Radiation crosslinking enhanced high-strength water-resistant artificial stone and preparation method thereof

Abstract

The application discloses high-strength water-resistant artificial stone with irradiation cross-linking enhancement and a preparation method thereof, and belongs to the technical field of artificial stone building materials. The high-strength water-resistant artificial stone comprises the following components in parts by mass: a ternary cementing system 15-25 parts, surface modified silica micro powder 50-60 parts, nano active calcium carbonate 3-7 parts, thermosetting resin 12-18 parts, initiator or curing agent 0.1-0.3 parts, accelerator 0.02-0.1 parts, triallyl isocyanurate 0.3-1.0 parts, polycarboxylic acid water reducing agent 0.1-0.5 parts, organic silicon defoaming agent 0.05-0.3 parts, wetting agent 0.05-0.5 parts and water 4-6 parts. When the initiator is added and the curing agent is not added, the artificial stone formula further comprises cross-linking monomer 2-4 parts. The silane coupling agent with the functions of hydrophobicity and irradiation cross-linking promotion is designed and synthesized, and the synergistic promotion of high strength and high water resistance of the artificial stone is realized.

Description

Technical Field

[0001] This invention relates to the field of artificial stone building materials technology, and more specifically, to a high-strength, water-resistant artificial stone enhanced by irradiation crosslinking and its preparation method. Background Technology

[0002] Artificial stone, as a substitute for natural stone, has been widely used in the field of building decoration. Traditional artificial stone is made by mixing, molding, and curing unsaturated polyester resin (UPR) or epoxy resin as binder and calcium carbonate powder, aluminum hydroxide powder or quartz sand as filler. However, existing artificial stone technologies have the following technical bottlenecks: (1) poor interfacial compatibility between resin and inorganic filler, with a large number of microcracks and pores in the interfacial transition zone, making it difficult to break through the strength barrier; (2) the degree of resin curing depends on the thermal curing of the initiator, and the crosslinking density is limited (usually only 70%-85%), resulting in insufficient flexural strength and wear resistance of the material; (3) after the resin is cured, there are unreacted active groups remaining, which are prone to water absorption and swelling during long-term use, resulting in poor water resistance; (4) no existing technologies have reported artificial stone that simultaneously achieves flexural strength ≥30MPa, compressive strength ≥120MPa, and water absorption ≤0.05%.

[0003] Extensive research has been conducted on polymer-modified artificial stone. Patent CN105399384A discloses a method of mixing and pressing polyvinyl acetate emulsion with quartz sand. However, this technology relies solely on physical compaction for densification, resulting in a lack of chemical bonding between the resin and filler, leading to limited interfacial adhesion strength. Furthermore, the resin curing process utilizes traditional thermosetting, resulting in insufficient crosslinking density. Patent CN104556903A discloses an inorganic artificial quartz stone slab and its preparation method, which improves the interfacial bonding between the inorganic filler and resin by adding a silane coupling agent to the resin system. However, in this technology, the silane coupling agent is only added as a physical blending component, failing to achieve directional grafting and high-density chemical bonding with the filler surface, resulting in limited interfacial reinforcement. It also relies on thermosetting, leading to insufficient crosslinking network integrity.

[0004] In existing technologies, coupling agents are mostly added to the resin system through direct physical blending, lacking pre-chemical modification and high-density grafting of inorganic filler surfaces. Furthermore, silane coupling agents have relatively limited functionality; for example, γ-aminopropyltriethoxysilane (KH550) only provides amino reaction sites, and γ-methacryloyloxypropyltrimethoxysilane (KH570) only provides vinyl reaction sites. Multifunctional coupling agents with both hydrophobic and radiation-driven crosslinking functions are lacking. Existing curing methods all rely on initiator-based thermal curing, and the crosslinking density is limited by the conversion rate of reactive groups on the resin molecular chain (typically ≤85%), with residual active groups becoming a cause of water absorption and degradation. Multifunctional silane coupling agents with both hydrophobic and radiation-driven crosslinking functions have not been reported; technologies that further enhance the crosslinking degree of the polymer matrix through high-energy radiation (such as electron beams or gamma rays) combined with radiation sensitizers, and synergistically apply radiation crosslinking and interfacial hydrophobic modification to artificial stone, have also not been disclosed. Summary of the Invention

[0005] To address the challenges of existing technologies, this invention provides a radiation-crosslinked enhanced high-strength water-resistant artificial stone and its preparation method. By designing and synthesizing a multifunctional silane coupling agent that combines hydrophobicity and radiation crosslinking promotion, a three-in-one synergistic enhancement of "high-density interfacial chemical bonding - hydrophobic shielding - radiation-sensitized deep crosslinking" is achieved, resulting in a synergistic improvement in the high strength and high water resistance of the artificial stone.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A type of irradiated crosslinked reinforced high-strength water-resistant artificial stone comprises the following components by weight: 15-25 parts of a ternary cementitious system, 50-60 parts of surface-modified silica powder, 3-7 parts of nano-activated calcium carbonate, 12-18 parts of thermosetting resin, 0.1-0.3 parts of initiator or curing agent, 0.02-0.1 parts of accelerator, 0.3-1.0 parts of triallyl isocyanurate, 0.1-0.5 parts of polycarboxylate superplasticizer, 0.05-0.3 parts of silicone defoamer, 0.05-0.5 parts of wetting agent, and 4-6 parts of water; when an initiator is added but no curing agent is added, the artificial stone formulation also includes 2-4 parts of crosslinking monomer.

[0008] Furthermore, the ternary cementitious system is composed of ordinary silicate cement, high belite sulfoaluminate cement, and gypsum, which are dry-mixed and homogenized.

[0009] Furthermore, the surface-modified silica powder is silica powder that has undergone surface chemical grafting treatment with tris(3-trimethoxysilylpropyl)isocyanurate grafted with fluorinated long-chain alkyl derivatives, wherein the fluorinated long-chain alkyl is perfluorooctylethyl or perfluorohexylethyl.

[0010] Further, tris(3-trimethoxysilylpropyl)isocyanurate grafted with fluorinated long-chain alkyl derivatives was dissolved in a solvent to prepare a coupling agent solution. The pH value was adjusted, and a hydrolysis reaction was carried out. After the reaction, dried silica powder was added and stirred to obtain surface-modified silica powder.

