Dustproof and antistatic artificial terrazzo and preparation method thereof

Abstract

The application discloses dustproof and anti-static artificial waterstone and a preparation method thereof. The dustproof and anti-static artificial waterstone prepared by the application comprises the following components: quartz stone particles, ceramic particles, cement, modified quartz sand, a dispersing agent, a defoaming agent, mercapto conductive carbon black, a multi-mercapto crosslinking agent, modified polyacrylic acid emulsion, water and dimethylphenyl phosphine; the modified polyacrylic acid emulsion is obtained by the following steps: polymerization of acrylate monomers and diphenyl p-styryl phosphine, reaction with 1-[4-(chloromethyl)phenyl]ethanone, reaction with potassium cyanide and ammonium carbonate, chlorination, and emulsification; the modified quartz sand is obtained by the following steps: grafting 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol on pretreated quartz sand, reaction with phosphorus trichloride, and reaction with p-hydroxystyrene; and polymerization of styrene and butadiene on the surface of the modified quartz sand; and the dustproof and anti-static artificial waterstone prepared by the application has good mechanical properties, antibacterial properties and anti-aging properties.

Description

Technical Field

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

[0002] Artificial terrazzo is a composite material made from cement or resin as a binder, mixed with various aggregates such as marble chips, quartz particles, and glass flakes. It is widely used in architectural decoration, favored for its customizable colors and patterns. Traditional terrazzo, due to its cost-effectiveness, flexible color and texture options, and ease of construction, has found widespread application in various buildings, including residential, commercial, and public facilities. However, with increasing demand and technological advancements, traditional terrazzo floors have gradually exposed some problems.

[0003] Traditional terrazzo floors can easily become rough and harbor dirt due to improper surface treatment, making daily cleaning and maintenance difficult. For certain specific application scenarios, such as electronic manufacturing workshops, laboratories, or hospitals, which have extremely high requirements for environmental cleanliness, terrazzo floors also need to have dust-proof and anti-static functions to prevent the 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, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A method for preparing dust-proof and anti-static artificial terrazzo, comprising the following steps:

[0007] (1) reacting acrylic acid, methyl methacrylate, butyl acrylate, and diphenyl phenyl 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; and reacting the pretreated polyacrylic acid resin, potassium cyanide, and ammonium carbonate to obtain a pre-modified polyacrylic acid resin;

[0008] (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;

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

[0010] (4) reacting pre-modified quartz sand with 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;

[0011] (5) Weigh the following raw materials, calculated 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 defoaming agent, 15-20 parts of mercapto 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 then demold, cure, grind, and polish to obtain dust-proof and anti-static artificial terrazzo.

[0012] Preferably, the preparation method of the pre-modified polyacrylic acid resin in step (1) is as follows: acrylic acid, methyl methacrylate, butyl acrylate, diphenyl p-phenylylphosphine, azobisisobutyronitrile, and isopropyl alcohol are mixed, heated to 82-85° C., refluxed and stirred for 2-3 hours, 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-phenylylphosphine, azobisisobutyronitrile, and isopropyl alcohol 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- The reaction was carried out at 70° C. for 5-6 hours, and the mixture was precipitated with diethyl ether, washed, and dried to obtain a pretreated polyacrylic acid resin; the mass ratio of the polyacrylic acid resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine, and N,N-dimethylformamide was 1:(0.2-0.3):(0.1-0.2):(30-40); the pretreated polyacrylic acid resin, potassium cyanide, ammonium carbonate, and N,N-dimethylformamide were mixed, the temperature was raised to 140-150° C., the reaction was carried out for 10-12 hours, and the mixture was precipitated with diethyl ether, filtered, washed, and dried to obtain a pre-modified polyacrylic acid resin; the mass ratio of the pretreated polyacrylic acid resin, potassium cyanide, 35 wt% ammonia water, and N,N-dimethylformamide was 1:(0.01-0.02):(0.5-0.7):(30-40).

