CN114956690B - Formula and method for preparing artificial stone by using fly ash and copper ore slag - Google Patents
Formula and method for preparing artificial stone by using fly ash and copper ore slag Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/08—Flue dust, i.e. fly ash
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/144—Slags from the production of specific metals other than iron or of specific alloys, e.g. ferrochrome slags
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
- C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention relates to the field of artificial stones, and solves the problems that in the existing artificial stones, the utilization of fly ash and copper ore slag belongs to an exploration stage, the defects of large formula difference and poor product quality generally exist, in particular to a formula and a method for preparing the artificial stones by utilizing the fly ash and the copper ore slag.
Description
Technical Field
The invention relates to the field of artificial stones, and particularly relates to a formula and a method for preparing artificial stones by utilizing fly ash and copper ore slag.
Background
The fly ash is waste residue with large discharge amount of coal consuming enterprises such as a thermal power plant and the like, is fine ash obtained by catching flue gas after coal is combusted, is main solid waste discharged by the coal consuming enterprises such as a coal-fired power plant and the like, is distributed in large and small thermal power plants and other coal consuming enterprises all over the country, produces a large amount of fly ash every year, generates flying dust to pollute the atmosphere if a large amount of fly ash is not treated, causes river silting if the fly ash is discharged into a water system, and has toxic chemical substances harmful to human bodies and organisms; copper ore slag is industrial solid waste generated in the copper smelting process, mainly exists in the form of water-quenched copper slag, is not recycled and is accumulated in the area of a copper smelting factory, occupies a large amount of land, and causes environmental pollution to influence local development.
The artificial stone is an artificial stone for decorating inner and outer walls, simulates the appearance texture of natural stone, has the characteristics of light weight, rich color, no mildew, no combustion, convenient installation and the like, is a new variety in the decoration of outer walls, has the advantages of low energy consumption, low carbon dioxide emission and the like when being produced by using solid waste materials, can greatly consume industrial wastes and change wastes into valuables, has the characteristics of high strength, good corrosion resistance, high temperature resistance and the like, can meet the first-level fire-proof requirement, and has the advantages which are particularly prominent in the society which currently pushes forward the green and environment-friendly concepts, and therefore, the production of solid waste based inorganic artificial stone plates becomes the main trend of the development of the plate industry.
However, in the aspect of the existing artificial stone, the utilization of the fly ash and the copper ore slag still belongs to an exploration stage, and the defects of large formula difference and poor product quality generally exist, so that a formula and a method for preparing the artificial stone by using the fly ash and the copper ore slag are urgently needed to improve the performance of the artificial stone so as to meet the market demand.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a formula and a method for preparing an artificial stone by using fly ash and copper ore slag, wherein the formula comprises the following steps: the method comprises the steps of crushing copper ore slag, adding cement and coal ash, uniformly mixing to obtain a primary mixed material, uniformly mixing the primary mixed material, water, modified styrene-butadiene latex and pigment to obtain a mixed slurry, adding the mixed slurry into a mold, flattening, vibrating, and performing hot press molding to obtain an artificial stone finished product, and solves the problems that the coal ash and copper ore slag are utilized in the conventional artificial stone aspect, the formula difference is large, and the product quality is poor.
The purpose of the invention can be realized by the following technical scheme:
a formula for preparing artificial stone by using fly ash and copper ore slag comprises the following components in parts by weight:
40-60 parts of cement, 20-35 parts of fly ash, 15-25 parts of copper ore slag, 2.5-15.5 parts of modified styrene-butadiene latex, 10-35 parts of water and 1-3 parts of pigment;
the modified styrene-butadiene latex is latex formed by polymerizing liquid polybutadiene, styrene, acrylic acid and a reinforcing agent as polymerization monomers, sodium dodecyl sulfate as an emulsifier and ammonium persulfate as an initiator at the temperature of 60-70 ℃.