[0011] Furthermore, the concentration of the coupling agent solution is 4-6 wt%, the mass ratio of the dried silica powder to the coupling agent solution is 1:(2-4), and the stirring reaction temperature is 50-70℃ for 3-5 h.

[0012] Furthermore, a hydrosilylation reaction was carried out on triallyl isocyanurate, trimethoxysilane, and platinum catalyst under nitrogen protection, followed by a nucleophilic substitution reaction with the addition of fluorinated long-chain alkyl groups and a basic catalyst to obtain tri(3-trimethoxysilylpropyl)isocyanurate grafted with fluorinated long-chain alkyl derivatives.

[0013] Furthermore, the reaction temperature for the hydrosilylation reaction is 80-90℃ and the reaction time is 6-8h, while the reaction temperature for the nucleophilic substitution reaction is 80-90℃ and the reaction time is 4-6h. The mass ratio of triallyl isocyanurate, trimethoxysilane, fluorinated long-chain alkyl group and basic catalyst is (80-120):(65-75):(25-35):(0.5-1.5), and the concentration of platinum catalyst in the hydrosilylation reaction system is 5-15ppm.

[0014] Furthermore, the thermosetting resin is at least one of unsaturated polyester resin and epoxy resin;

[0015] When an initiator is added without a curing agent, the thermosetting resin is an unsaturated polyester resin, the initiator is benzoyl peroxide or methyl ethyl ketone peroxide, the crosslinking monomer is styrene or methyl methacrylate, and the accelerator is dimethylaniline or cobalt naphthenate.

[0016] When a curing agent is added without an initiator, the thermosetting resin is epoxy resin, the curing agent is dicyandiamide or anhydride curing agent, and the accelerator is imidazole or tertiary amine compound.

[0017] A method for preparing irradiated crosslinking enhanced high-strength water-resistant artificial stone involves mixing the components evenly, molding the mixture into a mold, curing it after demolding to allow it to undergo preliminary thermosetting, irradiating crosslinking under nitrogen protection after curing, and then performing post-treatment to obtain irradiated crosslinking enhanced high-strength water-resistant artificial stone.

[0018] Furthermore, the high-energy rays used for irradiation crosslinking are electron beams or gamma rays; electron beam irradiation is used for artificial stone with a thickness ≤20mm; gamma ray irradiation or a combination of electron beam and gamma ray irradiation is used for artificial stone with a thickness >20mm and ≤50mm; and a combination of electron beam and gamma ray irradiation process is used for artificial stone with a thickness >50mm.

[0019] In summary, the present invention has the following beneficial effects:

[0020] (1) Multifunctional coupling agent with both hydrophobic and crosslinking functions: This invention designs and synthesizes tri(3-trimethoxysilylpropyl)isocyanurate grafted with fluorinated long-chain alkyl derivatives (T-IC-F). This coupling agent simultaneously contains three trimethoxysilyl anchoring groups, fluorinated long-chain hydrophobic groups, and retained allyl radiation-sensitizing groups (residual rate ≥30%). The three trimethoxysilyl groups form multi-point anchoring on the surface of silicon micropowder, and the surface grafting density is 2-3 times higher than that of monosilane coupling agents; the fluorinated long-chain alkyl groups endow silicon micropowder with low surface energy characteristics, forming a hydrophobic molecular layer; the retained allyl groups participate in the crosslinking reaction under irradiation conditions, promoting the synergistic crosslinking of the interface and the bulk phase. A single coupling agent simultaneously achieves three functions: "high-density bonding + hydrophobic shielding + radiation sensitization", avoiding the problems of poor compatibility and complex processes caused by adding multiple additives separately.

[0021] (2) Synergistic effect of high-density interfacial chemical bonding and hydrophobic shielding: The T-IC-F modified silica powder has a surface active functional group density ≥1.5mmol / g, and the number of chemical bonding sites with the resin matrix is ​​2-3 times that of traditional monosilane coupling agent modification, resulting in a 4-6 times increase in interfacial bonding strength. At the same time, the hydrophobic molecular layer formed by the fluorinated long-chain alkyl group in the interfacial region effectively blocks the path of water penetration along the interface, reducing the water absorption rate from 0.2%-0.5% of traditional artificial stone to ≤0.035%, the water contact angle ≥115°, and the flexural strength retention rate after 7 days of immersion in water ≥94%.

[0022] (3) Allyl promotes radiation-sensitized crosslinking: The allyl groups retained in T-IC-F (residual rate ≥30%) generate highly active free radicals under irradiation conditions, which work synergistically with TAIC (tracelyl isocyanurate) to increase the degree of crosslinking of the resin matrix from 70%-85% in traditional thermosetting to ≥95%, and reduce the irradiation dose from the conventional 50-100kGy to 20-40kGy. T-IC-F provides interfacial crosslinking nodes, and TAIC provides bulk crosslinking nodes. Together, they realize an integrated "interfacial-bulk" crosslinking network.

[0023] (4) Multi-scale filling and densification of nano-active calcium carbonate: Nano-active calcium carbonate (primary particle size 20-80nm, average aggregate particle size 300-500nm) is uniformly filled in the gaps between micron-sized silicon powder particles and the nano-sized pores in the interface transition zone, forming a "micron-submicron" multi-scale gradation, further blocking the water penetration channel, and reducing the water absorption rate to ≤0.035%.

[0024] (5) Synergistic reinforcement of the ternary cementitious system: P·II 52.5R type silicate cement, high belite sulfoaluminate cement (CSA) and gypsum constitute a ternary cementitious system, with a mass ratio of PC:CSA:gypsum = 80:15:5. PC is absolutely dominant (80%), providing long-term strength skeleton and continuous hydration capacity; CSA (15%) plays a role in rapid hardening and early strength and promotes setting, ensuring early strength development; gypsum (5%) precisely controls the formation rate and crystal size of ettringite. The hydration products CSH gel and ettringite crystals interpenetrate in the interface region, forming an organic-inorganic interpenetrating structure with the resin crosslinking network, further improving the density and strength of the material.

[0025] (6) Synergistic optimization of molding quality by additives: This invention introduces polycarboxylate superplasticizer, silicone defoamer, and wetting agent into the formulation. The superplasticizer effectively reduces the water-cement ratio, reducing water consumption while maintaining the fluidity of the slurry; the defoamer eliminates air bubbles introduced during mixing and molding, reducing internal defects; the wetting agent reduces the interfacial tension between the resin and inorganic filler, improving the uniformity of filler dispersion. The synergistic effect of the three agents gives the slurry better fluidity and uniformity before pressing, thus providing a more ideal initial structure for subsequent thermosetting and irradiation crosslinking.