[0013] Preferably, the preparation method of the polyacrylic acid emulsion in step (2) is as follows: pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum chloride, and N,N-dimethylformamide are mixed, heated to 40-45° C. and reacted for 2-3 hours. After the reaction, the mixture is precipitated with pure water, filtered, and redispersed in a 5wt% sodium hypochlorite solution, stirred for 2 hours, filtered, washed, and dried to obtain the modified polyacrylic acid resin; pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum chloride, N,N-dimethylformamide are mixed, heated to 40-45° C. and reacted for 2-3 hours. -dimethylformamide and 5wt% sodium hypochlorite solution in a mass ratio of 1:(0.4-0.6):(0.2-0.3):(20-30):(20-30); modified polyacrylic acid resin, 80wt% isopropyl alcohol aqueous solution, sodium lauryl sulfonate, 35wt% ammonia water, and pure water in a mass ratio of 1:(1-1.2):(0.2-0.4):(0.1-0.2):(1-1.2) are mixed at 80° C. to obtain a modified polyacrylic acid emulsion.

[0014] Preferably, the preparation method of the pre-modified quartz sand in step (3) is as follows: mixing quartz sand and ethanol, adjusting the pH to 4 with a 40wt% hydrochloric acid solution, adding vinyltrimethoxysilane and ultrasonically mixing for 10 minutes, heating to 80°C and stirring for 5-7 hours, filtering, washing and drying to obtain pre-treated quartz sand; the mass ratio of quartz sand, ethanol and vinyltrimethoxysilane is 1: (0.3-0.5): (50-60); mixing pre-treated quartz sand, dichloromethane, 2,6-bis (tert-butyl) -4- (mercaptomethyl) phenol and dimethylphenylphosphine, heating to 40-50°C and reacting for 10-12 hours, filtering, washing and drying to obtain pre-modified quartz sand; the mass ratio of pre-treated 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: pre-modified quartz sand, phosphorus trichloride, toluene, and organic tin are mixed in a mass ratio of 1: (0.3-0.5): (20-30): (0.03-0.04), heated to 40-50 ° C, filtered, and the filtered pre-modified quartz sand, toluene, and p-hydroxystyrene are mixed in a mass ratio of 1: (20-30): (0.8-1.0), heated to 60-70 ° C and reacted for 5-6 hours, filtered, washed, and dried to obtain phosphorus-containing quartz sand; under nitrogen protection, styrene, phosphorus-containing quartz sand, The method comprises the following steps: mixing cyclohexane in a mass ratio of 1:(5-6):(35-40) and heating to 60°C; adding n-butyl lithium in an amount of 0.01 times the mass of styrene for 3-5 minutes; adding n-butyl lithium in an amount of 0.03 times the mass of styrene again and reacting for 30-40 minutes; adding butadiene in an amount of 4-5 times the mass of styrene and continuing the reaction for 35-45 minutes; adding styrene again and reacting for 30-40 minutes, wherein the amount of styrene added this time is the same as that added for the first time; adding ethanol in an amount of 10-12 times the mass of styrene, and filtering, washing, and drying to obtain modified quartz sand.

[0016] Preferably, the preparation method of the mercaptolated conductive carbon black in step (5) is: mixing conductive carbon black and ethanol, adjusting the pH to 4 with a 40wt% hydrochloric acid solution, adding mercaptopropyltrimethoxysilane and ultrasonically mixing for 10 minutes, heating to 80°C and stirring for 5-7 hours, filtering, washing and drying to obtain the mercaptolated conductive carbon black; the mass ratio of conductive carbon black, ethanol and mercaptopropyltrimethoxysilane is 1: (0.3-0.5): (50-60); the preparation method of the polythiol crosslinking agent is: adding triethylamine and 2-mercaptoethanol in equal molar ratios to tetrahydrofuran with a mass of 10-12 times that of triethylamine, adding dichlorodimethylsilane with a molar mass of 0.45-0.5 times that of 2-mercaptoethanol, stirring for 24 hours, filtering, washing with ether and distilling under reduced pressure to obtain the polythiol crosslinking agent.

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

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

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[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, a dispersant, a defoamer, mercapto-conductive carbon black, a multi-mercapto crosslinking agent, a modified polyacrylic acid emulsion, water, and dimethylphenylphosphine; the modified polyacrylic acid emulsion is obtained by polymerizing an acrylate monomer and diphenyl-p-phenylenediphosphine, reacting with 1-[4-(chloromethyl)phenyl]ethanone, reacting with potassium cyanide and ammonium carbonate, and then chlorinating and emulsifying; 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, on the surface of which styrene and butadiene are polymerized.

