is produced by a 3R3016 Raymond mill. Granite crushed stone is fed into the 3R3016 Raymond mill for crushing, and then sieved through a 1200 mesh screen. The sieved material is 1200 mesh granite powder with a median diameter D. 50 It is 3.8μm.

[0067] Granite sand is composed of 30wt% median diameter D 50 It consists of 93.1 μm granite sand (70 mesh granite sand) and 15 wt% median diameter D.50 It is 52.9 μm granite sand (120 mesh granite sand), with the balance being the median diameter D. 50 It is composed of 168.7μm granite sand (40 mesh granite sand).

[0068] 40-mesh granite sand is produced by a 3R3016 Raymond mill. Granite crushed stone is fed into the 3R3016 Raymond mill for crushing, and then sieved through a 40-mesh screen. The sieved material is 40-mesh granite sand with a median diameter D. 50 It is 168.7 μm.

[0069] 70-mesh granite sand is produced by a 3R3016 Raymond mill. Granite crushed stone is fed into the 3R3016 Raymond mill for crushing, and then sieved through a 70-mesh screen. The sieved material is 70-mesh granite sand with a median diameter D. 50 It is 93.1 μm.

[0070] 120-mesh granite sand is produced by a 3R3016 Raymond mill. Granite crushed stone is fed into the 3R3016 Raymond mill for crushing, and then sieved through a 120-mesh screen. The sieved material is 120-mesh granite sand with a median diameter D. 50 It is 52.9 μm.

[0071] The difference in the preparation method of high-strength lightweight artificial stone slabs lies in the following: Step 1, 0.5 parts by weight of coupling agent KH-570, 0.5 parts by weight of coupling agent KH-591, 0.4 parts by weight of bis(dioctylpyrophosphoryloxy)ethylene titanate, 14 parts by weight of deionized water, and 28 parts by weight of ethanol are mixed to prepare a modified aqueous solution of 43.4 parts by weight. Then, 43.4 parts by weight of the modified aqueous solution and 8.1 parts by weight of median diameter D are taken... 50 Granite powder with a particle size of 8.7 μm and a median diameter D of 2.7 parts by weight. 50 Granite powder with a diameter of 3.8 μm and a median diameter D of 16.2 parts by weight. 50 Granite powder with a diameter of 19.3 μm and a median diameter D of 6 parts by weight 50 Hollow glass microspheres of 35 μm (D10000) and 2 parts by weight of median diameter D 50 Hollow glass microspheres of 15 μm C100, with a median diameter D of 12 parts by weight. 50 Hollow glass microspheres with a diameter of 50 μm (C35), 12 parts by weight, with a median diameter D 50 It is 93.1 μm granite sand (70 mesh granite sand), with a median diameter D of 6 parts by weight. 50 It is 52.9 μm granite sand (120 mesh granite sand), with 22 parts by weight of median diameter D. 50Granite sand with a particle size of 168.7 μm (40 mesh) was put into a kneader and kneaded for half an hour to mix it evenly. After vacuum drying for 6 hours to remove moisture and ethanol, the modified mixture of coupling agent compound was obtained. The remaining steps were the same.

[0072] The difference between Example 2 and Example 1-A is that the 8033 unsaturated polyester resin is replaced with JN-188 unsaturated polyester resin from Jiangyin Jinniu Fiberglass Materials Co., Ltd., while the other components remain unchanged.

[0073] The difference between Example 3 and Example 1-A is that the 8033 unsaturated polyester resin is replaced with the 855 unsaturated polyester resin from Changzhou Qiushuo Chemical Co., Ltd., while the other components remain unchanged.

[0074] The difference between Example 4 and Example 1-A is that polyurethane resin A containing active double bonds is replaced with polyurethane resin B containing active double bonds, while the other components remain unchanged.

[0075] The preparation method of polyurethane resin B containing active double bonds is as follows: Weigh 100g of maleic anhydride modified polyester diol, 165g of toluene, 10.52g of 1,4-butanediol, 50.06g of Wanhua MDI-50, and 0.04g of dibutyltin dilaurate T12 prepared in Example 1 and put them into a reaction vessel. Heat to 75°C and react for 100 minutes. Then cool to 60°C and add 4.4g of hydroxyethyl methacrylate for end-capping reaction for 30 minutes. Cool to 25°C in a water bath and discharge to obtain polyurethane resin B containing active double bonds with a solid content of 50wt%.