[0026] (7) Synergistic enhancement mechanism of irradiation crosslinking and interface hydrophobic modification: This invention achieves a breakthrough for the first time in the artificial stone system through the three-in-one synergistic enhancement mechanism of “T-IC-F construction of an integrated interface of ‘chemical bonding + hydrophobic shielding’ (interface enhancement and hydrophobicity) + TAIC and T-IC-F allyl synergistic sensitization irradiation crosslinking (bulk crosslinking and water resistance) + nano-active calcium carbonate multi-scale filling densification (pore sealing)”, with flexural strength ≥34MPa, compressive strength ≥130MPa, water absorption ≤0.05%, wear resistance pit length ≤12mm, water contact angle ≥115°, and strength retention rate ≥92% after immersion in water for 7 days. Detailed Implementation

[0027] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0028] The present invention discloses a radiation-crosslinked enhanced high-strength water-resistant artificial stone, comprising the following components by weight: 15-25 parts of a ternary cementitious system, 50-60 parts of surface-modified silica powder, 3-7 parts of nano-activated calcium carbonate, 12-18 parts of thermosetting resin, 0.1-0.3 parts of initiator or curing agent, 0.02-0.1 parts of accelerator, 0.3-1.0 parts of triallyl isocyanurate, 0.1-0.5 parts of polycarboxylate superplasticizer, 0.05-0.3 parts of silicone defoamer, 0.05-0.5 parts of wetting agent, and 4-6 parts of water; when an initiator is added but a curing agent is not added, the artificial stone formulation further includes 2-4 parts of crosslinking monomer.

[0029] The formula for this irradiated cross-linked enhanced high-strength water-resistant artificial stone is as follows: 15-25 parts by weight of ternary cementitious system, 50-60 parts by weight of surface-modified silica powder, 3-7 parts by weight of nano-activated calcium carbonate, 12-18 parts by weight of thermosetting resin, 0.1-0.3 parts by weight of initiator, 2-4 parts by weight of cross-linking monomer, 0.02-0.1 parts by weight of accelerator, 0.3-1.0 parts by weight of triallyl isocyanurate, 0.1-0.5 parts by weight of polycarboxylate superplasticizer, 0.05-0.3 parts by weight of silicone defoamer, and 0.05-0.05 parts by weight of wetting agent. 0.5 parts by weight, water 4-6 parts by weight; or: 15-25 parts by weight of ternary cementitious system, 50-60 parts by weight of surface-modified silica powder, 3-7 parts by weight of nano-activated calcium carbonate, 12-18 parts by weight of thermosetting resin, 0.1-0.3 parts by weight of curing agent, 0.02-0.1 parts by weight of accelerator, 0.3-1.0 parts by weight of triallyl isocyanurate, 0.1-0.5 parts by weight of polycarboxylate superplasticizer, 0.05-0.3 parts by weight of silicone defoamer, 0.05-0.5 parts by weight of wetting agent, water 4-6 parts by weight.

[0030] The ternary cementitious system is composed of ordinary silicate cement, high belite sulfoaluminate cement and gypsum dry-mixed. The mass ratio of ordinary silicate cement, high belite sulfoaluminate cement and gypsum is 80:15:5. The gypsum is dihydrate gypsum or anhydrite.

[0031] The thermosetting resin is at least one of unsaturated polyester resin and epoxy resin; when no curing agent is added but an initiator is added, the thermosetting resin is unsaturated polyester resin, the initiator is benzoyl peroxide or methyl ethyl ketone peroxide, the crosslinking monomer is styrene or methyl methacrylate, and the accelerator is dimethylaniline or cobalt naphthenate; when no initiator is added but a curing agent is added, the thermosetting resin is epoxy resin, the curing agent is dicyandiamide or anhydride curing agent, and the accelerator is imidazole or tertiary amine compound.

[0032] The surface-modified silica powder is silica powder that has undergone surface chemical grafting treatment with tris(3-trimethoxysilylpropyl)isocyanurate grafted with fluorinated long-chain alkyl derivatives, wherein the fluorinated long-chain alkyl is perfluorooctylethyl or perfluorohexylethyl.

[0033] Triallyl isocyanurate, trimethoxysilane, and a platinum catalyst were subjected to a hydrosilylation reaction under nitrogen protection at a temperature of 80-90℃ for 6-8 h, with a platinum catalyst concentration of 5-15 ppm. Following the reaction, a fluorinated long-chain alkyl group and a basic catalyst were added for a nucleophilic substitution reaction at a temperature of 80-90℃ for 4-6 h, yielding a tri(3-trimethoxysilylpropyl)isocyanurate grafted with a fluorinated long-chain alkyl derivative. Tris(3-trimethoxysilylpropyl)isocyanurate grafted with fluorinated long-chain alkyl derivatives is dissolved in a solvent (preferably a mixture of ethanol and water (95:5 by mass)) to prepare a 4-6 wt% coupling agent solution. The pH is adjusted to 4-5 (preferably glacial acetic acid), and hydrolyzed at 20-30°C for 20-40 min. Then, dried silica powder is added, and the mixture is stirred at 50-70°C for 3-5 h. The mass ratio of dried silica powder to coupling agent solution is 1:(2-4). After the reaction is complete, the mixture is filtered, washed multiple times with ethanol, vacuum dried at 70-90°C for 3-5 h, and ground through a 100-300 mesh sieve to obtain surface-modified silica powder.

[0034] The present invention discloses a method for preparing a radiation-crosslinked reinforced high-strength water-resistant artificial stone, comprising the following steps:

[0035] Mix all components thoroughly (when adding an initiator but not a curing agent to the artificial stone formula, the mixing method is as follows: dry mix the ternary cementitious system, surface-modified silica powder, and nano-activated calcium carbonate together, then add the thermosetting resin, crosslinking monomer, initiator, accelerator, triallyl isocyanurate, polycarboxylate superplasticizer, silicone defoamer, and wetting agent, continue stirring, add deionized water, and stir; when adding a curing agent but not an initiator to the artificial stone formula, the mixing method is as follows: dry mix the ternary cementitious system, surface-modified silica powder, and nano-activated calcium carbonate together, then add the thermosetting resin, curing agent, accelerator, triallyl isocyanurate, polycarboxylate superplasticizer, silicone defoamer, and wetting agent, continue stirring, add deionized water, and stir), then mold the mixture, demold it, and cure it to allow the mixture to initially heat-cur. After curing, perform irradiation crosslinking under nitrogen protection, and then perform post-treatment to obtain irradiation-crosslinked enhanced high-strength water-resistant artificial stone.