[0021] First, acrylic acid, methyl methacrylate, butyl acrylate, and diphenyl(p-phenyl)phosphine are polymerized under the action of an initiator to form a polyacrylic acid resin. The resin's molecular chain contains a triphenylphosphine structure. 1-[4-(chloromethyl)phenyl]ethanone and the triphenylphosphine structure form a quaternary phosphonium salt structure with antibacterial properties, and a formyl 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 the halamine can further enhance the material's antibacterial properties. 4-Vinylbenzoyl chloride is grafted onto the benzene ring structure of the polyacrylic acid backbone through a Friedel-Crafts reaction, thereby introducing a vinyl group.

[0022] Secondly, vinyltrimethoxysilane is used to treat the surface of the quartz stone to make it have vinyl groups on the surface. 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol is grafted on it through the reaction of thiol and alkenyl groups. It is 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-butyl lithium, the vinyl groups on p-hydroxystyrene undergo anionic polymerization with styrene and butadiene, and styrene-butadiene-styrene block copolymer is wrapped on the surface of the quartz stone, giving the material good toughness.

[0023] Finally, quartz stone particles, ceramic particles, cement, modified quartz sand, dispersant, defoaming agent, thiol-conductive carbon black, polythiol crosslinking agent, modified polyacrylic acid emulsion, water, and dimethylphenylphosphine are mixed to obtain artificial terrazzo. Polyacrylic acid emulsion, as an adhesive, can be used as an effective adhesive to combine the various components together to enhance the density of the material. In addition to giving terrazzo good antistatic properties, the thiol-conductive carbon black can indirectly improve the dust-proof performance of terrazzo by reducing electrostatic adsorption. The thiol groups on the thiol-conductive carbon black and the thiol groups on the polythiol crosslinking agent can also undergo electrophilic addition of thiol groups to the double bonds on the surface of polyacrylic acid emulsion and modified quartz sand under the action of a catalyst to form more crosslinking sites, further enhancing the density and mechanical properties of the material. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0025] In the following examples and comparative examples, the defoaming agent 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 2-4 mm, purchased from Lingshou County Baiyi Mineral Products Processing Plant; the ceramic particle mesh size is 20-40 mesh, purchased from Lingshou County Zhengdong Mineral Products Co., Ltd.; the organotin is dibutyltin dilaurate; the conductive carbon black model is HC-80; the quartz sand particle size is 100 mesh, purchased from Haicheng Mileda Mineral Products Sales Co., Ltd.

[0026] Example 1:

[0027] A method for preparing dust-proof and anti-static artificial terrazzo, comprising the following steps

[0028] (1) Acrylic acid, methyl methacrylate, butyl acrylate, diphenyl phenyl phosphine, azobisisobutyronitrile and isopropyl alcohol were mixed in a mass ratio of 1:0.7:0.5:0.3:0.01:20, heated to 85°C and refluxed with stirring for 3 hours, and then subjected to reduced pressure rotary evaporation and vacuum drying to obtain polyacrylic acid resin; polyacrylic acid resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine and N,N-dimethylformamide were mixed in a mass ratio of 1:0.2:0.1:30, heated to 70°C and reacted for 6 hours, precipitated with ether, washed and dried to obtain pretreated polyacrylic acid resin; pretreated polyacrylic acid resin, potassium cyanide, ammonium carbonate and N,N-dimethylformamide were mixed in a mass ratio of 1:0.01:0.5:30, heated to 150°C and reacted for 12 hours, precipitated with ether, filtered, washed and dried to obtain pre-modified polyacrylic acid resin;

[0029] (2) Pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum chloride, and N,N-dimethylformamide were mixed, heated to 45° C. for reaction for 3 h, and after the reaction, precipitated with pure water, filtered, and redispersed in a 5 wt% sodium hypochlorite solution, stirred for 2 h, filtered, washed, and dried to obtain a modified polyacrylic resin; the mass ratio of the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum chloride, N,N-dimethylformamide, and 5 wt% sodium hypochlorite solution was 1:0.4:0.2:20:20; the modified polyacrylic resin, 80 wt% isopropyl alcohol aqueous solution, sodium lauryl sulfate, 35 wt% ammonia water, and pure water were mixed at a mass ratio of 1:1:0.2:0.1:1 at 80° C. to obtain a modified polyacrylic emulsion;

[0030] (3) Quartz sand and ethanol were mixed, and the pH was adjusted to 4 using a 40 wt% hydrochloric acid solution. Vinyltrimethoxysilane was added and ultrasonically mixed for 10 min, and then the mixture was heated to 80°C and stirred for 7 h. The mixture was filtered, washed, and dried to obtain pretreated quartz sand. The mass ratio of quartz sand, ethanol, and vinyltrimethoxysilane was 1:0.3:50. The pretreated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine were mixed in a mass ratio of 1:20:0.3:0.01, and the mixture was heated to 50°C and reacted for 12 h. The pre-modified quartz sand was obtained by filtering, washing, and drying.

