Dustproof anti-static artificial terrazzo and preparation method thereof

Abstract

The invention discloses a dustproof anti-static artificial terrazzo and a preparation method thereof. The dustproof anti-static artificial terrazzo prepared by the invention is prepared from the following components: quartz stone particles, ceramic particles, cement, modified quartz sand, a dispersing agent, a defoaming agent, sulfhydrylated conductive carbon black, a multi-sulfydryl cross-linking agent, modified polyacrylic emulsion, water and dimethylphenylphosphine. The modified polyacrylic acid emulsion is obtained by polymerizing an acrylate monomer and diphenyl p-styryl phosphine, reacting with 1-[4-(chloromethyl) phenyl] ethanone, reacting with potassium cyanide and ammonium carbonate, and chlorinating and emulsifying; the modified quartz sand is prepared by grafting pretreated quartz sand with 2, 6-bis (tert-butyl)-4-(mercaptomethyl) phenol, reacting with phosphorus trichloride, and then reacting with p-hydroxystyrene; and styrene and butadiene are polymerized on the surface of the terrazzo. The dustproof anti-static artificial terrazzo prepared by the invention has good mechanical, antibacterial and anti-aging properties.

Description

Technical Field

[0001] The present invention relates to the technical field of artificial terrazzo, and specifically to a dust-proof and anti-static artificial terrazzo and a preparation method thereof. Background Art

[0002] Artificial terrazzo is a composite material made by mixing cement or resin as an adhesive with various aggregates such as marble chips, quartz particles, glass flakes, etc. It is widely used in the field of architectural decoration and is favored for its customizable colors and patterns. Traditional terrazzo has been widely used in various buildings due to its high cost-effectiveness, freely adjustable colors and textures, and convenient construction, covering various occasions including residential, commercial spaces, public facilities, etc. However, with the improvement of usage requirements and the progress of technology, some problems have gradually emerged in traditional terrazzo floors.

[0003] Due to improper surface treatment, traditional terrazzo floors are prone to becoming rough and accumulating dirt, making daily cleaning and maintenance difficult. For certain specific application scenarios, such as electronic manufacturing workshops, laboratories, or hospitals where extremely high environmental cleanliness requirements are imposed, terrazzo floors also need to have the functions of dust prevention and anti-static to prevent potential risks brought by dust accumulation and static electricity accumulation. Summary of the Invention

[0004] The purpose of the present invention is to provide a dust-proof and anti-static artificial terrazzo and a preparation method thereof to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solutions:

[0006] A preparation method of a dust-proof and anti-static artificial terrazzo, comprising the following steps:

[0007] (1) React acrylic acid, methyl methacrylate, butyl acrylate, and diphenyl styrylphosphine to obtain polyacrylic acid resin; react the polyacrylic acid resin with 1-[4-(chloromethyl)phenyl]ethanone to obtain pretreated polyacrylic acid resin; react the pretreated polyacrylic acid resin with potassium cyanide and ammonium carbonate to obtain pre-modified polyacrylic acid resin;

[0008] (2) After reacting the pre-modified acrylic resin with 4-vinylbenzoyl chloride, chlorinate it with sodium hypochlorite solution to obtain modified polyacrylic acid resin; emulsify the modified polyacrylic acid resin to obtain modified polyacrylic acid emulsion;

[0009] (3) React pretreated quartz sand, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine to obtain pre-modified quartz sand;

[0010] (4) React the pre-modified quartz sand with phosphorus trichloride, and then react with p-hydroxystyrene to obtain phosphorus-containing quartz sand; polymerize styrene, phosphorus-containing quartz sand, and butadiene to obtain modified quartz sand;

[0011] (5) Weigh the following raw materials. By mass, 50-60 parts of quartz stone particles, 70-80 parts of ceramic particles, 140-160 parts of cement, 20-30 parts of modified quartz sand, 5-10 parts of dispersant, 5-10 parts of defoamer, 15-20 parts of mercapto-functionalized conductive carbon black, 5-7 parts of multi-mercapto cross-linking agent, 30-40 parts of modified polyacrylate emulsion, 60-80 parts of water, and 5-6 parts of dimethylphenylphosphine. Mix the above raw materials, pour them into a mold for curing, and obtain the dust-proof and anti-static artificial terrazzo after demolding, curing, grinding, and polishing.

[0012] Preferably, the preparation method of the pre-modified polyacrylate resin in step (1) is as follows: Mix acrylic acid, methyl methacrylate, butyl acrylate, diphenylstyrylphosphine, azobisisobutyronitrile, and isopropanol, heat up to 82-85 °C and reflux and stir for 2-3 h, and obtain polyacrylate resin through rotary evaporation under reduced pressure and vacuum drying; the mass ratio of acrylic acid, methyl methacrylate, butyl acrylate, diphenylstyrylphosphine, azobisisobutyronitrile, and isopropanol is: 1:(0.7-0.8):(0.5-0.6):(0.3-0.5):(0.01-0.02):(20-30); Mix the polyacrylate resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine, and N,N-dimethylformamide, heat up to 65-70 °C and react for 5-6 h, and obtain the pretreated polyacrylate resin through precipitation with ether, washing, and drying; the mass ratio of polyacrylate resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine, and N,N-dimethylformamide is 1:(0.2-0.3):(0.1-0.2):(30-40); Mix the pretreated polyacrylate resin, potassium cyanide, ammonium carbonate, and N,N-dimethylformamide, heat up to 140-150 °C and react for 10-12 h, and obtain the pre-modified polyacrylate resin through precipitation with ether, filtration, washing, and drying; the mass ratio of the pretreated polyacrylate resin, potassium cyanide, 35 wt% ammonia water, and N,N-dimethylformamide is 1:(0.01-0.02):(0.5-0.7):(30-40).