[0036] Irradiation crosslinking uses high-energy rays, specifically electron beams or gamma rays. For artificial stone with a thickness ≤20mm, electron beam irradiation with an energy of 1.5-3.0 MeV is used. For artificial stone with a thickness >20mm and ≤50mm, gamma ray irradiation or a combination of electron beam and gamma ray irradiation is used. For artificial stone with a thickness >50mm, a combination of electron beam and gamma ray irradiation is used. After irradiation, the material is placed at 70-90℃ for 1-3 hours to eliminate residual free radicals generated during irradiation and release the thermal stress accumulated inside the material, resulting in high-strength, water-resistant artificial stone enhanced by irradiation crosslinking.

[0037] Example 1 (15mm thick sheet, electron beam irradiation)

[0038] A radiation-crosslinked reinforced high-strength water-resistant artificial stone comprises the following components by weight: 20 parts of a ternary cementitious system, 55 parts of surface-modified silica powder, 5 parts of nano-activated calcium carbonate, 15 parts of unsaturated polyester resin (phthalic type, solid content 65%), 3 parts of styrene (crosslinking monomer), 0.2 parts of benzoyl peroxide (initiator), 0.05 parts of cobalt naphthenate (accelerator), 0.6 parts of triallyl isocyanurate (TAIC, radiation sensitizer), 0.3 parts of polycarboxylate superplasticizer (powder, water reduction rate ≥35%), 0.15 parts of silicone defoamer (powder), 0.2 parts of alkylphenol polyoxyethylene ether wetting agent, and 5 parts of deionized water.

[0039] Preparation method:

[0040] (1) Preparation of T-IC-F: 100 parts by mass of triallyl isocyanurate (TAIC), 70 parts by mass of trimethoxysilane (controlling the amount of feed so that some allyl groups in the TAIC molecule participate in the hydrosilylation reaction, and the allyl residual rate is ≥30%), and platinum catalyst (chloroplatinic acid, 10 ppm) were added to the reactor and stirred and mixed evenly under nitrogen protection; the reaction system was heated to 85°C and reacted for 7 h to allow some allyl groups of TAIC to undergo a hydrosilylation reaction with trimethoxysilane to obtain an allyl-containing tri(3-trimethoxysilylpropyl) isocyanurate intermediate (allyl residual rate ≥30%); perfluorooctylethanol (C8F) was added to the tri(3-trimethoxysilylpropyl) isocyanurate intermediate. 17 30 parts by weight of CH2CH2OH were reacted at 85°C for 5 hours under the action of an alkaline catalyst (triethylamine, 1 part by weight) to allow the active methylene group on the isocyanurate ring of the intermediate to undergo a nucleophilic substitution reaction with perfluorooctylethanol, introducing a fluorinated long-chain alkyl group. After the reaction was completed, unreacted small molecules and byproducts were removed by vacuum distillation to obtain a pale yellow transparent liquid product, tris(3-trimethoxysilylpropyl)isocyanurate grafted with a fluorinated long-chain alkyl derivative (abbreviated as T-IC-F), with an allyl residue of ≥30% in the molecule (at least 0.8 allyl groups retained per molecule on average).

[0041] (2) Preparation of surface-modified silica powder: Silica powder (particle size 10-100 μm, SiO2 content ≥98%) was vacuum dried at 120℃ for 4 h to remove surface adsorbed moisture; T-IC-F was dissolved in an ethanol-water mixed solvent (ethanol to water mass ratio of 95:5) to prepare a coupling agent solution with T-IC-F content of 5wt%, the pH was adjusted to 4.5 with glacial acetic acid, and hydrolyzed at 25℃ for 30 min; the dried silica powder was added to the coupling agent solution at a silica powder to coupling agent solution mass ratio of 1:3, and stirred at 60℃ for 4 h; after the reaction was completed, the mixture was filtered, washed three times with ethanol, vacuum dried at 80℃ for 4 h, and ground through a 200-mesh sieve to obtain surface-modified silica powder. The surface active functional group density of the silica powder was ≥1.5 mmol / g, and the water contact angle was ≥110° (proving successful grafting of hydrophobic long chains).

[0042] The grafting rate of surface-modified silica powder was determined by thermogravimetric analysis (TGA). Surface-modified silica powder and unmodified silica powder (blank control) were thoroughly washed with ethanol to remove physically adsorbed unreacted coupling agents. After vacuum drying, the samples were heated from room temperature to 800℃ at a rate of 15℃ / min under a nitrogen atmosphere. The thermogravimetric values ​​W1 (surface-modified silica powder) and W0 (unmodified silica powder) before and after modification were recorded. The grafting rate G was calculated using the formula G=[(W1–W0) / (100%-W0)]×100%.

[0043] Each T-IC-F molecule contains one isocyanurate ring active functional group (i.e., n=1). The molar mass of the T-IC-F coupling agent is M=615.85 g / mol (based on the tris(3-trimethoxysilylpropyl)isocyanurate skeleton; this value is the theoretical molar mass before grafting with fluorinated long-chain alkyl groups, excluding the grafted fluorinated long-chain alkyl portion). The surface active functional group density D (mmol / g) is calculated according to the grafting rate G and molar mass M using the formula D=[G×1000] / [M×(1-G / 100)]. Triple parallel tests are performed, and the average value is taken.

[0044] Test method for water contact angle of surface-modified silica powder:

[0045] The sessile drop method was used to test the contact angle using a contact angle measuring instrument. Surface-modified silica powder was pressed into a smooth, circular sheet (13 mm in diameter, 2 mm thick) under 15 MPa pressure. 3 μL of deionized water was dropped onto the sheet surface using a microsyringe. After the droplet stabilized for 30 seconds, an image of the droplet was acquired. The static water contact angle was calculated using the Young-Laplace equation. Five different locations were tested for each sample, and the average value was taken. Three independent pressed samples were tested in parallel, and the results are expressed as "mean ± standard deviation". Test conditions: temperature (20 ± 2) °C, relative humidity (50 ± 5)%.