[0076] 100g of maleic anhydride polyol, 7g of ethylene glycol, 0.1g of antioxidant, and 400g of toluene were added to a reactor, heated to 45℃, and stirred for 25min. 41g of MDI was added, and the reactor temperature was controlled at 75℃ for 1 hour. A catalyst was added to continue the reaction. When the viscosity reached 5.0×103mPa·s / 25℃, the remaining MDI was added and reacted for 40min. The product was then discharged to obtain maleic anhydride polyurethane resin with a solid content of 31%.

[0077] The difference between Control Group 1 and Example 1-A is that the artificial stone slab is made from the following raw materials in the following weight percentages: 10 wt% of 8033 unsaturated polyester resin, 1 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% of coupling agent KH-570, 0.5 wt% of coupling agent KH-591, 0.4 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 35 wt% of quartz powder, and 52 wt% of quartz sand.

[0078] The difference between Control Group 2 and Example 1-A is that the artificial stone slab is made from the following raw materials in weight percentages: 11 wt% of 8033 unsaturated polyester resin, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% of coupling agent KH-570, 0.5 wt% of coupling agent KH-591, 0.4 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 35 wt% of quartz powder, and 52 wt% of quartz sand.

[0079] The difference between Comparative Example 1 and Example 1-A is that the artificial stone slab is made from the following raw materials in weight percentages: 11 wt% of 8033 unsaturated polyester resin, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% of coupling agent KH-570, 0.5 wt% of coupling agent KH-591, 0.4 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0080] The difference between Comparative Example 2 and Example 1-A is that the artificial stone slab was made from the following raw materials in weight percentages: 10 wt% JN-188 unsaturated polyester resin, 0.1 wt% methyl ethyl ketone peroxide, 0.05 wt% colorless accelerator T-8A, 0.4 wt% triallyl isocyanate, 0.05 wt% BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% coupling agent KH-570, 0.5 wt% coupling agent KH-591, 0.4 wt% bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% quartz powder, 20 wt% hollow glass microspheres, and 40 wt% quartz sand.

[0081] The difference between Comparative Example 3 and Example 1-A is that the artificial stone slab was made from the following raw materials in weight percentages: 10 wt% of 855 unsaturated polyester resin, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% of coupling agent KH-570, 0.5 wt% of coupling agent KH-591, 0.4 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0082] The difference between Comparative Example 4 and Example 1-A is that polyurethane resin A containing active double bonds is replaced with ordinary polyurethane resin C which does not contain active double bonds, while the other components remain unchanged.

[0083] The preparation method of ordinary polyurethane resin C without active double bonds is as follows: Weigh 100g of polyester diol with a molecular weight of 2000 (N56 polyester polyol from Yantai Huada Chemical Industry Co., Ltd.), 175.6g of toluene, 10.52g of 1,4-butanediol, 50.06g of Wanhua MDI-50, and 0.04g of dibutyltin dilaurate T12 and add them to the reaction vessel. Heat to 75℃ and react for 100 minutes. Then cool to 60℃ and add 15g of Phoenix brand epoxy resin E44 for end-capping reaction for 30 minutes. Cool to 25℃ in a water bath and discharge to obtain ordinary polyurethane resin C without active double bonds with a solid content of 50wt%.