[0013] Preferably, the preparation method of the modified polyacrylic acid emulsion in step (2) is as follows: Mix the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum trichloride, and N,N-dimethylformamide, heat up to 40 - 45°C and react for 2 - 3 h. After the reaction, precipitate with pure water, filter, redisperse in a 5 wt% sodium hypochlorite solution, stir for 2 h, filter, wash, and dry to obtain the modified acrylic resin; the mass ratio of the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum trichloride, N,N-dimethylformamide, and 5 wt% sodium hypochlorite solution is 1:(0.4 - 0.6):(0.2 - 0.3):(20 - 30):(20 - 30); Mix the modified acrylic resin, 80 wt% isopropyl alcohol aqueous solution, sodium dodecyl sulfonate, 35 wt% ammonia water, and pure water according to the mass ratio of 1:(1 - 1.2):(0.2 - 0.4):(0.1 - 0.2):(1 - 1.2) at 80°C to obtain the modified polyacrylic acid emulsion.

[0014] Preferably, the preparation method of the pre-modified quartz sand in step (3) is as follows: Mix quartz sand and ethanol, adjust the pH to 4 with a 40 wt% hydrochloric acid solution, add vinyltrimethoxysilane and ultrasonically mix for 10 min, then heat up to 80°C and stir for 5 - 7 h, filter, wash, and dry to obtain the pretreated quartz sand; the mass ratio of quartz sand, ethanol, and vinyltrimethoxysilane is 1:(0.3 - 0.5):(50 - 60); Mix the pretreated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine, heat up to 40 - 50°C and react for 10 - 12 h, filter, wash, and dry to obtain the pre-modified quartz sand; the mass ratio of the pretreated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine is 1:(20 - 30):(0.3 - 0.5):(0.01 - 0.02).

[0015] Preferably, the preparation method of the modified quartz sand in step (4) is as follows: Mix pre-modified quartz sand, phosphorus trichloride, toluene, and organotin in a mass ratio of 1:(0.3 - 0.5):(20 - 30):(0.03 - 0.04). After heating to 40 - 50 °C, filter. Then mix the filtered pre-modified quartz sand, toluene, and p-hydroxystyrene in a mass ratio of 1:(20 - 30):(0.8 - 1.0), heat to 60 - 70 °C and react for 5 - 6 h. After filtration, washing, and drying, obtain phosphorus-containing quartz sand. Under nitrogen protection, mix styrene, phosphorus-containing quartz sand, and cyclohexane in a mass ratio of 1:(5 - 6):(35 - 40) and heat to 60 °C. Add n-butyllithium which is 0.01 times the mass of styrene and react for 3 - 5 min. Then add n-butyllithium which is 0.03 times the mass of styrene again and react for 30 - 40 min. Add butadiene which is 4 - 5 times the mass of styrene and continue to react for 35 - 45 min. Then add styrene again and react for 30 - 40 min. The addition amount of styrene this time is the same as the mass of styrene added for the first time. Add ethanol which is 10 - 12 times the mass of styrene. After filtration, washing, and drying, obtain modified quartz sand.

[0016] Preferably, the preparation method of the mercapto-functionalized conductive carbon black in step (5) is as follows: Mix conductive carbon black and ethanol, adjust the pH to 4 using a 40 wt% hydrochloric acid solution. Add 3-mercaptopropyltrimethoxysilane and ultrasonically mix for 10 min. Then heat to 80 °C and stir for 5 - 7 h. After filtration, washing, and drying, obtain mercapto-functionalized conductive carbon black. The mass ratio of conductive carbon black, ethanol, and 3-mercaptopropyltrimethoxysilane is 1:(0.3 - 0.5):(50 - 60). The preparation method of the multi-mercapto crosslinking agent is as follows: Add equimolar amounts of triethylamine and 2-mercaptoethanol to tetrahydrofuran which is 10 - 12 times the mass of triethylamine. Add dichlorodimethylsilane which is 0.45 - 0.5 times the molar amount of 2-mercaptoethanol and stir for 24 h. After filtration, washing with ether, and vacuum distillation, obtain the multi-mercapto crosslinking agent.

[0017] Preferably, the particle size of the quartz sand is 200 mesh.

[0018] The present invention also provides an anti-dust and anti-static artificial terrazzo prepared by the preparation method of the anti-dust and anti-static artificial terrazzo according to the above.

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0020] The dust-proof and anti-static artificial terrazzo prepared by the present invention comprises the following components: quartz stone particles, ceramic particles, cement, modified quartz sand, dispersant, defoamer, mercapto-functionalized conductive carbon black, multi-mercapto cross-linking agent, modified polyacrylate emulsion, water, dimethylphenylphosphine; the modified polyacrylate emulsion is obtained by polymerizing acrylate monomers and diphenylstyrylphosphine, reacting with 1-[4-(chloromethyl)phenyl]ethanone, then reacting with potassium cyanide and ammonium carbonate, and then subjecting to chlorination and emulsification; the modified quartz sand is obtained by grafting 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol onto pretreated quartz sand, reacting with phosphorus trichloride, and then reacting with p-hydroxystyrene to obtain phosphorus-containing quartz sand, and then polymerizing styrene and butadiene on its surface.