[0046] (3) Add the ternary cementitious system (the ternary cementitious system is composed of P·II52.5R type silicate cement (PC), high belite sulfoaluminate cement (CSA) and anhydrite, and the mass ratio of the three is PC:CSA:anhydrite=80:15:5), surface modified silica powder and nano-active calcium carbonate to the mixer and dry mix for 3 minutes;

[0047] (4) Add unsaturated polyester resin, styrene, benzoyl peroxide, accelerator, TAIC, polycarboxylate superplasticizer, silicone defoamer, and alkylphenol polyoxyethylene ether wetting agent, and continue stirring for 4 minutes to make the resin evenly coat the inorganic powder.

[0048] (5) Add deionized water and stir for 2 minutes to partially hydrate the cement components and obtain the mixture;

[0049] (6) The mixture is loaded into the mold and vibrated and pressed under vacuum conditions. The molding pressure is 12MPa, the vacuum degree is -0.095MPa, and the molding thickness is 15mm.

[0050] (7) After demolding, place it at 60℃ for 24 hours to allow the resin to initially heat-cur and the cement to continue hydrating;

[0051] (8) The product in step (7) is irradiated and crosslinked using an electron beam accelerator. The electron beam energy is 2.0 MeV, the total irradiation dose is 25 kGy, the dose rate is 10 kGy / pass, and a double-sided irradiation process (irradiation dose of 12.5 kGy per side) is used under nitrogen protection.

[0052] (9) After irradiation, place it at 80°C for 2 hours to eliminate residual free radicals generated during irradiation and release the thermal stress accumulated inside the material to obtain high-strength water-resistant artificial stone with irradiation crosslinking enhancement.

[0053] Example 2 (30mm thick medium-thick plate, γ-ray irradiation)

[0054] A radiation-crosslinked reinforced high-strength water-resistant artificial stone comprises the following components by weight: 15 parts of a ternary cementitious system, 60 parts of surface-modified silica powder, 4 parts of nano-activated calcium carbonate, 15 parts of epoxy resin (bisphenol A type, epoxy equivalent 190), 5 parts of curing agent methyl hexahydrophthalic anhydride, 0.1 parts of accelerator 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), 0.5 parts of triallyl isocyanurate (TAIC, radiation sensitizer), 0.25 parts of polycarboxylate superplasticizer (powder, water reduction rate ≥35%), 0.12 parts of silicone defoamer (powder), 0.15 parts of fatty alcohol polyoxyethylene ether wetting agent, and 4 parts of deionized water.

[0055] The preparation method is the same as in Example 1, except that the molding thickness is 30 mm and Co-60 γ-ray irradiation is used (total irradiation dose is 20 kGy, alternating on both sides, dose rate is 1.0 kGy / pass).

[0056] Example 3 (40mm thick plate, combined irradiation)

[0057] A radiation-crosslinked reinforced high-strength water-resistant artificial stone comprises the following components by weight: 22 parts of a ternary cementitious system, 53 parts of surface-modified silica powder, 6 parts of nano-activated calcium carbonate, 14 parts of unsaturated polyester resin (isophthalic type, solid content 70%), 2.5 parts of styrene, 0.2 parts of benzoyl peroxide, 0.05 parts of accelerator (cobalt naphthenate), 0.8 parts of triallyl isocyanurate (TAIC, radiation sensitizer), 0.35 parts of polycarboxylate superplasticizer (powder, water reduction rate ≥35%), 0.18 parts of silicone defoamer (powder), 0.25 parts of alkylphenol polyoxyethylene ether wetting agent, and 5.5 parts of deionized water.

[0058] Prepared according to the above formula and the method of Example 1, the difference is that the molding thickness is 40mm, and the combined process of electron beam double-sided irradiation (total irradiation dose 25kGy, dose rate 10kGy / pass) + Co-60 γ-ray irradiation (total irradiation dose 15kGy, double-sided alternation, dose rate 1kGy / pass) is adopted.

[0059] Example 4 (High-performance verification example)

[0060] A radiation-crosslinked reinforced high-strength water-resistant artificial stone comprises the following components by weight: 18 parts of a ternary cementitious system, 58 parts of surface-modified silica powder, 5 parts of nano-activated calcium carbonate, 16 parts of epoxy resin (bisphenol A type, epoxy equivalent 190), 5.5 parts of curing agent methyl hexahydrophthalic anhydride, 0.12 parts of accelerator (DMP-30), 0.7 parts of triallyl isocyanurate (TAIC, radiation sensitizer), 0.3 parts of polycarboxylate superplasticizer (powder, water reduction rate ≥35%), 0.15 parts of silicone defoamer (powder), 0.2 parts of fatty alcohol polyoxyethylene ether wetting agent, and 4.5 parts of deionized water.

[0061] Prepared according to the above formula and the method of Example 1, the difference being: the molding thickness is 20 mm, and electron beam double-sided irradiation is used (total irradiation dose of 30 kGy, dose rate of 10 kGy / pass).

[0062] Comparative Example 1

[0063] Artificial stone was prepared according to the formulation and method of Example 1, except that unmodified silica powder was used instead of surface-modified silica powder.

[0064] Comparative Example 2

[0065] Artificial stone was prepared according to the formulation and method of Example 1, except that tris(3-trimethoxysilylpropyl)isocyanurate intermediate (ungrafted with fluorinated long-chain alkyl) was used instead of tris(3-trimethoxysilylpropyl)isocyanurate grafted with fluorinated long-chain alkyl derivatives for surface modification of silica powder.

[0066] Comparative Example 3

[0067] Artificial stone was prepared according to the formulation and method of Example 1, except that unmodified ordinary silica powder was used to replace nano-active calcium carbonate.

[0068] Comparative Example 4

[0069] Artificial stone was prepared according to the formulation and method of Example 1, except that TAIC irradiation sensitizer was not added.

[0070] Comparative Example 5

[0071] Artificial stone was prepared according to the formulation and method of Example 1, except that the irradiation crosslinking treatment step was not performed.

[0072] Comparative Example 6

[0073] Artificial stone was prepared according to the formulation and method of Example 1, except that γ-methacryloyloxypropyltrimethoxysilane (KH570, a monofunctional silane coupling agent) was used instead of tris(3-trimethoxysilylpropyl)isocyanurate grafted with fluorinated long-chain alkyl derivatives for surface modification of silica powder.