[0084] The difference between Example 5 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 10.08 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1.12 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.2 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% of coupling agent KH-570, 0.5 wt% of coupling agent KH-591, 0.4 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0085] The difference between Example 6 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 9.72 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1.08 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.6 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% of coupling agent KH-570, 0.5 wt% of coupling agent KH-591, 0.4 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0086] The difference between Comparative Example 5 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 10.26 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1.14 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% of coupling agent KH-570, 0.5 wt% of coupling agent KH-591, 0.4 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0087] The difference between Comparative Example 6 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 10.17 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1.13 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.1 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% of coupling agent KH-570, 0.5 wt% of coupling agent KH-591, 0.4 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0088] The difference between Comparative Example 7 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 9.54 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1.06 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.8 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.5 wt% of coupling agent KH-570, 0.5 wt% of coupling agent KH-591, 0.4 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0089] The difference between Example 7 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 10 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.7 wt% of coupling agent KH-570, 0.7 wt% of coupling agent KH-591, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0090] The difference between Example 8 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 10 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.2 wt% of coupling agent KH-570, 0.2 wt% of coupling agent KH-591, 0.1 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0091] The difference between Example 9 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 10 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.7 wt% of coupling agent KH-570, 0.7 wt% of coupling agent KH-591, 0.6 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0092] The difference between Comparative Example 8 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 10 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 1.4 wt% of coupling agent KH-570, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0093] The difference between Comparative Example 9 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 10 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.1 wt% of coupling agent KH-570, 0.1 wt% of coupling agent KH-591, 0.05 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0094] The difference between Comparative Example 10 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the following weight percentages: 10 wt% of 8033 unsaturated polyester resin (Jiangyin Shunsheng Composite Materials Co., Ltd.), 1 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, 0.05 wt% of BASF Efka PB 2770 silicone-free defoamer, 0.8 wt% of coupling agent KH-570, 0.8 wt% of coupling agent KH-591, 0.64 wt% of bis(dioctyl pyrophosphoryloxy)ethylene titanate, 27 wt% of quartz powder, 20 wt% of hollow glass microspheres, and 40 wt% of quartz sand.

[0095] The difference between Example 10 and Example 1-A is that the quartz powder consists of 100 wt% median diameter D 50 It is composed of quartz powder with a particle size of 19.1 μm (325 mesh quartz powder).

[0096] The difference between Example 11 and Example 1-A is that the quartz sand consists of 37.5 wt% median diameter D 50It is quartz sand with a diameter of 92.8 μm (70 mesh quartz sand) and a median diameter of 62.5 wt%. 50 It is composed of quartz sand with a diameter of 168.5 μm (40 mesh quartz sand).

[0097] The difference between Example 12 and Example 1-A is that the hollow glass microspheres are composed of 100 wt% median diameter D 50 It is composed of 50μm hollow glass microspheres C35 (true density 0.37±0.02g / cm3).

[0098] The difference between Example 13 and Example 1-A is that the quartz powder consists of 100 wt% median diameter D 50 It consists of quartz powder with a diameter of 19.1 μm (325 mesh). The quartz sand has a median diameter of 37.5 wt%. 50 It is quartz sand with a diameter of 92.8 μm (70 mesh quartz sand) and a median diameter of 62.5 wt%. 50 It consists of 168.5 μm silica sand (40 mesh silica sand). The hollow glass microspheres are composed of 100 wt% median diameter D. 50 It is composed of 50μm hollow glass microspheres C35 (true density 0.37±0.02g / cm3).

[0099] The difference between Example 14 and Example 1-A is that the quartz powder consists of 100 wt% median diameter D 50 It consists of quartz powder with a diameter of 19.1 μm (325 mesh). The quartz sand has a median diameter of 37.5 wt%. 50 It is quartz sand with a diameter of 92.8 μm (70 mesh quartz sand) and a median diameter of 62.5 wt%. 50 It consists of 168.5 μm silica sand (40 mesh silica sand). The hollow glass microspheres are composed of 25 wt% median diameter D. 50 Hollow glass microspheres with a diameter of 35 μm (D10000) and a median diameter of 25 wt% (D) 50 Hollow glass microspheres of 15 μm (C100), with the balance being the median diameter D. 50 It consists of 50μm hollow glass microspheres (C35).

[0100] Performance testing: 1. Density measurement: GB / T 35160.1-2017 Synthetic Stone Test Methods Part 1: Determination of density and water absorption. 2. Flexural strength: GB / T 35160.2-2017 Synthetic Stone Test Methods Part 2: Determination of flexural strength. 3. Compressive strength: GB / T 35160.3-2017 Synthetic Stone Test Methods Part 3: Determination of compressive strength. 4. Coefficient of thermal expansion: GB / T 35160.5-2017 Synthetic Stone Test Methods Part 5: Determination of thermochromic properties. 5. Impact strength: GB / T 35160.6-2017 Synthetic Stone Test Methods Part 6: Determination of impact resistance. If a 1kg steel ball is dropped from a height difference of X cm from the artificial stone slab without damage, but is damaged when dropped from a height difference of X+5 cm, then the impact strength is X cm.