[0021] First, acrylic acid, methyl methacrylate, butyl acrylate, and diphenylstyrylphosphine are polymerized under the action of an initiator to form a polyacrylate resin. The molecular chain of the resin contains a triphenylphosphine structure. 1-[4-(chloromethyl)phenyl]ethanone reacts with the triphenylphosphine structure to form a quaternary phosphonium salt structure with antibacterial properties, and a formyl group structure is introduced. The formyl group undergoes addition, substitution, cyclization, and rearrangement under the action of potassium cyanide and ammonium carbonate to form a hydantoin structure. After chlorination with sodium hypochlorite, the combination of the quaternary phosphonium salt and haloamine can further improve the antibacterial properties of the material; 4-vinylbenzoyl chloride is grafted onto the benzene ring structure of the polyacrylate main chain through a Friedel-Crafts reaction, thereby introducing a vinyl group.

[0022] Second, the surface of the quartz stone is treated with vinyltrimethoxysilane to make its surface carry vinyl groups. 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol is grafted through the reaction of mercapto and alkenyl groups, and then successively reacted with phosphorus trichloride and p-hydroxystyrene to form a phosphite structure with antioxidant properties, and a vinyl group is introduced. Under the action of n-butyllithium, the vinyl groups on p-hydroxystyrene and styrene and butadiene undergo an anionic polymerization reaction, and a styrene-butadiene-styrene block copolymer is wrapped on the surface of the quartz stone, endowing the material with good toughness.

[0023] Finally, the quartz stone particles, ceramic particles, cement, modified quartz sand, dispersant, defoamer, mercapto-functionalized conductive carbon black, multi-mercapto cross-linking agent, modified polyacrylate emulsion, water, and dimethylphenylphosphine are mixed to obtain artificial terrazzo. The polyacrylate emulsion, as an adhesive, can effectively bind the components together and enhance the compactness of the material; the mercapto-functionalized conductive carbon black can not only endow the terrazzo with good antistatic properties, but also indirectly improve the dust-proof performance of the terrazzo by reducing electrostatic adsorption. The mercapto groups on the mercapto-functionalized conductive carbon black and the mercapto groups on the multi-mercapto cross-linking agent can also undergo electrophilic addition with the double bonds on the surface of the polyacrylate emulsion and the modified quartz sand under the action of a catalyst to form more cross-linking sites, further enhancing the compactness and mechanical properties of the material. Detailed implementation mode

[0024] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0025] In the following examples and comparative examples, the defoamer model is JP-8925W; the dispersant model is JZM-0157; the cement is ordinary Portland cement P.O42.5; the quartz stone particle size is 2-4mm, purchased from Baiyi Mineral Products Processing Factory, Lingshou County; the ceramic particle mesh number is 20-40 mesh, purchased from Zhengdong Mineral Products Co., Ltd., Lingshou County; the organotin is dibutyltin dilaurate; the conductive carbon black model is HC-80; the quartz sand particle size is 100 mesh, purchased from Mileda Mineral Products Sales Co., Ltd., Haicheng City.

[0026] Example 1:

[0027] A preparation method of dust-proof and antistatic artificial terrazzo, comprising the following steps

[0028] (1) Mix acrylic acid, methyl methacrylate, butyl acrylate, diphenyl styrylphosphine, azobisisobutyronitrile, and isopropanol according to a mass ratio of 1:0.7:0.5:0.3:0.01:20, heat up to 85°C and reflux and stir for 3h, and obtain polyacrylic acid resin through rotary evaporation under reduced pressure and vacuum drying; Mix polyacrylic acid resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine, and N,N-dimethylformamide according to a mass ratio of 1:0.2:0.1:30, heat up to 70°C and react for 6h, and obtain pretreated polyacrylic acid resin through precipitation with ether, washing and drying; Mix the pretreated polyacrylic acid resin, potassium cyanide, ammonium carbonate, and N,N-dimethylformamide according to a mass ratio of 1:0.01:0.5:30, heat up to 150°C and react for 12h, and obtain pre-modified polyacrylic acid resin through precipitation with ether, filtration, washing and drying;

[0029] (2) Mix the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum trichloride, and N,N-dimethylformamide, heat up to 45 °C and react for 3 h. After the reaction, precipitate with pure water, filter, redisperse in a 5 wt% sodium hypochlorite solution, stir for 2 h, filter, wash, and dry to obtain the modified polyacrylic resin; the mass ratio of the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum trichloride, N,N-dimethylformamide, and 5 wt% sodium hypochlorite solution is 1:0.4:0.2:20:20; mix the modified polyacrylic resin, 80 wt% isopropyl alcohol aqueous solution, sodium dodecyl sulfonate, 35 wt% ammonia water, and pure water according to the mass ratio of 1:1:0.2:0.1:1 at 80 °C to obtain the modified polyacrylic emulsion;