[0074] Comparative Example 7

[0075] Artificial stone was prepared according to the formulation and method of Example 1, except that unmodified ordinary silica powder was used to replace the ternary cementitious system.

[0076] Comparative Example 8

[0077] Artificial stone was prepared according to the formulation and method of Example 1, except that the mortar was molded to a thickness of 60 mm and only single-sided electron beam irradiation was used (electron beam energy 2.0 MeV, total irradiation dose 25 kGy, dose rate 10 kGy / pass).

[0078] The results showed that the molding thickness far exceeded the effective penetration depth of the electron beam (about 15-20 mm), and effective cross-linking was only achieved within a depth of about 15 mm on the surface, with insufficient internal cross-linking.

[0079] Comparative Example 9

[0080] Artificial stone was prepared according to the formulation and method of Example 1, except that T-IC-F used an excess of trimethoxysilane (120 parts by mass) during the synthesis process to reduce the residual rate of allyl to below 5%, and then used this T-IC-F to modify the surface of silica powder.

[0081] In the above embodiments and comparative examples:

[0082] The nano-activated calcium carbonate was purchased from Jiangxi Tuobang New Material Technology Co., Ltd., model 303, with a primary particle size of 20-80nm and an average aggregate particle size of 300-500nm.

[0083] The unsaturated polyester resin was purchased from Changzhou Yunnuo Composite Materials Technology Co., Ltd., model: A400-972;

[0084] The polycarboxylate superplasticizer was purchased from Shanghai Hengchuang Chemical Co., Ltd., product number Sika 540P;

[0085] The silicone defoamer was purchased from Jinan Ninghui Chemical Technology Co., Ltd., model / item number 12;

[0086] Alkylphenol polyoxyethylene ether wetting agent was purchased from Shanghai Shifeng Biotechnology Co., Ltd., product number A95821;

[0087] The silicon micro powder was purchased from Jiangsu Lianrui New Material Co., Ltd. (actually crystalline silicon micro powder), product number NOVOPOWDERDC, with a particle size of 10μm and a SiO2 content of ≥98%.

[0088] P·II52.5R type Portland cement was purchased from Anhui Conch Cement Co., Ltd., with the product number P·II52.5R;

[0089] High-belite sulfoaluminate cement was purchased from Tangshan Arctic Bear Building Materials Co., Ltd., product number BS-WHS;

[0090] The anhydrite was purchased from Suzhou Zhongdian Desulfurization Gypsum Supply Co., Ltd., with a particle size ≤45μm;

[0091] The epoxy resin was purchased from Shanghai Yuanbang Trading Co., Ltd. (actually bisphenol A type liquid epoxy resin), item number YPE-127.

[0092] 2,4,6-Tris(dimethylaminomethyl)phenol was purchased from Jinan Yuno Chemical Co., Ltd., product number DMP-30;

[0093] Cobalt naphthenate was purchased from Shandong Yanggu Futai Chemical Co., Ltd., and its model number is RCo-N10.

[0094] Performance testing methods

[0095] (1) Compressive strength and flexural strength: The compressive strength was tested according to GB / T 9966.1-2020 "Test methods for natural stone - Part 1: Compressive strength test after drying, water saturation and freeze-thaw cycles" with a specimen size of 70mm×70mm×actual thickness. The flexural strength was tested according to GB / T 17671-2021 "Test method for strength of cement mortar (ISO method)" with 5 parallel specimens in each group and the average value was taken.

[0096] (2) Water absorption rate: Tested according to JC / T 908-2013 "Artificial Stone" standard. The specimen size is 100mm×100mm×actual thickness. The test surface is the molded surface and no edge sealing treatment is performed. The specimen is dried at 80±2℃ for 48h until constant weight, then weighed. After being immersed in distilled water at (20±2)℃ for 48h, it is taken out, wiped dry, and weighed. The water absorption rate is calculated. Five parallel specimens are used in each group, and the average value is taken.

[0097] (3) Abrasion resistance: Tested according to GB / T 12988-2009 "Test Method for Abrasion Resistance of Inorganic Flooring Materials" standard, with 5 parallel specimens in each group and the average value taken.

[0098] (4) Bending strength retention rate: After immersing the specimen in distilled water at (20±2)℃ for 7 days, the bending strength was tested according to the JC / T 908-2013 standard for artificial stone. The ratio of the bending strength after immersion to the bending strength before immersion was calculated. Five parallel specimens were used in each group, and the average value was taken.

[0099] (5) Water contact angle: Tested according to GB / T 30447-2013 "Method for measuring contact angle of nanofilm", with 5 parallel specimens in each group and the average value taken.

[0100] (6) Cross-sectional cross-linking uniformity: The gel content was tested according to GB / T 18474-2001 "Test method for cross-linking degree of cross-linked polyethylene (PE-X) pipes and fittings". Samples were taken from the surface, center and back of the specimen to determine the gel content. The range of the gel content at the three locations was calculated. Three specimens were used in each group, and the average value was taken.

[0101] Performance test results

[0102] Table 1 shows the performance test results of the artificial stones prepared in Examples 1-4 and Comparative Examples 1-9.

[0103] Table 1

[0104]

[0105] Table 2 shows the performance test results of the artificial stones prepared in Examples 1-4 and Comparative Examples 1-9.

[0106] Table 2

[0107]

[0108] Note: The range of gel content in the cross section is the maximum difference in gel content at the surface, center, and back. The smaller the range, the better the cross-linking uniformity. The artificial stone prepared in Comparative Example 5 was not cross-linked by irradiation; the resin cross-linking relied solely on thermosetting and did not involve an assessment of the uniformity of irradiation cross-linking.

[0109] As can be seen from Tables 1 and 2:

[0110] (1) The mechanical and water resistance properties of the artificial stones prepared in Examples 1-4 all reached high standards: flexural strength ≥35.8MPa (up to 40.2MPa in Example 4), compressive strength ≥138.5MPa (up to 155.8MPa in Example 4), water absorption ≤0.030% (as low as 0.016% in Example 4), abrasion resistance (grinding pit length) ≤10.8mm, flexural strength retention rate after 7 days of immersion in water ≥95.2%, water contact angle ≥116°, and cross-sectional gel content range ≤2.4%. The reasonable introduction of additives further optimized the slurry dispersibility and molding density, resulting in a slight improvement in various properties compared to before the modification. Example 4, as a high-performance verification example, fully demonstrates that the technical solution of this invention has sufficient performance margin.