[0031] (4) Pre-modified quartz sand, phosphorus trichloride, toluene, and organic tin are mixed in a mass ratio of 1:0.3:20:0.03, heated to 50°C, and filtered. The filtered pre-modified quartz sand, toluene, and p-hydroxystyrene are mixed in a mass ratio of 1:20:0.8, heated to 70°C for reaction for 6h, filtered, washed, and dried to obtain phosphorus-containing quartz sand; under nitrogen protection, styrene, phosphorus-containing quartz sand, and cyclohexane are mixed in a mass ratio of 1:5:35 and heated to 60°C, 0.01 times the mass of styrene n-butyl lithium is added for 5 minutes, 0.03 times the mass of styrene n-butyl lithium is added again, and the reaction is carried out for 40 minutes, 4 times the mass of styrene butadiene is added and the reaction is continued for 45 minutes, and styrene is added again for reaction for 40 minutes, and the amount of styrene added this time is the same as the mass of styrene added for the first time; 12 times the mass of styrene ethanol is added, and the modified quartz sand is obtained after filtering, washing, and drying;

[0032] (5) Conductive carbon black and ethanol were mixed, and the pH value was adjusted to 4 using a 40 wt% hydrochloric acid solution. After adding mercaptopropyl trimethoxysilane and ultrasonically mixing for 10 minutes, the mixture was heated to 80°C and stirred for 7 hours, filtered, washed, and dried to obtain mercaptolated conductive carbon black; the mass ratio of conductive carbon black, ethanol, and mercaptopropyl trimethoxysilane was 1:0.3:50; triethylamine and 2-mercaptoethanol in equal molar ratios were added to tetrahydrofuran (10 times the mass of triethylamine), and dichlorodimethylsilane (0.45 times the molar amount of 2-mercaptoethanol) was added, stirred for 24 hours, filtered, washed with ether, and evaporated under reduced pressure. The method comprises the following steps: distilling the conductive carbon black to obtain a multi-thiol crosslinking agent; the mass ratio of conductive carbon black, ethanol, and mercaptopropyltrimethoxysilane is 1:0.3:50; weighing the following raw materials, by mass, 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-conductive carbon black, 5 parts of multi-thiol crosslinking agent, 30 parts of modified polyacrylic acid emulsion, 60 parts of water, and 5 parts of dimethylphenylphosphine; mixing the above raw materials, pouring the mixture into a mold for curing, and obtaining a dust-proof and anti-static artificial terrazzo through demoulding, curing, grinding, and polishing.

[0033] Example 2:

[0034] A method for preparing dust-proof and anti-static artificial terrazzo comprises the following steps:

[0035] (1) Acrylic acid, methyl methacrylate, butyl acrylate, diphenyl phosphine, azobisisobutyronitrile and isopropyl alcohol were mixed in a mass ratio of 1:0.75:0.55:0.4:0.01:25, heated to 83°C and refluxed with stirring for 2.5 hours, and then subjected to reduced pressure rotary evaporation and vacuum drying to obtain polyacrylic acid resin; polyacrylic acid resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine and N,N-dimethylformamide were mixed in a mass ratio of 1:0.25:0.15:35, heated to 67°C and reacted for 5.5 hours, precipitated with ether, washed and dried to obtain pretreated polyacrylic acid resin; pretreated polyacrylic acid resin, potassium cyanide, ammonium carbonate and N,N-dimethylformamide were mixed in a mass ratio of 1:0.01:0.6:35, heated to 145°C and reacted for 11 hours, precipitated with ether, filtered, washed and dried to obtain pre-modified polyacrylic acid resin;