As a further scheme of the invention: the preparation method of the modified styrene-butadiene latex comprises the following steps:
adding liquid polybutadiene, styrene, acrylic acid, a reinforcing agent, sodium dodecyl sulfate and deionized water into a three-neck flask provided with an electric stirrer, a thermometer and a constant-pressure dropping funnel, stirring and dropwise adding a sodium hydroxide solution under the conditions that the temperature is 20-25 ℃ and the stirring rate is 800-1000r/min to adjust the pH value to 7-9, controlling the dropwise adding rate to be 1-2 drops/s, then stirring and dropwise adding an ammonium persulfate solution under the condition that the temperature is increased to 60-70 ℃, controlling the dropwise adding rate to be 1-2 drops/s, continuing stirring for reaction for 4-5 hours after the dropwise adding is finished, and adjusting the solid content of a reaction product to be 35-45% after the reaction is finished to obtain the modified styrene-butadiene latex.
As a further scheme of the invention: the dosage ratio of the liquid polybutadiene, the styrene, the acrylic acid, the reinforcing agent, the sodium dodecyl sulfate, the deionized water and the ammonium persulfate solution is 50-60g:40-50g:10-20g:15-45g:3.0-4.5g:300-500mL:15-20mL, the mass fraction of the ammonium persulfate solution is 10-15%, the average molecular weight of the liquid polybutadiene is 1000-3000, and the mass fraction of the sodium hydroxide solution is 15-20%.
As a further scheme of the invention: the preparation method of the reinforcing agent comprises the following steps:
a1: adding phenol and chloroform into a four-neck flask provided with an electric stirrer, a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at the temperature of-2-2 ℃ and the stirring speed of 200-300r/min until the phenol is completely dissolved, then dropwise adding a bromine solution while stirring, controlling the dropwise adding speed to be 1-2 drops/s, continuing stirring and reacting for 1-2 hours after the dropwise adding is finished, then regulating the pH to be 7 by using saturated sodium bisulfite, standing for layering, and carrying out rotary evaporation on an organic phase to remove the solvent, thus obtaining an intermediate 1;
a2: adding fuming sulfuric acid into a three-neck flask provided with an electric stirrer and a thermometer, adding the intermediate 1 while stirring under the conditions that the temperature is 20-25 ℃ and the stirring rate is 150-250r/min, controlling the adding rate to be 0.5-1g/min, continuing stirring and reacting for 4-5 hours under the condition that the temperature is raised to 140-145 ℃ after the adding is finished, cooling a reaction product to room temperature after the reaction is finished, dissolving the reaction product with hot water at 90-95 ℃, cooling to 0-5 ℃, carrying out vacuum filtration, placing a filter cake into a vacuum drying box, and drying for 10-15 hours under the condition that the temperature is 40-50 ℃ to obtain an intermediate 2;
a3: adding tetrahydrofuran, magnesium chips, iodine particles and the intermediate 2 into a four-neck flask provided with an electric stirrer, a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, stirring and heating to reflux reaction under the condition of stirring speed of 300-500r/min, controlling the heating speed to be 2-3 ℃/min, then continuing stirring and reacting for 1.5-2.5h, then dropwise adding 3-bromo-1-propylene under stirring, controlling the dropwise adding speed to be 1-2 drops/s, continuing stirring and reacting for 2-3h after the dropwise adding is finished, adding a reaction product into ice water after the reaction is finished, extracting for 2-3 times by using anhydrous ether, combining extract liquor, and rotationally evaporating the extract liquor to remove a solvent to obtain a reinforcing agent.
As a further scheme of the invention: the dosage ratio of the phenol solution, the chloroform solution and the bromine solution in the step A1 is 0.5mol:50-60mL:50-60mL, wherein the bromine solution is bromine according to a volume ratio of 1:1 in chloroform.
As a further scheme of the invention: the dosage ratio of the fuming sulfuric acid to the intermediate 1 in the step A2 is 30mL:10g.