[0030] (3) Mix quartz sand and ethanol, adjust the pH to 4 with a 40 wt% hydrochloric acid solution, add vinyltrimethoxysilane and mix ultrasonically for 10 min, then heat up to 80 °C and stir for 7 h, filter, wash, and dry to obtain the pretreated quartz sand; the mass ratio of quartz sand, ethanol, and vinyltrimethoxysilane is 1:0.3:50; mix the pretreated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine according to the mass ratio of 1:20:0.3:0.01, heat up to 50 °C and react for 12 h, filter, wash, and dry to obtain the pre-modified quartz sand;

[0031] (4) Mix the pre-modified quartz sand, phosphorus trichloride, toluene, and organotin according to the mass ratio of 1:0.3:20:0.03, heat up to 50 °C, filter, and then mix the filtered pre-modified quartz sand, toluene, and p-hydroxystyrene according to the mass ratio of 1:20:0.8, heat up to 70 °C and react for 6 h, filter, wash, and dry to obtain the phosphorus-containing quartz sand; under nitrogen protection, mix styrene, phosphorus-containing quartz sand, and cyclohexane according to the mass ratio of 1:5:35 and heat up to 60 °C, add n-butyllithium 0.01 times the mass of styrene after 5 min, then add n-butyllithium 0.03 times the mass of styrene again, react for 40 min, add butadiene 4 times the mass of styrene and continue to react for 45 min, then add styrene again and react for 40 min, and the addition amount of styrene this time is the same as the mass of styrene added for the first time; add ethanol 12 times the mass of styrene, filter, wash, and dry to obtain the modified quartz sand;

[0032] (5) Mix carbon black and ethanol, adjust the pH to 4 with 40wt% hydrochloric acid solution, add 3-mercaptopropyltrimethoxysilane and mix ultrasonically for 10 min, then heat to 80 °C and stir for 7 h. Filter, wash and dry to obtain mercapto-functionalized carbon black. The mass ratio of carbon black, ethanol and 3-mercaptopropyltrimethoxysilane is 1:0.3:50. Add equimolar amounts of triethylamine and 2-mercaptoethanol to tetrahydrofuran which is 10 times the mass of triethylamine, add dichlorodimethylsilane which is 0.45 times the molar amount of 2-mercaptoethanol, stir for 24 h, filter, wash with ether and distill under reduced pressure to obtain a multi-mercapto crosslinking agent. The mass ratio of carbon black, ethanol and 3-mercaptopropyltrimethoxysilane is 1:0.3:50. Weigh the following raw materials by mass fraction: 50 parts of quartz stone particles, 70 parts of ceramic particles, 140 parts of cement, 20 parts of modified quartz sand, 5 parts of dispersant, 5 parts of defoamer, 15 parts of mercapto-functionalized carbon black, 5 parts of multi-mercapto crosslinking agent, 30 parts of modified polyacrylic acid emulsion, 60 parts of water, 5 parts of dimethylphenylphosphine. Mix the above raw materials and pour them into a mold for curing. After demolding, curing, grinding and polishing, a dust-proof and anti-static artificial terrazzo is obtained.

[0033] Example 2:

[0034] A preparation method of a dust-proof and anti-static artificial terrazzo, comprising the following preparation steps:

[0035] (1) Mix acrylic acid, methyl methacrylate, butyl acrylate, diphenylstyrylphosphine, azobisisobutyronitrile and isopropanol according to the mass ratio of 1:0.75:0.55:0.4:0.01:25, heat to 83 °C and reflux and stir for 2.5 h. After rotary evaporation under reduced pressure and vacuum drying, a polyacrylic acid resin is obtained. Mix the polyacrylic acid resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine and N,N-dimethylformamide according to the mass ratio of 1:0.25:0.15:35, heat to 67 °C and react for 5.5 h. After precipitation with ether, washing and drying, a pretreated polyacrylic acid resin is obtained. Mix the pretreated polyacrylic acid resin, potassium cyanide, ammonium carbonate and N,N-dimethylformamide according to the mass ratio of 1:0.01:0.6:35, heat to 145 °C and react for 11 h. After precipitation with ether, filtering, washing and drying, a pre-modified polyacrylic acid resin is obtained.

[0036] (2) Mix the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum trichloride, and N,N-dimethylformamide, heat up to 43 °C and react for 2.5 h. After the reaction is completed, precipitate with pure water, filter, redisperse in a 5 wt% sodium hypochlorite solution, stir for 2 h, filter, wash, and dry to obtain the modified polyacrylic resin; the mass ratio of the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum trichloride, N,N-dimethylformamide, and 5 wt% sodium hypochlorite solution is 1:0.5:0.25:25:25; mix the modified polyacrylic resin, 80 wt% isopropyl alcohol aqueous solution, sodium dodecyl sulfonate, 35 wt% ammonia water, and pure water at a mass ratio of 1:1.1:0.3:0.15:1.1 at 80 °C to obtain the modified polyacrylic emulsion;

[0037] (3) Mix quartz sand and ethanol, adjust the pH to 4 with a 40 wt% hydrochloric acid solution, add vinyltrimethoxysilane and mix ultrasonically for 10 min, then heat up to 80 °C and stir for 6 h, filter, wash, and dry to obtain the pretreated quartz sand; the mass ratio of quartz sand, ethanol, and vinyltrimethoxysilane is 1:0.4:55; mix the pretreated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine at a mass ratio of 1:25:0.4:0.01, heat up to 45 °C and react for 11 h, filter, wash, and dry to obtain the pre-modified quartz sand;