[0036] (2) Pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum chloride, and N,N-dimethylformamide were mixed, heated to 43° C. and reacted for 2.5 hours. After the reaction, the mixture was precipitated with pure water, filtered, and redispersed in a 5wt% sodium hypochlorite solution, stirred for 2 hours, filtered, washed, and dried to obtain a modified polyacrylic resin; the mass ratio of the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum chloride, N,N-dimethylformamide, and 5wt% sodium hypochlorite solution was 1:0.5:0.25:25:25; the modified polyacrylic resin, 80wt% isopropyl alcohol aqueous solution, sodium lauryl sulfate, 35wt% ammonia water, and pure water were mixed at a mass ratio of 1:1.1:0.3:0.15:1.1 at 80° C. to obtain a modified polyacrylic emulsion;

[0037] (3) Quartz sand and ethanol were mixed, and the pH was adjusted to 4 using a 40 wt% hydrochloric acid solution. Vinyltrimethoxysilane was added and ultrasonically mixed for 10 min, and then the mixture was heated to 80°C and stirred for 6 h. The mixture was filtered, washed, and dried to obtain pretreated quartz sand. The mass ratio of quartz sand, ethanol, and vinyltrimethoxysilane was 1:0.4:55. The pretreated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine were mixed in a mass ratio of 1:25:0.4:0.01, and the mixture was heated to 45°C and reacted for 11 h. The pre-modified quartz sand was obtained by filtering, washing, and drying.

[0038] (4) Pre-modified quartz sand, phosphorus trichloride, toluene, and organic tin are mixed in a mass ratio of 1:0.4:25:0.03, heated to 45°C, and filtered. The filtered pre-modified quartz sand, toluene, and p-hydroxystyrene are mixed in a mass ratio of 1:25:0.9, heated to 65°C for reaction for 5.5h, filtered, washed, and dried to obtain phosphorus-containing quartz sand; under nitrogen protection, styrene, phosphorus-containing quartz sand, and cyclohexane are mixed in a mass ratio of 1:5.5:36 and heated to 60°C, 0.01 times the mass of styrene of n-butyl lithium is added for 4 minutes, 0.03 times the mass of styrene of n-butyl lithium is added again, and the reaction is carried out for 35 minutes, 4.5 times the mass of styrene of butadiene is added and the reaction is continued for 37 minutes, and styrene is added again for reaction for 35 minutes. The amount of styrene added this time is the same as the mass of styrene added for the first time; 11 times the mass of styrene of ethanol is added, and the modified quartz sand is obtained after filtering, washing, and drying;

[0039] (5) Conductive carbon black and ethanol were mixed, and the pH value was adjusted to 4 using a 40 wt% hydrochloric acid solution. After adding mercaptopropyl trimethoxysilane and ultrasonically mixing for 10 min, the mixture was heated to 80°C and stirred for 6 h, filtered, washed, and dried to obtain mercaptolated conductive carbon black. The mass ratio of conductive carbon black, ethanol, and mercaptopropyl trimethoxysilane was 1:0.4:55. Equal molar ratios of triethylamine and 2-mercaptoethanol were added to tetrahydrofuran (11 times the mass of triethylamine), and dichlorodimethylsilane (0.47 times the molar amount of 2-mercaptoethanol) was added, and stirred for 2 min. 4h, filtered, washed with ether, and distilled under reduced pressure to obtain a polythiol crosslinking agent; weigh the following raw materials, in parts by mass: 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 defoaming agent, 17 parts of thiol conductive carbon black, 6 parts of polythiol 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 dust-proof and anti-static artificial terrazzo after demoulding, curing, grinding, and polishing.

[0040] Example 3:

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

[0042] (1) Acrylic acid, methyl methacrylate, butyl acrylate, diphenyl phenyl phosphine, azobisisobutyronitrile and isopropyl alcohol were mixed in a mass ratio of 1:0.8:0.6:0.5:0.02:30, heated to 82°C and refluxed with stirring for 2 hours, and then subjected to reduced pressure rotary evaporation and vacuum drying to obtain polyacrylic acid resin; polyacrylic acid resin, 1-[4-(chloromethyl)phenyl]ethanone, triethylamine and N,N-dimethylformamide were mixed in a mass ratio of 1:0.3:0.2:40, heated to 65°C and reacted for 5 hours, precipitated with ether, washed and dried to obtain pretreated polyacrylic acid resin; pretreated polyacrylic acid resin, potassium cyanide, ammonium carbonate and N,N-dimethylformamide were mixed in a mass ratio of 1:0.02:0.7:40, heated to 140°C and reacted for 10 hours, precipitated with ether, filtered, washed and dried to obtain pre-modified polyacrylic acid resin;