As a further scheme of the invention: the tetrahydrofuran, the magnesium chips, the iodine granules, the intermediate 2 and the 3-bromo-1-propene in the step A3 are 50-60mL:3-5g:0.2-1g:0.1mol:0.11-0.13mol.
As a further scheme of the invention: a method for preparing artificial stone by using fly ash and copper ore slag comprises the following steps:
the method comprises the following steps: weighing 40-60 parts of cement, 20-35 parts of fly ash, 15-25 parts of copper ore slag, 2.5-15.5 parts of modified styrene-butadiene latex, 10-35 parts of water and 1-3 parts of pigment according to parts by weight for later use;
step two: crushing copper ore slag, adding cement and fly ash, and uniformly mixing to obtain a primary mixed material;
step three: uniformly mixing the primary mixed material, water, modified styrene-butadiene latex and pigment to obtain mixed slurry;
step four: adding the mixed slurry into a mold, flattening, conveying the mixture to a vibrating machine by using a conveying belt, vibrating for 10-15s, and carrying out hot press molding under the conditions that the temperature is 100-140 ℃ and the pressure is 6-12MPa to obtain the artificial stone finished product.
The invention has the beneficial effects that:
the invention relates to a formula and a method for preparing an artificial stone by utilizing coal ash and copper ore slag, which are characterized in that the copper ore slag is crushed, then cement and the coal ash are added and uniformly mixed to obtain a primary mixed material, the primary mixed material, water, modified styrene-butadiene latex and pigment are uniformly mixed to obtain mixed slurry, the mixed slurry is added into a mold and smoothed, and then vibration and hot press molding are carried out to obtain an artificial stone finished product; the artificial stone formula mainly uses cement, fly ash and copper ore slag as main raw materials, the fly ash and the copper ore slag are reasonably used, waste materials are changed into valuable materials, resources are saved, green production is realized, the mechanical property of the artificial stone is effectively improved by adding modified styrene-butadiene latex for enhancing modification, and the purpose of preparing the artificial stone with excellent performance is realized;
firstly, brominating phenol by bromine to introduce bromine atoms on a benzene ring to obtain an intermediate 1, then, performing sulfonation reaction on the intermediate 1 under the action of fuming sulfuric acid to introduce sulfonic acid groups on the benzene ring to obtain an intermediate 2, then, performing Grignard reaction on the intermediate 2 and magnesium chips to generate a Grignard reagent, then, performing nucleophilic substitution reaction on the Grignard reagent and 3-bromine-1-propylene to introduce alkenyl to obtain a reinforcing agent, and polymerizing polybutadiene, styrene and acrylic acid by using the reinforcing agent as a polymerization monomer to prepare modified styrene-butadiene latex; the modified styrene-butadiene latex provides a flexible molecular chain segment through a long chain of polybutadiene, has good elastic toughness and stability, is endowed with certain strength and hardness through a rigid benzene ring structure on styrene and a reinforcing agent, and can improve the thermal stability of the modified styrene-butadiene latexQualitatively, the hydrophilicity and dispersion stability of the latex polymer can be improved by the sulfonic acid group on the reinforcing agent and the carboxyl group on the acrylic acid, and in addition, -SO 3 The structure can reduce the sensitivity of the latex polymer to salt cations and improve the salt resistance of a latex system, after the modified styrene-butadiene latex is uniformly mixed with cement, fly ash and copper ore slag particles, latex particles can fill or accumulate on the surfaces or pores of the cement, fly ash and copper ore slag particles through physical or chemical action so as to block pores and cracks in mixed slurry, so that the compactness of the artificial stone is realized, in addition, the latex polymer accumulated on the surfaces or pores of the cement, fly ash and copper ore slag particles is gradually changed into a continuous elastic and flexible plastic film along with the gradual consumption of water in the modified styrene-butadiene latex, the pores and cracks of the artificial stone system can be filled, and then the elastic and flexible plastic film is connected with the cement, fly ash and copper ore slag particles in a staggered manner to form a compact three-dimensional network structure, so that the artificial stone is endowed with good mechanical properties, the penetration of water is prevented, the water absorption performance of the artificial stone is reduced, and the high mechanical properties of the artificial stone with long-acting effect are maintained.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