[0101] Table 1: Test parameters of artificial stone in Examples 1-A, 1-B, 2-4, Control Groups 1-2 and Comparative Examples 1-4

[0102]

[0103]

[0104] Based on Examples 1-A, 2-3, and Control Groups 1-2, and in conjunction with Table 1, it can be seen that replacing part of the quartz sand and quartz powder with hollow glass microspheres leads to a decrease in the compressive and flexural properties of the prepared artificial stone. However, the compressive strength of the prepared artificial stone slab is ≥150MPa, the flexural strength is ≥25MPa, and the coefficient of thermal expansion is <2*10. -5 Even at ℃, it still maintains good mechanical properties and dimensional stability, meeting normal usage requirements, and can reduce the density of artificial stone from 2.36±0.01 to ≤2.0g / cm³. 3 This enables the lightweight design of artificial stone.

[0105] Based on Examples 1-A, 23, Control Groups 1-2, and Comparative Examples 1-3, and in conjunction with Table 1, it can be seen that using commercially available unsaturated polyester resin combined with epoxy-terminated polyurethane resin containing double bonds in the main chain as the main adhesive can improve the impact toughness, compression performance, bending performance, and dimensional stability of artificial stone.

[0106] Based on Examples 1-A, 23, and Comparative Examples 1-3, and in conjunction with Table 1, it can be seen that the artificial stone prepared in Examples 1-3 contains 20 wt% hollow glass microspheres, which can effectively reduce the overall density (≤2.0 g / cm³). 3 And the compressive strength is ≥100MPa, the flexural strength is ≥20MPa, and the coefficient of thermal expansion is <2*10.-5 / ℃, ensuring overall mechanical properties and dimensional stability while achieving lightweight design of artificial stone.

[0107] Based on Examples 1-A, 24, and Comparative Example 4, and referring to Table 1, it can be seen that ordinary polyurethane resin C, which does not contain active double bonds, has a plasticizing effect, improving processing viscosity and impact toughness. However, the compressive and flexural properties of the prepared artificial stone show a decreasing trend. Compared with artificial stone prepared from polyurethane resins with epoxy-terminated main chains containing double bonds or polyurethane resins with propylene-terminated main chains containing double bonds in the main adhesive, the artificial stone in Examples 1 and 4 of this invention has superior overall performance, endowing the artificial stone with good impact toughness, compressive properties, flexural properties, and dimensional stability.

[0108] Adding hollow glass microspheres to artificial stone slabs can also give artificial stone good sound and heat insulation properties.

[0109] Table 2: Test parameters of artificial stone in Examples 1-A, 5-6 and Comparative Examples 5-7

[0110]

[0111] Based on Examples 1-A, 5-6, and Comparative Examples 5-7, and referring to Table 2, it can be seen that controlling the addition amount of triallyl isocyanate to 0.2-0.6 wt% ensures that the prepared artificial stone has good impact toughness, dimensional stability, compressive strength, and flexural strength. Excessive addition of triallyl isocyanate leads to a significant increase in the rigidity of the artificial stone but a severe decrease in impact toughness.

[0112] Table 3: Test parameters of artificial stone in Examples 1-A, 7-9 and Comparative Examples 8-10

[0113]

[0114] Based on Examples 1-A, 7-9, and Comparative Examples 8-10, and referring to Table 3, it can be seen that controlling the addition amount of the coupling agent compound to 0.5-2.0 wt% ensures that the artificial stone has good overall performance. More preferably, the addition amount of the coupling agent compound is controlled to 1.2-1.5 wt%.

[0115] Based on Examples 1-A and 7 and Table 3, it can be seen that the mechanical properties of artificial stone prepared by combining methacryloyloxysilane KH570, mercaptosilane KH591, and chelated titanate coupling agent are slightly better than those of artificial stone prepared by combining methacryloyloxysilane KH570 and mercaptosilane KH591. Therefore, adding an appropriate amount of chelated titanate coupling agent to the coupling agent compound can improve the mechanical properties of artificial stone.

[0116] Based on Examples 1-A and Comparative Example 8, and referring to Table 3, it can be seen that the artificial stone prepared by the coupling agent complex has better overall performance than that prepared by adding only methacryloyloxysilane KH570. Excessive addition of KH570 also leads to an excessive increase in crosslinking density, resulting in excessive rigidity and a significant decrease in impact toughness of the artificial stone. Therefore, the artificial stone prepared by using the coupling agent complex composed of methacryloyloxysilane KH570, mercaptosilane KH591, and chelated titanate coupling agent, or the coupling agent complex composed of methacryloyloxysilane KH570 and mercaptosilane KH591, has superior overall performance.