[0038] (4) Mix the pre-modified quartz sand, phosphorus trichloride, toluene, and organotin at a mass ratio of 1:0.4:25:0.03, heat up to 45 °C, filter, and then mix the filtered pre-modified quartz sand, toluene, and p-hydroxystyrene at a mass ratio of 1:25:0.9, heat up to 65 °C and react for 5.5 h, filter, wash, and dry to obtain the phosphorus-containing quartz sand; under nitrogen protection, mix styrene, phosphorus-containing quartz sand, and cyclohexane at a mass ratio of 1:5.5:36 and heat up to 60 °C, add n-butyllithium 0.01 times the mass of styrene after 4 min, then add n-butyllithium 0.03 times the mass of styrene again, react for 35 min, add butadiene 4.5 times the mass of styrene and continue to react for 37 min, then add styrene again and react for 35 min, and the amount of styrene added this time is the same as the mass of styrene added for the first time; add ethanol 11 times the mass of styrene, filter, wash, and dry to obtain the modified quartz sand;

[0039] (5) Mix carbon black and ethanol, adjust the pH to 4 with 40wt% hydrochloric acid solution, add 3-mercaptopropyltrimethoxysilane and ultrasonically mix for 10 min, then heat to 80 °C and stir for 6 h. Filter, wash and dry to obtain mercapto-functionalized carbon black. The mass ratio of carbon black, ethanol and 3-mercaptopropyltrimethoxysilane is 1:0.4:55. Add equimolar amounts of triethylamine and 2-mercaptoethanol to tetrahydrofuran which is 11 times the mass of triethylamine, add dichlorodimethylsilane which is 0.47 times the molar amount of 2-mercaptoethanol, stir for 24 h, filter, wash with ether and distill under reduced pressure to obtain a multi-mercapto crosslinking agent. Weigh the following raw materials by mass fraction: 55 parts of quartz stone particles, 77 parts of ceramic particles, 153 parts of cement, 25 parts of modified quartz sand, 7 parts of dispersant, 3 parts of defoamer, 17 parts of mercapto-functionalized carbon black, 6 parts of multi-mercapto crosslinking agent, 35 parts of modified polyacrylic acid emulsion, 70 parts of water, and 6 parts of dimethylphenylphosphine. Mix the above raw materials, pour them into a mold for curing, and obtain the dust-proof and anti-static artificial terrazzo after demolding, curing, grinding and polishing.

[0040] Example 3:

[0041] A preparation method of dust-proof and anti-static artificial terrazzo, comprising the following steps

[0042] (1) Mix acrylic acid, methyl methacrylate, butyl acrylate, diphenyl styrylphosphine, azobisisobutyronitrile and isopropanol in a mass ratio of 1:0.8:0.6:0.5:0.02:30, heat to 82 °C and reflux and stir for 2 h, and obtain polyacrylic acid resin by rotary evaporation under reduced pressure and vacuum drying. Mix polyacrylic acid resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine and N,N-dimethylformamide in a mass ratio of 1:0.3:0.2:40, heat to 65 °C and react for 5 h, and obtain pretreated polyacrylic acid resin by precipitation with ether, washing and drying. Mix the pretreated polyacrylic acid resin, potassium cyanide, ammonium carbonate and N,N-dimethylformamide in a mass ratio of 1:0.02:0.7:40, heat to 140 °C and react for 10 h, and obtain pre-modified polyacrylic acid resin by precipitation with ether, filtration, washing and drying.

[0043] (2) Mix the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum trichloride, and N,N-dimethylformamide, heat up to 40 °C and react for 2 h. After the reaction, precipitate with pure water, filter, redisperse in a 5 wt% sodium hypochlorite solution, stir for 2 h, filter, wash, and dry to obtain the modified polyacrylic resin; the mass ratio of the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum trichloride, N,N-dimethylformamide, and 5 wt% sodium hypochlorite solution is 1:0.6:0.3:30:30; mix the modified polyacrylic resin, 80 wt% isopropyl alcohol aqueous solution, sodium dodecyl sulfonate, 35 wt% ammonia water, and pure water at a mass ratio of 1:1.2:0.4:0.2:1.2 at 80 °C to obtain the modified polyacrylic emulsion;

[0044] (3) Mix quartz sand and ethanol, adjust the pH to 4 with a 40 wt% hydrochloric acid solution, add vinyltrimethoxysilane and mix ultrasonically for 10 min, then heat up to 80 °C and stir for 5 h, filter, wash, and dry to obtain the pretreated quartz sand; the mass ratio of quartz sand, ethanol, and vinyltrimethoxysilane is 1:0.5:60; mix the pretreated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine at a mass ratio of 1:30:0.5:0.02, heat up to 40 °C and react for 10 h, filter, wash, and dry to obtain the pre-modified quartz sand;

[0045] (4) Mix the pre-modified quartz sand, phosphorus trichloride, toluene, and organotin at a mass ratio of 1:0.5:30:0.04, heat up to 40 °C, filter, and then mix the filtered pre-modified quartz sand, toluene, and p-hydroxystyrene at a mass ratio of 1:30:1.0, heat up to 60 °C and react for 5 h, filter, wash, and dry to obtain the phosphorus-containing quartz sand; under nitrogen protection, mix styrene, phosphorus-containing quartz sand, and cyclohexane at a mass ratio of 1:6:40 and heat up to 60 °C, add n-butyllithium 0.01 times the mass of styrene for 3 min, then add n-butyllithium 0.03 times the mass of styrene again, react for 30 min, add butadiene 5 times the mass of styrene and continue to react for 35 min, then add styrene again and react for 30 min, and the addition amount of styrene this time is the same as the mass of styrene added for the first time; add ethanol 12 times the mass of styrene, filter, wash, and dry to obtain the modified quartz sand;