this embodiment is a method for preparing a reinforcing agent, including the steps of:
a1: 0.5mol of phenol and 50mL of chloroform were added to a four-necked flask equipped with an electric stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, and stirred at a temperature of-2 ℃ and a stirring rate of 200r/min until the phenol was completely dissolved, and then 50mL of bromine was added dropwise under stirring in a volume ratio of 1:1 is dissolved in chloroform to form a bromine solution, the dropping speed is controlled to be 1 drop/s, the mixture is continuously stirred and reacts for 1 hour after the dropping is finished, then saturated sodium bisulfite is used for adjusting the pH value to be 7, then the mixture is kept stand and layered, and the organic phase is rotated and evaporated to remove the solvent, thus obtaining an intermediate 1;
a2: adding 30mL of fuming sulfuric acid into a three-neck flask provided with an electric stirrer and a thermometer, adding 10g of the intermediate 1 while stirring under the conditions that the temperature is 20 ℃ and the stirring rate is 150r/min, controlling the adding rate to be 0.5g/min, continuing stirring and reacting for 4 hours under the condition that the temperature is raised to 140 ℃ after the adding is finished, cooling a reaction product to room temperature after the reaction is finished, dissolving the reaction product with hot water at 90 ℃, cooling to 0 ℃, carrying out vacuum filtration, placing a filter cake into a vacuum drying oven, and drying for 10 hours under the condition that the temperature is 40 ℃ to obtain an intermediate 2;
a3: adding 50mL of tetrahydrofuran, 3g of magnesium chips, 0.2g of iodine granules and 0.1mol of intermediate 2 into a four-neck flask provided with an electric stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, heating to reflux reaction while stirring at the stirring speed of 300r/min, controlling the heating rate to be 2 ℃/min, then continuing to stir for reaction for 1.5h, then dropwise adding 0.11mol 3-bromo-1-propylene while stirring, controlling the dropwise adding rate to be 1 drop/s, continuing to stir for reaction for 2h after the dropwise addition is finished, adding a reaction product into ice water after the reaction is finished, then extracting for 2 times by using anhydrous ether, combining extract liquor, and rotationally evaporating the extract liquor to remove a solvent to obtain the reinforcing agent.
Example 2:
this embodiment is a method for preparing a reinforcing agent, comprising the steps of:
a1: 0.5mol of phenol and 60mL of chloroform were added to a four-necked flask equipped with an electric stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, stirred at a temperature of 2 ℃ and a stirring rate of 300r/min until the phenol was completely dissolved, and then 60mL of bromine was added dropwise under stirring in a volume ratio of 1:1 is dissolved in chloroform to form a bromine solution, the dropping speed is controlled to be 2 drops/s, the mixture is continuously stirred and reacts for 2 hours after the dropping is finished, then saturated sodium bisulfite is used for adjusting the pH value to be 7, then the mixture is kept stand and layered, and the organic phase is rotated and evaporated to remove the solvent, thus obtaining an intermediate 1;
a2: adding 30mL of fuming sulfuric acid into a three-neck flask provided with an electric stirrer and a thermometer, adding 10g of the intermediate 1 while stirring under the conditions that the temperature is 25 ℃ and the stirring rate is 250r/min, controlling the adding rate to be 1g/min, continuing stirring and reacting for 5 hours under the condition that the temperature is raised to 145 ℃ after the adding is finished, cooling a reaction product to room temperature after the reaction is finished, dissolving the reaction product with 95 ℃ hot water, cooling to 5 ℃, carrying out vacuum filtration, placing a filter cake into a vacuum drying oven, and drying for 15 hours under the condition that the temperature is 50 ℃ to obtain an intermediate 2;
a3: adding 60mL of tetrahydrofuran, 5g of magnesium chips, 1g of iodine granules and 0.1mol of intermediate 2 into a four-neck flask provided with an electric stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, heating to reflux reaction while stirring at the stirring speed of 500r/min, controlling the heating rate to be 3 ℃/min, then continuing to stir for reaction for 2.5 hours, then dropwise adding 0.13mol of 3-bromo-1-propene while stirring, controlling the dropwise adding rate to be 2 drops/s, continuing to stir for reaction for 3 hours after the dropwise addition is finished, adding a reaction product into ice water after the reaction is finished, then extracting for 3 times by using anhydrous ether, combining extract liquor, and rotationally evaporating the extract liquor to remove a solvent to obtain a reinforcing agent.