[0117] Table 4: Test parameters of artificial stone in Examples 1-A and 10-14

[0118]

[0119] Based on Examples 1-A and 10-14 and Table 4, it can be seen that optimizing the gradation of quartz powder, quartz sand, and hollow glass microspheres can improve the mechanical properties, impact strength, and dimensional stability of artificial stone.

[0120] To further improve the compressive and flexural properties of artificial stone slabs, the inventors added inorganic fiber fillers with high aspect ratios as reinforcing materials to the artificial stone formulation. Specifically, the difference between Example 16 and Example 1-A is that the high-strength lightweight artificial stone slab is made from the following raw materials in the indicated weight percentages: 10 wt% of 8033 unsaturated polyester resin, 1 wt% of polyurethane resin A containing active double bonds, 0.1 wt% of methyl ethyl ketone peroxide, 0.05 wt% of colorless accelerator T-8A, 0.4 wt% of triallyl isocyanate, and 0.05 wt% of BASF Efka PB. 2770 silicone-free defoamer, 0.5wt% coupling agent KH-570, 0.5wt% coupling agent KH-591, 0.4wt% bis(dioctylpyrophosphoryloxy)ethylene titanate, 24wt% quartz powder, 5wt% Jushi 562A chopped raw filaments, 20wt% hollow glass microspheres, and 38wt% quartz sand.

[0121] Before use, the Jushi 562A chopped raw fibers are modified with a coupling agent complex aqueous solution. Specifically, 1 part by weight of coupling agent KH-570, 1 part by weight of coupling agent KH-591, 0.8 parts by weight of bis(dioctylpyrophosphono)ethylene titanate, 28 parts by weight of deionized water, and 56 parts by weight of ethanol are mixed evenly to form a coupling agent complex aqueous solution. 5 parts by weight of Jushi 562A chopped raw fibers are added to the coupling agent complex aqueous solution and ultrasonically dispersed for 30 minutes. After draining, the fibers are vacuum dried for 2 hours.

[0122] The density of the high-strength lightweight artificial stone slab in Example 16 is 1.972 g / cm³. 3 The compressive strength is 184.3 MPa, the flexural strength is 35.1 MPa, and the coefficient of thermal expansion is 1.76 × 10⁻⁶. -5 The temperature was / ℃, and the impact strength was 60cm. This demonstrates that adding high aspect ratio chopped glass fibers can improve the mechanical properties, dimensional stability, and impact toughness of artificial stone slabs, giving them superior lightweight and high-strength properties. The mechanical properties of the artificial stone in Example 16 are comparable to those of the artificial stone in Control Group 1. This means that adding high aspect ratio chopped glass fibers can compensate for the loss of mechanical properties caused by the incorporation of hollow glass microspheres, while also improving the impact toughness and dimensional stability of the artificial stone slab, further enhancing its market competitiveness.

[0123] It should be noted that this specific embodiment is merely an explanation of the technical solution of the present invention and is not intended to limit the present invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A high-strength, lightweight artificial stone slab, characterized in that: The high-strength lightweight artificial stone slab is made from the following raw materials in the indicated weight percentages: 8-16 wt% modified unsaturated resin binder, 0.5-0.8 wt% compound curing agent, 0.05% colorless accelerator T-8A, 0.05-0.2 wt% defoamer, 0.5-2.0 wt% coupling agent compound, 15-30 wt% inorganic mineral powder, 15-25 wt% hollow glass microspheres, and 35-50 wt% inorganic mineral sand; the hollow glass microspheres have a particle size distribution of 5-100 μm and a true density of 0.14-1.3 g / cm³. 3 ; The modified unsaturated resin adhesive is composed of unsaturated polyester resin and polyurethane resin containing active double bonds; the raw materials for producing polyurethane resin containing active double bonds include maleic anhydride modified polyester polyol; the polyurethane resin containing active double bonds is end-capped with bisphenol A epoxy resin or with hydroxyethyl methacrylate. The compound curing agent consists of a peroxide initiator and triallyl isocyanurate; the amount of triallyl isocyanurate added is controlled at 0.2-0.4 wt%. The coupling agent complex consists of methacryloxysilane and mercaptosilane.