[0043] (2) Pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum chloride, and N,N-dimethylformamide were mixed, heated to 40° C. for reaction for 2 h, and after the reaction, precipitated with pure water, filtered, and redispersed in a 5 wt% sodium hypochlorite solution, stirred for 2 h, filtered, washed, and dried to obtain a modified polyacrylic resin; the mass ratio of the pre-modified acrylic resin, 4-vinylbenzoyl chloride, aluminum chloride, N,N-dimethylformamide, and 5 wt% sodium hypochlorite solution was 1:0.6:0.3:30:30; the modified polyacrylic resin, 80 wt% isopropyl alcohol aqueous solution, sodium lauryl sulfate, 35 wt% ammonia water, and pure water were mixed at 80° C. in a mass ratio of 1:1.2:0.4:0.2:1.2 to obtain a modified polyacrylic emulsion;

[0044] (3) Quartz sand and ethanol were mixed, and the pH was adjusted to 4 using a 40 wt% hydrochloric acid solution. Vinyltrimethoxysilane was added and ultrasonically mixed for 10 min, and then the mixture was heated to 80°C and stirred for 5 h. The mixture was filtered, washed, and dried to obtain pretreated quartz sand. The mass ratio of quartz sand, ethanol, and vinyltrimethoxysilane was 1:0.5:60. The pretreated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine were mixed in a mass ratio of 1:30:0.5:0.02, and the mixture was heated to 40°C and reacted for 10 h. The pre-modified quartz sand was obtained by filtering, washing, and drying.

[0045] (4) Pre-modified quartz sand, phosphorus trichloride, toluene, and organic tin are mixed in a mass ratio of 1:0.5:30:0.04, heated to 40°C, and filtered. The filtered pre-modified quartz sand, toluene, and p-hydroxystyrene are mixed in a mass ratio of 1:30:1.0, heated to 60°C for reaction for 5h, filtered, washed, and dried to obtain phosphorus-containing quartz sand; under nitrogen protection, styrene, phosphorus-containing quartz sand, and cyclohexane are mixed in a mass ratio of 1:6:40 and heated to 60°C, 0.01 times the mass of styrene of n-butyl lithium is added for 3 minutes, and 0.03 times the mass of styrene of n-butyl lithium is added again, and the reaction is carried out for 30 minutes, 5 times the mass of styrene of butadiene is added, and the reaction is continued for 35 minutes, and styrene is added again for reaction for 30 minutes, and the amount of styrene added this time is the same as the mass of styrene added for the first time; 12 times the mass of styrene of ethanol is added, and the modified quartz sand is obtained after filtering, washing, and drying;

[0046] (5) Conductive carbon black and ethanol were mixed, and the pH was adjusted to 4 using a 40 wt% hydrochloric acid solution. Mercaptopropyl trimethoxysilane was added and ultrasonically mixed for 10 min. The mixture was heated to 80°C and stirred for 5 h. The mixture was filtered, washed, and dried to obtain mercaptolated conductive carbon black. The mass ratio of conductive carbon black, ethanol, and mercaptopropyl trimethoxysilane was 1:0.5:60. Equal molar ratios of triethylamine and 2-mercaptoethanol were added to tetrahydrofuran (12 times the mass of triethylamine), and dichlorodimethylsilane (0.5 times the molar amount of 2-mercaptoethanol) was added. The mixture was stirred for 24 h. h, filtering, washing with ether, and distilling under reduced pressure to obtain a polythiol crosslinking agent; weighing 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 polythiol crosslinking agent, 40 parts of modified polyacrylic acid emulsion, 80 parts of water, and 6 parts of dimethylphenylphosphine, mixing the above raw materials, pouring them into a mold for curing, and demolding, curing, grinding, and polishing to obtain a dust-proof and anti-static artificial terrazzo.

[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 isopropyl alcohol are mixed in a mass ratio of 1:0.75:0.55:0.4:0.01:25, heated to 83° C., refluxed and stirred for 2.5 h, and subjected to reduced pressure rotary evaporation and vacuum drying to obtain a polyacrylic acid resin; polyacrylic acid resin, 80 wt % isopropyl alcohol aqueous solution, sodium lauryl sulfate, 35 wt % 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 the polythiol crosslinking agent is not 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. The above raw materials are mixed, poured into a mold for curing, and demolded, cured, ground, and polished to obtain dust-proof and anti-static artificial terrazzo.