[0046] (5) Conductive carbon black and ethanol are mixed, and the pH value is adjusted to 4 using a 40 wt % hydrochloric acid solution. After adding mercaptopropyl trimethoxysilane and ultrasonically mixing for 10 min, the temperature is raised to 80° C. and stirred for 5 h, filtered, washed, and dried to obtain mercapto conductive carbon black; the mass ratio of conductive carbon black, ethanol, and mercaptopropyl trimethoxysilane is 1:0.5:60; triethylamine and 2-mercaptoethanol in equal molar ratios are added to tetrahydrofuran with a mass of 12 times that of triethylamine, dichlorodimethylsilane with a molar mass of 0.5 times that of 2-mercaptoethanol is added, and the mixture is stirred for 24 hours. h, obtain a multi-thiol cross-linking agent by filtering, washing with ether and distilling under reduced pressure; weigh the following raw materials, by mass: 60 parts of quartz stone particles, 80 parts of ceramic particles, 160 parts of cement, 30 parts of modified quartz sand, 10 parts of dispersant, 10 parts of defoaming agent, 20 parts of thiol conductive carbon black, 7 parts of multi-thiol cross-linking agent, 40 parts of modified polyacrylic acid emulsion, 80 parts of water, and 6 parts of dimethylphenylphosphine, mix the above raw materials, pour them into a mold for curing, and obtain dust-proof and anti-static artificial terrazzo through demolding, curing, grinding and polishing.

[0047] Comparative Example 1:

[0048] The difference between Comparative Example 1 and Example 2 is that step (2) is not included, and step (1) is modified as follows: acrylic acid, methyl methacrylate, butyl acrylate, diphenyl phosphine, azobisisobutyronitrile, and isopropanol are mixed in a mass ratio of 1:0.75:0.55:0.4:0.01:25, the temperature is raised to 83°C, refluxed and stirred for 2.5 hours, and polyacrylic acid resin is obtained by vacuum rotary evaporation and vacuum drying; polyacrylic acid resin, 80wt% isopropanol aqueous solution, sodium dodecyl sulfate, 35wt% ammonia water, and pure water are mixed in a mass ratio of 1:1.1:0.3:0.15:1.1 at 80°C to obtain a modified polyacrylic acid emulsion.

[0049] Comparative Example 2:

[0050] The difference between Comparative Example 1 and Example 2 is that the quartz sand and conductive carbon black are not modified, and no polythiol crosslinking agent is added. Specifically, steps (3) and (4) are not included, and step (5) is modified as follows: weigh the following raw materials, by mass: 55 parts of quartz stone particles, 77 parts of ceramic particles, 153 parts of cement, 25 parts of quartz sand, 7 parts of dispersant, 3 parts of defoaming agent, 17 parts of conductive carbon black, 35 parts of modified polyacrylic acid emulsion, and 70 parts of water; mix the above raw materials, pour them into a mold for curing, and obtain dust-proof and antistatic artificial terrazzo after demolding, curing, grinding and polishing.

[0051] Test Example 1:

[0052] Antibacterial performance test:

[0053] The terrazzo prepared in the examples and comparative examples was crushed. After crushing, it was filtered using a 0.08 nm standard sieve to obtain a powder with a particle size less than 0.08 nm. 2 g of the powder was placed in a filter paper with a diameter of 1 cm, and the filter paper was placed in a solid medium smeared with a bacterial solution and cultured at 37 °C for 12 h. The size of the antibacterial zone was measured by the Oxford cup method. The results are shown in Table 1.

[0054] Table 1 Statistical results of antibacterial performance test

[0055] Inhibition zone diameter / mm Inhibition zone diameter / mm Example 1 17.4 Comparative Example 1 11.2 Example 2 17.5 Comparative Example 2 17.3 Example 3 17.5

[0056] From the experimental data in Table 1, it can be found that the artificial terrazzo prepared by the present invention has good antibacterial properties; in Comparative Example 1, the polyacrylic resin was not subjected to antibacterial modification. By comparison, the antibacterial properties of Examples 1-3 are better than those of Comparative Example 1, indicating that acrylic acid, methyl methacrylate, butyl acrylate, and diphenyl styrylphosphine are polymerized under the action of an initiator to form a polyacrylic resin. The molecular chain of the resin contains a triphenylphosphine structure, and 1-[4-(chloromethyl)phenyl]ethanone and the triphenylphosphine structure form a quaternary phosphonium salt structure with antibacterial properties, and a formyl group structure is introduced. The formyl group undergoes addition, substitution, cyclization, and rearrangement under the action of potassium cyanide and ammonium carbonate to form a hydantoin structure. After chlorination with sodium hypochlorite, the combination of the quaternary phosphonium salt and haloamine can further improve the antibacterial properties of the material.

[0057] Test Example 2:

[0058] Test of mechanical properties:

[0059] Test method: According to the standard GB 28635—2012 "Concrete Pavement Bricks", the flexural strength of the terrazzo prepared in the examples and comparative examples was tested. The results are shown in Table 2.