Example 3:
this embodiment is a method for preparing a modified styrene-butadiene latex, including the following steps:
50g of liquid polybutadiene with the average molecular weight of 1000, 40g of styrene, 10g of acrylic acid, 15g of the reinforcing agent from example 1, 3.0g of sodium dodecyl sulfate and 300mL of deionized water are added into a three-neck flask provided with an electric stirrer, a thermometer and a constant-pressure dropping funnel, 15% by mass of sodium hydroxide solution is added dropwise while stirring at the temperature of 20 ℃ and the stirring rate of 800r/min to adjust the pH to 7, the dropping rate is controlled to be 1 drop/s, then 15mL of 10% by mass of ammonium persulfate solution is added dropwise while stirring at the temperature of 60 ℃, the dropping rate is controlled to be 1 drop/s, stirring reaction is continued for 4 hours after the dropping is finished, and the solid content of a reaction product is adjusted to be 35% after the reaction is finished, so that the modified styrene-butadiene latex is obtained.
Example 4:
this embodiment is a method for preparing a modified styrene-butadiene latex, including the following steps:
60g of liquid polybutadiene with the average molecular weight of 3000, 50g of styrene, 20g of acrylic acid, 45g of the reinforcing agent from example 2, 4.5g of sodium dodecyl sulfate and 500mL of deionized water are added into a three-neck flask provided with an electric stirrer, a thermometer and a constant-pressure dropping funnel, 20% by mass of sodium hydroxide solution is added dropwise while stirring at the temperature of 25 ℃ and the stirring rate of 1000r/min to adjust the pH to 9, the dropping rate is controlled to be 2 drops/s, then 20mL of ammonium persulfate solution with the mass fraction of 15% is added dropwise while stirring at the temperature of 70 ℃, the dropping rate is controlled to be 2 drops/s, stirring reaction is continued for 5 hours after the dropping is finished, and the solid content of the reaction product is adjusted to 45% after the reaction is finished, so that the modified styrene-butadiene latex is obtained.
Example 5:
the embodiment is a method for preparing artificial stone by using fly ash and copper ore slag, which comprises the following steps:
the method comprises the following steps: weighing 40 parts of cement, 20 parts of fly ash, 15 parts of copper ore slag, 2.5 parts of modified styrene-butadiene latex from example 3, 10 parts of water and 1 part of pigment according to parts by weight for later use;
step two: crushing copper ore slag, adding cement and fly ash, and uniformly mixing to obtain a primary mixed material;
step three: uniformly mixing the primary mixed material, water, modified styrene-butadiene latex and pigment to obtain mixed slurry;
step four: adding the mixed slurry into a mold, flattening, conveying the mixed slurry to a vibrating machine by using a conveying belt, vibrating for 10s, and carrying out hot press molding under the conditions that the temperature is 100 ℃ and the pressure is 6MPa to obtain the artificial stone finished product.