[0051] Test Example 1:

[0052] Antibacterial performance test:

[0053] The terrazzo prepared in the Examples and Comparative Examples was pulverized and filtered through a 0.08 nm standard sieve to obtain a powder with a particle size of less than 0.08 nm. 2 g of the powder was placed on a 1 cm diameter filter paper. The filter paper was then placed on a solid culture medium smeared with a bacterial solution and incubated at 37°C for 12 h. The size of the inhibition zone was determined using the Oxford cup method. The results are shown in Table 1.

[0054] Table 1 Statistics of antibacterial performance test results

[0055] Diameter of inhibition ring / mm Diameter of inhibition ring / 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 acid resin was not modified for antibacterial purposes. By comparison, the antibacterial properties of Examples 1 to 3 are better than those of Comparative Example 1, indicating that acrylic acid, methyl methacrylate, butyl acrylate, and diphenyl-p-phenylphenylphosphine are polymerized under the action of an initiator to generate a polyacrylic acid resin. The resin molecular chain contains a triphenylphosphine structure, and 1-[4-(chloromethyl)phenyl]ethanone and the triphenylphosphine structure generate a quaternary phosphonium salt structure with antibacterial properties, and a formyl structure is introduced. The formyl group undergoes addition, substitution, cyclization, and rearrangement under the action of potassium cyanide and ammonium carbonate to generate a hydantoin structure. After chlorination with sodium hypochlorite, the combination of the quaternary phosphonium salt and the halamine can further improve the antibacterial properties of the material.

[0057] Test Example 2:

[0058] Mechanical properties test:

[0059] Test Method: The flexural strength of the terrazzo prepared in the Examples and Comparative Examples was tested according to the standard GB 28635-2012 "Concrete Pavement Bricks." The results are shown in Table 2.

[0060] Anti-aging performance test:

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

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

[0063]

[0064] From the experimental data in Table 2, it can be found that the artificial terrazzo prepared by the present invention has good mechanical properties and anti-aging properties; Comparative Example 2 does not modify the quartz sand and conductive carbon black, and does not add a polythiol crosslinking agent. 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, indicating that the surface of the quartz stone is treated with vinyl trimethoxysilane to have a vinyl surface, and 2,6-bis (tert-butyl) -4- (mercaptomethyl) phenol is grafted on it through the reaction of mercapto and alkenyl, and then reacted with phosphorus trichloride and p-hydroxystyrene in sequence to generate a phosphite structure with antioxidant properties, and vinyl is introduced. Under the action of n-butyl lithium, the vinyl on the p-hydroxystyrene undergoes anionic polymerization with styrene and butadiene, and a phosphite structure with antioxidant properties is generated. Styrene-butadiene-styrene block copolymer is wrapped to give the material good toughness; quartz stone particles, ceramic particles, cement, modified quartz sand, dispersant, defoaming agent, thiol-conductive carbon black, modified polyacrylic acid emulsion, water, and dimethylphenylphosphine are mixed to obtain artificial terrazzo. Polyacrylic acid emulsion, as an adhesive, can be used as an effective adhesive to combine the various components together to enhance the density of the material; in addition to giving terrazzo good antistatic properties, the thiol-conductive carbon black can indirectly improve the dust-proof performance of terrazzo by reducing electrostatic adsorption. The thiol groups on the thiol-conductive carbon black and the thiol groups on the polythiol crosslinking agent can also undergo electrophilic addition of thiol groups and double bonds on the surface of polyacrylic acid emulsion and modified quartz sand under the action of a catalyst to form more crosslinking sites, further enhancing the density and mechanical properties of the material.

[0065] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A method for preparing 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 polyacrylic acid resin; reacting polyacrylic acid resin and 1-[4-(chloromethyl)phenyl]ethanone to obtain pretreated polyacrylic acid resin; reacting pretreated polyacrylic acid resin, potassium cyanide, and ammonium carbonate to obtain pre-modified polyacrylic acid resin; (2) reacting the pre-modified polyacrylic acid resin with 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) Pretreated quartz sand, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine are reacted to obtain pre-modified quartz sand; the preparation method of the pretreated quartz sand is as follows: quartz sand and ethanol are mixed, the pH is adjusted to 4 with hydrochloric acid, vinyltrimethoxysilane is added, and ultrasonic mixing is performed for 10 minutes, the temperature is raised to 80°C, and stirring is performed for 5-7 hours, and the pretreated quartz sand is filtered, washed, and dried to obtain the pretreated quartz sand; the mass ratio of quartz sand, ethanol, and vinyltrimethoxysilane is 1:(0.3-0.5):(50-60); (4) reacting pre-modified quartz sand with 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, calculated 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 defoaming agent, 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 then demold, cure, grind, and polish to obtain dust-proof and anti-static artificial terrazzo.