[0111] (2) Analysis of the relationship between water absorption rate and water contact angle:

[0112] The water contact angle of the artificial stone prepared in Comparative Example 3 (without nano-activated calcium carbonate) was 117°, which was basically the same as the 119° of the artificial stone prepared in Example 1. This indicates that the water contact angle is mainly determined by the hydrophobic long chains in T-IC-F, and the contribution of nano-activated calcium carbonate to the surface contact angle is limited. The main function of nano-activated calcium carbonate is multi-scale filling and densification. The water absorption rate of the artificial stone prepared in Comparative Example 3 was 0.09%, which was significantly higher than the 0.025% of the artificial stone prepared in Example 1, proving that nano-activated calcium carbonate effectively blocked the water penetration channels by sealing the nanoscale pores at the interface.

[0113] (3) Analysis of water resistance and hydrophobicity:

[0114] The artificial stone prepared in Comparative Example 1 (unmodified silica powder) had a water absorption rate of 0.24%, a water contact angle of only 86°, and a strength retention rate of only 77.0% after immersion in water, which was significantly lower than that of the artificial stone prepared in Example 1. This demonstrates that the hydrophobic molecular layer constructed by the T-IC-F surface chemical grafting pretreatment is the key to improving water resistance.

[0115] The artificial stone prepared in Comparative Example 2 (an intermediate without grafted fluorinated long-chain alkyl groups) had a water absorption rate of 0.11% and a water contact angle of 96°, which was higher than that of the artificial stone prepared in Comparative Example 1, but still significantly lower than that of the artificial stone prepared in Example 1. This demonstrates that the introduction of fluorinated long-chain alkyl groups is key to constructing an effective hydrophobic barrier layer, and its low surface energy properties increased the water contact angle from 96° to 119° and reduced the water absorption rate from 0.11% to 0.025%.

[0116] The artificial stone prepared in Comparative Example 9 (with an allyl residue rate of <5% in T-IC-F) had a water absorption rate of 0.095% and a cross-sectional gel content range of 4.0%, all of which were lower than those of the artificial stone prepared in Example 1. This demonstrates that the allyl groups retained in the T-IC-F molecule (with a residue rate ≥30%) are key active sites participating in irradiation crosslinking. If the allyl residue rate is too low, T-IC-F only functions as a common coupling agent to play a role in interfacial bonding and hydrophobicity, and cannot provide an effective "interfacial chemical bridge" function. The crosslinking network between the interface and the bulk phase cannot be integrated, resulting in a decrease in crosslinking uniformity.

[0117] The cross-sectional gel content of the artificial stone prepared in Comparative Example 4 (without TAIC sensitizer) was 3.5% (higher than the 1.9% of the artificial stone prepared in Example 1), and its water absorption rate of 0.075% was also higher than that of the artificial stone prepared in Example 1. This indicates that there is a synergistic effect between TAIC and the allyl groups retained in T-IC-F: T-IC-F provides interfacial crosslinking nodes, and TAIC provides bulk crosslinking nodes, together achieving an integrated "interfacial-bulk" crosslinking network.

[0118] The artificial stone prepared in Comparative Example 5 (without irradiation crosslinking) had a water absorption rate of 0.17% and a strength retention rate of only 81.0% after immersion in water, which was significantly lower than that in Example 1. This indicates that irradiation crosslinking increases the degree of resin crosslinking to over 95%, significantly reducing the free chain segments that can absorb water and swell, thus forming a double water-resistant guarantee with the hydrophobic shielding layer.

[0119] The artificial stone prepared in Comparative Example 6 (KH570 instead of T-IC-F) had a water absorption rate of 0.12% and a water contact angle of only 93°, with all properties lower than those in Example 1. This demonstrates that T-IC-F achieves a hydrophobic effect that traditional monosilane coupling agents cannot achieve through a hydrophobic molecular layer constructed with fluorinated long-chain alkyl groups.

[0120] (4) Analysis of the role of adjuvants:

[0121] This invention introduces a polycarboxylate superplasticizer, a silicone defoamer, and a wetting agent into the formulation. These three agents synergistically optimize the processing performance and molding quality of the slurry: the superplasticizer effectively reduces the water-cement ratio, reducing water consumption while maintaining fluidity and increasing matrix density; the defoamer eliminates air bubbles introduced during mixing and molding, reducing internal defects; and the wetting agent reduces the interfacial tension between the resin and inorganic fillers, improving filler dispersion uniformity. The synergistic effect of these three agents gives the slurry better fluidity and uniformity before pressing, thus providing a more ideal initial structure for subsequent thermosetting and radiation crosslinking, ultimately resulting in further optimization of flexural strength, compressive strength, and water absorption.

[0122] (5) Analysis of the compatibility between irradiation penetration depth and process:

[0123] The artificial stone prepared by Comparative Example 8 (thickness 60 mm, exceeding the preferred thickness range of this invention, irradiated only on one side with an electron beam) exhibited a high cross-sectional gel content variation of 14.0%, a water absorption rate of 0.36%, and a flexural strength of only 26.2 MPa, all of which were significantly inferior to those of Example 3. This thickness (60 mm) far exceeded the effective penetration depth of the electron beam (the penetration depth of a 2.0 MeV electron beam is approximately 15-20 mm), resulting in effective cross-linking only within a surface depth of approximately 15 mm, with severely insufficient internal cross-linking. In contrast, Example 3 (thickness 40 mm) employed a combined electron beam irradiation process (25 kGy + γ-ray irradiation 15 kGy), with a total dose of 40 kGy, and a cross-sectional gel content variation of only 2.4%, ensuring uniform cross-linking across the entire thickness range.

[0124] (6) Quantitative analysis of the contribution of each component to performance:

[0125] The water absorption rate of the artificial stone prepared in Comparative Example 3 (without nano-activated calcium carbonate) was 0.09%, which was higher than that of the artificial stone prepared in Example 1 (0.025%). Combined with the fact that the water contact angle of the artificial stone prepared in Comparative Example 3 (117°) was basically the same as that of the artificial stone prepared in Example 1 (119°), it further verifies that the main contribution of nano-activated calcium carbonate is multi-scale filling and densification (sealing nanoscale pores) rather than surface hydrophobic modification.