[0060] Test of anti-aging performance:

[0061] The anti-aging performance was tested in an ultraviolet aging chamber. The ultraviolet intensity was 250 W / m 2 , the aging temperature was 60 °C, and the aging time was 20 days. After aging, the flexural strength was tested according to the test method of mechanical properties and the flexural strength retention rate was calculated. The results are shown in Table 2.

[0062] Table 2 Statistical results of mechanical properties and anti-aging performance test

[0063]

[0064] It can be found from the experimental data in Table 2 that the artificial terrazzo prepared by the present invention has good mechanical properties and anti-aging properties; in Comparative Example 2, quartz sand and conductive carbon black were not modified, and no multi-mercapto cross-linking agent was added. The mechanical properties of Examples 1 to 3 are better than those of Comparative Examples 1 to 2, and the flexural strength retention rate of Examples 1 to 3 is greater than that of Comparative Example 2. This shows that the surface of quartz stone is treated with vinyltrimethoxysilane to make its surface carry vinyl groups. Through the reaction of mercapto and vinyl groups, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol is grafted, and then reacted with phosphorus trichloride and p-hydroxystyrene in sequence to generate a phosphite structure with antioxidant properties, and vinyl groups are introduced. Under the action of n-butyllithium, the vinyl groups on p-hydroxystyrene and styrene and butadiene undergo anionic polymerization reactions to wrap a styrene-butadiene-styrene block copolymer on the surface of quartz stone, endowing the material with good toughness; mixing quartz stone particles, ceramic particles, cement, modified quartz sand, dispersant, defoaming agent, mercapto-functionalized conductive carbon black, modified polyacrylate emulsion, water, and dimethylphenylphosphine to obtain artificial terrazzo. The polyacrylate emulsion, as an adhesive, can effectively bind each component together to enhance the compactness of the material; in addition to endowing the terrazzo with good antistatic properties, the mercapto-functionalized conductive carbon black can indirectly improve the dust-proof performance of the terrazzo by reducing electrostatic adsorption. The mercapto groups on the mercapto conductive carbon black and the mercapto groups on the multi-mercapto cross-linking agent can also undergo electrophilic addition reactions with the double bonds on the surface of the polyacrylate emulsion and modified quartz sand under the action of a catalyst to form more cross-linking sites, further enhancing the compactness and mechanical properties of the material.

[0065] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be construed as limiting the claimed claim.

Claims

1. A preparation method of dust-proof and anti-static artificial terrazzo, characterized in that, The following steps are involved: (1) reacting acrylic acid, methyl methacrylate, butyl acrylate, and diphenyl phosphine to obtain a polyacrylic acid resin; reacting the polyacrylic acid resin and 1-[4-(chloromethyl)phenyl]ethanone to obtain a pretreated polyacrylic acid resin; reacting the pretreated polyacrylic acid resin, potassium cyanide, and ammonium carbonate to obtain a pre-modified polyacrylic acid resin; (2) reacting a pre-modified acrylic resin and 4-vinylbenzoyl chloride, and then chlorinating with a sodium hypochlorite solution to obtain a modified polyacrylic acid resin; emulsifying the modified polyacrylic acid resin to obtain a modified polyacrylic acid emulsion; (3) reacting pretreated quartz sand, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine to obtain pre-modified quartz sand; (4) reacting pre-modified quartz sand and phosphorus trichloride, and then reacting with p-hydroxystyrene to obtain phosphorus-containing quartz sand; polymerizing styrene, phosphorus-containing quartz sand, and butadiene to obtain modified quartz sand; (5) Weigh the following raw materials, by mass: 50-60 parts of quartz stone particles, 70-80 parts of ceramic particles, 140-160 parts of cement, 20-30 parts of modified quartz sand, 5-10 parts of dispersant, 5-10 parts of defoamer, 15-20 parts of thiol conductive carbon black, 5-7 parts of polythiol crosslinking agent, 30-40 parts of modified polyacrylic acid emulsion, 60-80 parts of water, and 5-6 parts of dimethylphenylphosphine; mix the above raw materials, pour them into a mold for curing, and obtain dust-proof and antistatic artificial terrazzo through demolding, curing, grinding and polishing.

2. The preparation method of a dust-proof and anti-static artificial terrazzo according to claim 1, characterized in that, The preparation method of the pre-modified polyacrylic acid resin in step (1) is as follows: acrylic acid, methyl methacrylate, butyl acrylate, diphenyl p-phenylyl phosphine, azobisisobutyronitrile and isopropanol are mixed, heated to 82-85°C, refluxed and stirred for 2-3h, and subjected to reduced pressure rotary evaporation and vacuum drying to obtain polyacrylic acid resin; the mass ratio of acrylic acid, methyl methacrylate, butyl acrylate, diphenyl p-phenylyl phosphine, azobisisobutyronitrile and isopropanol is: 1:(0.7-0.8):(0.5-0.6):(0.3-0.5):(0.01-0.02):(20-30); polyacrylic acid resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine and N,N-dimethylformamide are mixed, heated to 65-70°C, and stirred for 2-3h. ℃ for reaction for 5-6h, precipitated with ether, washed and dried to obtain a pretreated polyacrylic acid resin; the mass ratio of polyacrylic acid resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine and N,N-dimethylformamide is 1:(0.2-0.3):(0.1-0.2):(30-40); the pretreated polyacrylic acid resin, potassium cyanide, ammonium carbonate and N,N-dimethylformamide are mixed, the temperature is raised to 140-150℃ for reaction for 10-12h, precipitated with ether, filtered, washed and dried to obtain a pre-modified polyacrylic acid resin; the mass ratio of pretreated polyacrylic acid resin, potassium cyanide, 35wt% ammonia water and N,N-dimethylformamide is 1:(0.01-0.02):(0.5-0.7):(30-40).