Example 6:
the embodiment is a method for preparing artificial stone by using fly ash and copper ore slag, which comprises the following steps:
the method comprises the following steps: weighing 60 parts of cement, 35 parts of fly ash, 25 parts of copper ore slag, 15.5 parts of modified styrene-butadiene latex from example 4, 35 parts of water and 3 parts of pigment according to parts by weight for later use;
step two: crushing copper ore slag, adding cement and fly ash, and uniformly mixing to obtain a primary mixed material;
step three: uniformly mixing the primary mixed material, water, modified styrene-butadiene latex and pigment to obtain mixed slurry;
step four: and adding the mixed slurry into a mold, flattening, conveying the mixture to a vibrating machine by using a conveying belt, vibrating for 15s, and performing hot press molding under the conditions that the temperature is 140 ℃ and the pressure is 12MPa to obtain a finished artificial stone.
Comparative example 1:
comparative example 1 differs from example 4 in that no reinforcing agent is added.
Comparative example 2:
comparative example 2 is different from example 6 in that a modified styrene-butadiene latex is not added.
Comparative example 3:
comparative example 3 is different from example 6 in that the modified styrene-butadiene latex used is the modified styrene-butadiene latex of comparative example 1.
Comparative example 4:
comparative example 4 is the environment-friendly fly ash imitated natural artificial stone prepared according to application number cn201110341137.X and the production method embodiment 3 thereof.
The artificial stones of examples 5 to 6 and comparative examples 2 to 4 were measured for their properties, and the results are shown in the following table:
referring to the data in the table, it can be seen that the mechanical properties and water absorption of the artificial stone can be enhanced by adding the modified styrene-butadiene latex according to the comparison between the example 6 and the comparative example 2, the modified styrene-butadiene latex with the reinforcing agent has a better lifting effect according to the comparison between the example 6 and the comparative example 3, and the performance of the artificial stone in the invention is far higher than that of the artificial stone in the prior art according to the comparison between the example 6 and the comparative example 4.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. The formula for preparing the artificial stone by using the fly ash and the copper ore slag is characterized by comprising the following components in parts by weight:
40-60 parts of cement, 20-35 parts of fly ash, 15-25 parts of copper ore slag, 2.5-15.5 parts of modified styrene-butadiene latex, 10-35 parts of water and 1-3 parts of pigment;
the modified styrene-butadiene latex is latex formed by polymerizing liquid polybutadiene, styrene, acrylic acid and a reinforcing agent serving as polymerization monomers, sodium dodecyl sulfate serving as an emulsifier and ammonium persulfate serving as an initiator at the temperature of 60-70 ℃;
the preparation method of the reinforcing agent comprises the following steps:
a1: adding phenol and chloroform into a four-neck flask provided with an electric stirrer, a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at the temperature of-2-2 ℃ and the stirring speed of 200-300r/min until the phenol is completely dissolved, then dropwise adding a bromine solution while stirring, controlling the dropwise adding speed to be 1-2 drops/s, continuing stirring and reacting for 1-2 hours after the dropwise adding is finished, then regulating the pH to be 7 by using saturated sodium bisulfite, standing for layering, and carrying out rotary evaporation on an organic phase to remove the solvent, thus obtaining an intermediate 1;
a2: adding fuming sulfuric acid into a three-neck flask provided with an electric stirrer and a thermometer, adding the intermediate 1 while stirring under the conditions that the temperature is 20-25 ℃ and the stirring rate is 150-250r/min, controlling the adding rate to be 0.5-1g/min, continuing stirring and reacting for 4-5 hours under the condition that the temperature is raised to 140-145 ℃ after the adding is finished, cooling a reaction product to room temperature after the reaction is finished, dissolving the reaction product with hot water at 90-95 ℃, cooling to 0-5 ℃, carrying out vacuum filtration, placing a filter cake into a vacuum drying box, and drying for 10-15 hours under the condition that the temperature is 40-50 ℃ to obtain an intermediate 2;
a3: adding tetrahydrofuran, magnesium chips, iodine particles and the intermediate 2 into a four-neck flask provided with an electric stirrer, a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, heating to reflux reaction while stirring under the condition of stirring speed of 300-500r/min, controlling the heating speed to be 2-3 ℃/min, continuing to stir for reaction for 1.5-2.5h, then dropwise adding 3-bromo-1-propylene while stirring, controlling the dropwise adding speed to be 1-2 drops/s, continuing to stir for reaction for 2-3h after the dropwise addition is finished, adding a reaction product into ice water after the reaction is finished, extracting for 2-3 times by using anhydrous ether, combining extract liquor, and rotationally evaporating the extract liquor to remove a solvent to obtain a reinforcing agent.