[0126] The water absorption rate of the artificial stone prepared in Comparative Example 7 (without ternary cementing system) was 0.065%, which was higher than that of the artificial stone prepared in Example 1 (0.025%), indicating that the hydration products of the ternary cementing system fill the interfacial pores and make an important contribution to reducing the water absorption rate.

[0127] In summary, this invention achieves a breakthrough in artificial stone systems for the first time through a multi-synergistic enhancement mechanism: "T-IC-F constructs an integrated interface of 'chemical bonding + hydrophobic shielding' (interface enhancement and hydrophobicity) + TAIC and T-IC-F retain allyl groups for synergistic sensitization and irradiation crosslinking (bulk crosslinking and water resistance) + nano-active calcium carbonate multi-scale filling and densification (pore sealing) + ternary cementitious system inorganic skeleton support + defoamer / wetting agent / water reducing agent synergistic optimization of molding quality + differentiated irradiation process to ensure crosslinking uniformity". This breakthrough results in high flexural strength ≥34MPa, compressive strength ≥130MPa, water absorption ≤0.035%, wear resistance pit length ≤12mm, water contact angle ≥115°, and strength retention rate ≥94% after 7 days of immersion. This solves the technical problem of existing polymer artificial stone systems that struggle to achieve both high strength, ultra-low water absorption, and long-term water resistance.

[0128] The above description is merely a preferred embodiment of the present invention. The scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, any improvements and modifications made without departing from the principles of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. A high-strength, water-resistant artificial stone reinforced by irradiation crosslinking, characterized in that, The artificial stone formulation, by weight, includes the following components: 15-25 parts of ternary cementitious system, 50-60 parts of surface-modified silica powder, 3-7 parts of nano-activated calcium carbonate, 12-18 parts of thermosetting resin, 0.1-0.3 parts of initiator or curing agent, 0.02-0.1 parts of accelerator, 0.3-1.0 parts of triallyl isocyanurate, 0.1-0.5 parts of polycarboxylate superplasticizer, 0.05-0.3 parts of silicone defoamer, 0.05-0.5 parts of wetting agent, and 4-6 parts of water; when an initiator is added but no curing agent is added, the artificial stone formulation also includes 2-4 parts of crosslinking monomer.

2. The high-strength, water-resistant artificial stone reinforced by irradiation crosslinking according to claim 1, characterized in that, The ternary cementitious system is composed of ordinary silicate cement, high belite sulfoaluminate cement and gypsum dry-mixed.

3. The high-strength, water-resistant artificial stone reinforced by irradiation crosslinking according to claim 1, characterized in that, The surface-modified silica powder is silica powder that has undergone surface chemical grafting treatment with tris(3-trimethoxysilylpropyl)isocyanurate grafted with fluorinated long-chain alkyl derivatives, wherein the fluorinated long-chain alkyl is perfluorooctylethyl or perfluorohexylethyl.

4. The high-strength, water-resistant artificial stone reinforced by irradiation crosslinking according to claim 1, characterized in that, Tris(3-trimethoxysilylpropyl)isocyanurate grafted with fluorinated long-chain alkyl derivatives was dissolved in a solvent to prepare a coupling agent solution. The pH value was adjusted, and a hydrolysis reaction was carried out. After the reaction, dried silica powder was added and stirred to obtain surface-modified silica powder.

5. The high-strength, water-resistant artificial stone reinforced by irradiation crosslinking according to claim 4, characterized in that, The concentration of the coupling agent solution is 4-6 wt%, the mass ratio of the dried silica powder to the coupling agent solution is 1:(2-4), and the stirring reaction temperature is 50-70℃ for 3-5 h.

6. The high-strength, water-resistant artificial stone reinforced by irradiation crosslinking according to claim 4, characterized in that, Triallyl isocyanurate, trimethoxysilane, and platinum catalyst were subjected to a hydrosilylation reaction under nitrogen protection. Then, a fluorinated long-chain alkyl group and a basic catalyst were added to carry out a nucleophilic substitution reaction to obtain a fluorinated long-chain alkyl derivative grafted with tri(3-trimethoxysilylpropyl)isocyanurate.

7. The high-strength, water-resistant artificial stone reinforced by irradiation crosslinking according to claim 6, characterized in that, The reaction temperature for the hydrosilylation reaction is 80-90℃ and the reaction time is 6-8h, while the reaction temperature for the nucleophilic substitution reaction is 80-90℃ and the reaction time is 4-6h. The mass ratio of triallyl isocyanurate, trimethoxysilane, fluorinated long-chain alkyl group and basic catalyst is (80-120):(65-75):(25-35):(0.5-1.5), and the concentration of platinum catalyst in the hydrosilylation reaction system is 5-15ppm.

8. The high-strength, water-resistant artificial stone reinforced by irradiation crosslinking according to claim 1, characterized in that, The thermosetting resin is at least one of unsaturated polyester resin and epoxy resin; When an initiator is added without a curing agent, the thermosetting resin is an unsaturated polyester resin, the initiator is benzoyl peroxide or methyl ethyl ketone peroxide, the crosslinking monomer is styrene or methyl methacrylate, and the accelerator is dimethylaniline or cobalt naphthenate. When a curing agent is added without an initiator, the thermosetting resin is epoxy resin, the curing agent is dicyandiamide or anhydride curing agent, and the accelerator is imidazole or tertiary amine compound.

9. A method for preparing irradiation-crosslinked reinforced high-strength water-resistant artificial stone as described in any one of claims 1-8, characterized in that, The components are mixed evenly, then the mixture is molded and cured after demolding to allow the mixture to undergo initial thermosetting. After curing, it is irradiated and cross-linked under nitrogen protection. After irradiation and cross-linking, post-treatment is carried out to obtain irradiated and cross-linked reinforced high-strength water-resistant artificial stone.

10. The method for preparing a radiation-crosslinked reinforced high-strength water-resistant artificial stone according to claim 9, characterized in that, The high-energy rays used for irradiation crosslinking are electron beams or gamma rays; electron beam irradiation is used for artificial stone with a thickness ≤20mm; gamma ray irradiation or a combination of electron beam and gamma ray irradiation is used for artificial stone with a thickness >20mm and ≤50mm; and a combination of electron beam and gamma ray irradiation is used for artificial stone with a thickness >50mm.

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