3. The preparation method of an anti-dust and anti-static artificial terrazzo according to claim 1, characterized in that, The preparation method of the polyacrylic acid emulsion described in step (2) is as follows: Mix the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum trichloride, and N,N-dimethylformamide, heat up to 40 - 45 °C and react for 2 - 3 h. After the reaction, precipitate with pure water, filter, redisperse in a 5 wt% sodium hypochlorite solution, stir for 2 h, filter, wash, and dry to obtain the modified polyacrylic acid resin; The mass ratio of the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum trichloride, N,N-dimethylformamide, and 5 wt% sodium hypochlorite solution is 1:(0.4 - 0.6):(0.2 - 0.3):(20 - 30):(20 - 30); Mix the modified polyacrylic acid resin, 80 wt% isopropyl alcohol aqueous solution, sodium dodecyl sulfonate, 35 wt% ammonia water, and pure water at a mass ratio of 1:(1 - 1.2):(0.2 - 0.4):(0.1 - 0.2):(1 - 1.2) at 80 °C to obtain the modified polyacrylic acid emulsion.

4. The preparation method of a dust-proof and anti-static artificial terrazzo according to claim 1, characterized in that, The preparation method of the pre-modified quartz sand described in step (3) is as follows: Mix quartz sand and ethanol, adjust the pH to 4 with a 40 wt% hydrochloric acid solution, add vinyltrimethoxysilane and mix ultrasonically for 10 min, then heat up to 80 °C and stir for 5 - 7 h, filter, wash, and dry to obtain the pretreated quartz sand; The mass ratio of quartz sand, ethanol, and vinyltrimethoxysilane is 1:(0.3 - 0.5):(50 - 60); Mix the pretreated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine, heat up to 40 - 50 °C and react for 10 - 12 h, filter, wash, and dry to obtain the pre-modified quartz sand; The mass ratio of the pretreated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine is 1:(20 - 30):(0.3 - 0.5):(0.01 - 0.02).

5. The preparation method of a dust-proof and anti-static artificial terrazzo according to claim 1, characterized in that, The preparation method of the modified quartz sand described in step (4) is as follows: Mix the pre-modified quartz sand, phosphorus trichloride, toluene, and organotin at a mass ratio of 1:(0.3 - 0.5):(20 - 30):(0.03 - 0.04), heat up to 40 - 50 °C, then filter. Mix the filtered pre-modified quartz sand, toluene, and p-hydroxystyrene at a mass ratio of 1:(20 - 30):(0.8 - 1.0), heat up to 60 - 70 °C and react for 5 - 6 h, filter, wash, and dry to obtain the phosphorus-containing quartz sand; Under nitrogen protection, mix styrene, the phosphorus-containing quartz sand, and cyclohexane at a mass ratio of 1:(5 - 6):(35 - 40) and heat up to 60 °C. Add n-butyllithium at 0.01 times the mass of styrene for 3 - 5 min, then add n-butyllithium at 0.03 times the mass of styrene again, react for 30 - 40 min, add butadiene at 4 - 5 times the mass of styrene and continue to react for 35 - 45 min, then add styrene again and react for 30 - 40 min. The amount of styrene added this time is the same as the mass of styrene added for the first time; Add ethanol at 10 - 12 times the mass of styrene, filter, wash, and dry to obtain the modified quartz sand.

6. The preparation method of a dust-proof and anti-static artificial terrazzo according to claim 1, characterized in that, The preparation method of the mercapto-functionalized conductive carbon black described in step (5) is as follows: Mix conductive carbon black and ethanol, adjust the pH to 4 with a 40 wt% hydrochloric acid solution, add 3-mercaptopropyltrimethoxysilane and ultrasonically mix for 10 min, then raise the temperature to 80 °C and stir for 5 - 7 h, followed by filtration, washing, and drying to obtain the mercapto-functionalized conductive carbon black; the mass ratio of conductive carbon black, ethanol, and 3-mercaptopropyltrimethoxysilane is 1:(0.3 - 0.5):(50 - 60); the preparation method of the multi-mercapto crosslinking agent is: Add equimolar amounts of triethylamine and 2-mercaptoethanol to tetrahydrofuran in an amount 10 - 12 times the mass of triethylamine, add dichlorodimethylsilane in an amount 0.45 - 0.5 times the molar amount of 2-mercaptoethanol, stir for 24 h, and obtain the multi-mercapto crosslinking agent through filtration, washing with ether, and vacuum distillation.

7. The preparation method of an anti-dust and anti-static artificial terrazzo according to claim 4, characterized in that, The particle size of the quartz sand is 200 mesh.

8. A dust-proof and anti-static artificial terrazzo prepared by the preparation method of the dust-proof and anti-static artificial terrazzo according to any one of claims 1 - 7.

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