2. The method for preparing the 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-phenylylphosphine, azobisisobutyronitrile and isopropyl alcohol 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-phenylylphosphine, azobisisobutyronitrile and isopropyl alcohol 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 ℃ 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, heated 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 method for preparing the dust-proof and anti-static artificial terrazzo according to claim 1, characterized in that: The preparation method of the polyacrylic acid emulsion in step (2) is as follows: pre-modified polyacrylic acid resin, 4-vinylbenzoyl chloride, aluminum chloride, and N,N-dimethylformamide are mixed, the mixture is heated to 40-45° C. and reacted for 2-3 hours. After the reaction is completed, the mixture is precipitated with pure water, filtered, and redispersed in a 5wt% sodium hypochlorite solution, stirred for 2 hours, filtered, washed, and dried to obtain a modified polyacrylic acid resin; The mass ratio of pre-modified polyacrylic acid resin, 4-vinylbenzoyl chloride, aluminum trichloride, N,N-dimethylformamide and 5wt% sodium hypochlorite solution is 1:(0.4-0.6):(0.2-0.3):(20-30):(20-30); the modified polyacrylic acid resin, 80wt% isopropyl alcohol aqueous solution, sodium lauryl sulfonate, 35wt% ammonia water and pure water are mixed 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 a modified polyacrylic acid emulsion.

4. The method for preparing dust-proof and anti-static artificial terrazzo according to claim 1, characterized in that: The preparation method of the pre-modified quartz sand in step (3) is as follows: pre-treated quartz sand, dichloromethane, 2,6-bis(tert-butyl)-4-(mercaptomethyl)phenol, and dimethylphenylphosphine are mixed, the mixture is heated to 40-50°C and reacted for 10-12 hours, and the pre-modified quartz sand is obtained by filtering, washing, and drying; the mass ratio of the pre-treated 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 method for preparing dust-proof and anti-static artificial terrazzo according to claim 1, characterized in that: The preparation method of the modified quartz sand in step (4) is as follows: pre-modified quartz sand, phosphorus trichloride, toluene, and organic tin are mixed in a mass ratio of 1: (0.3-0.5): (20-30): (0.03-0.04), heated to 40-50 ° C, filtered, and the filtered pre-modified quartz sand, toluene, and p-hydroxystyrene are mixed in a mass ratio of 1: (20-30): (0.8-1.0), heated to 60-70 ° C, reacted for 5-6 hours, filtered, washed, and dried to obtain phosphorus-containing quartz sand; under nitrogen protection, styrene, phosphorus-containing quartz sand, cyclohexane Alkanes are mixed in a mass ratio of 1:(5-6):(35-40) and the temperature is raised to 60°C. After adding n-butyl lithium in an amount of 0.01 times the mass of styrene for 3-5 minutes, n-butyl lithium in an amount of 0.03 times the mass of styrene is added again and the reaction is carried out for 30-40 minutes. After adding butadiene in an amount of 4-5 times the mass of styrene and the reaction is continued for 35-45 minutes, styrene is added again and the reaction is carried out for 30-40 minutes. The amount of styrene added this time is the same as that of the first addition. Ethanol in an amount of 10-12 times the mass of styrene is added, and the modified quartz sand is obtained by filtration, washing, and drying.

6. The method for preparing dust-proof and anti-static artificial terrazzo according to claim 1, characterized in that: The preparation method of the polythiol crosslinking agent in step (5) is as follows: adding triethylamine and 2-mercaptoethanol in equal molar ratios to tetrahydrofuran with a mass of 10-12 times that of triethylamine, adding dichlorodimethylsilane with a molar mass of 0.45-0.5 times that of 2-mercaptoethanol, stirring for 24 hours, filtering, washing with ether, and distilling under reduced pressure to obtain the polythiol crosslinking agent.

7. The method for preparing dust-proof and anti-static artificial terrazzo according to claim 1, characterized in that: The quartz sand has a particle size of 200 meshes.

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

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