2. The high-strength lightweight artificial stone slab according to claim 1, characterized in that: The high-strength lightweight artificial stone slab is made from the following raw materials in the indicated weight percentages: 10-12 wt% modified unsaturated resin binder, 0.5-0.8 wt% compound curing agent, 0.05% colorless accelerator T-8A, 0.05-0.2 wt% defoamer, 0.8-1.2 wt% coupling agent compound, 24-30 wt% inorganic mineral powder, 18-24 wt% hollow glass microspheres, and 40-45 wt% inorganic mineral sand; the inorganic mineral powder is any one of granite powder, quartz powder, basalt powder, and volcanic rock powder; the inorganic mineral sand is any one of granite sand, quartz sand, basalt sand, and volcanic rock sand.

3. The high-strength lightweight artificial stone slab according to claim 1, characterized in that: The peroxide initiator is any one of methyl ethyl ketone peroxide, cyclohexanone peroxide, and benzoyl peroxide.

4. The high-strength lightweight artificial stone slab according to claim 1, characterized in that: The inorganic ore powder consists of 26-32 wt% median diameter D 50 It is an inorganic mineral powder with a diameter of 8-10 μm and a median diameter of 8-12 wt%. 50 It consists of inorganic mineral powder with a particle size of 3-5 μm and the balance being the median diameter D. 50 It consists of inorganic mineral powder with a particle size of 15-20 μm.

5. A high-strength lightweight artificial stone slab according to claim 4, characterized in that: The inorganic ore powder consists of 30±0.5wt% median diameter D 50 It is an inorganic mineral powder with a particle size of 8-10 μm and a median diameter D of 10 ± 0.5 wt%. 50 It consists of inorganic mineral powder with a particle size of 3-5 μm and the balance being the median diameter D. 50 It consists of inorganic mineral powder with a particle size of 15-20 μm.

6. The high-strength lightweight artificial stone slab according to claim 1, characterized in that: The inorganic ore sand is composed of 20-35 wt% median diameter D 50 It consists of inorganic mineral sand with a diameter of 90-100 μm and a median diameter of 10-20 wt%. 50 It consists of inorganic mineral sand with a diameter of 45-55 μm and the balance being the median diameter D. 50 It consists of inorganic mineral sand with a particle size of 160-180 μm.

7. A high-strength lightweight artificial stone slab according to claim 6, characterized in that: The inorganic ore sand is composed of 30±0.5wt% median diameter D 50 It is an inorganic mineral sand with a diameter of 90-100 μm and a median diameter of 15 ± 0.5 wt%. 50 It consists of inorganic mineral sand with a diameter of 45-55 μm and the balance being the median diameter D. 50 It consists of inorganic mineral sand with a particle size of 160-180 μm.

8. A high-strength lightweight artificial stone slab according to claim 1, characterized in that: The hollow glass microspheres are composed of 25-35 wt% median diameter D 50 Hollow glass microspheres with a diameter of 28-35 μm and a median diameter of 10-15 wt% D 50 Hollow glass microspheres of 10-20 μm, with the balance being the median diameter D. 50 It consists of hollow glass microspheres of 50-55 μm.

9. A high-strength lightweight artificial stone slab according to claim 7, characterized in that: The hollow glass microspheres are composed of 30±0.5wt% median diameter D 50 Hollow glass microspheres of 28-35 μm, with a median diameter D of 10 ± 0.5 wt%. 50 Hollow glass microspheres of 10-20 μm, with the balance being the median diameter D. 50 It consists of hollow glass microspheres of 50-55 μm.

10. A method for preparing a high-strength lightweight artificial stone slab according to any one of claims 1-9, characterized in that: Includes the following steps: Step 1: Mix the coupling agent compound, inorganic ore powder, hollow glass microspheres, and inorganic ore sand evenly to obtain a modified mixture of coupling agent compound. Step 2: Under nitrogen protection and at a temperature of 0-10℃, mix the accurately measured coupling agent compound modified mixture with the modified unsaturated resin binder, compound curing agent, colorless accelerator T-8A, and defoamer evenly. Then, vacuum defoaming treatment is performed for 15-30 minutes, and low-temperature nitrogen is introduced to restore the temperature to room temperature to obtain the injection molding slurry. Step 3: Place the injection slurry into the molding mold, and after pressing and medium-temperature curing, obtain the semi-finished artificial stone. The semi-finished artificial stone can be cut and polished to obtain the finished artificial stone.

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