2. The formulation for preparing artificial stone by using fly ash and copper ore slag according to claim 1, wherein the modified styrene-butadiene latex is prepared by the following steps:
adding liquid polybutadiene, styrene, acrylic acid, a reinforcing agent, sodium dodecyl sulfate and deionized water into a three-neck flask provided with an electric stirrer, a thermometer and a constant-pressure dropping funnel, stirring and dropwise adding a sodium hydroxide solution under the conditions that the temperature is 20-25 ℃ and the stirring speed is 800-1000r/min to adjust the pH value to 7-9, controlling the dropwise adding speed to be 1-2 drops/s, then heating to 60-70 ℃, stirring and dropwise adding an ammonium persulfate solution under the conditions that the dropwise adding speed is 1-2 drops/s, continuing stirring and reacting for 4-5 hours after the dropwise adding is finished, and adjusting the solid content of a reaction product to 35-45% after the reaction is finished to obtain the modified styrene-butadiene latex.
3. The formula for preparing the artificial stone by using the fly ash and the copper ore slag as claimed in claim 2, wherein the dosage ratio of the liquid polybutadiene, the styrene, the acrylic acid, the reinforcing agent, the sodium dodecyl sulfate, the deionized water and the ammonium persulfate solution is 50-60g:40-50g:10-20g:15-45g:3.0-4.5g:300-500mL:15-20mL, the mass fraction of the ammonium persulfate solution is 10-15%, the average molecular weight of the liquid polybutadiene is 1000-3000, and the mass fraction of the sodium hydroxide solution is 15-20%.
4. The formulation for preparing artificial stone from fly ash and copper ore slag according to claim 1, wherein the ratio of the phenol, chloroform and bromine solution in step A1 is 0.5mol:50-60mL:50-60mL, wherein the bromine solution is bromine according to a volume ratio of 1:1 in chloroform.
5. The formula for preparing artificial stone by using fly ash and copper ore slag as claimed in claim 1, wherein the dosage ratio of fuming sulfuric acid and the intermediate 1 in the step A2 is 30mL:10g.
6. The formulation for producing artificial stone using fly ash and copper ore slag according to claim 1, wherein the tetrahydrofuran, magnesium scale, iodine particle, intermediate 2 and 3-bromo-1-propene of step A3 are 50-60mL:3-5g:0.2-1g:0.1mol:0.11-0.13mol.
7. A method for preparing artificial stone by using fly ash and copper ore slag is characterized in that the artificial stone is prepared by the formula for preparing the artificial stone by using the fly ash and the copper ore slag according to claim 1, and comprises the following steps:
the method comprises the following steps: weighing 40-60 parts of cement, 20-35 parts of fly ash, 15-25 parts of copper ore slag, 2.5-15.5 parts of modified styrene-butadiene latex, 10-35 parts of water and 1-3 parts of pigment according to parts by weight for later use;
step two: crushing copper ore slag, adding cement and fly ash, and uniformly mixing to obtain a primary mixed material;
step three: uniformly mixing the primary mixed material, water, modified styrene-butadiene latex and pigment to obtain mixed slurry;
step four: adding the mixed slurry into a mold, flattening, conveying the mixture to a vibrating machine by using a conveying belt, vibrating for 10-15s, and carrying out hot press molding under the conditions that the temperature is 100-140 ℃ and the pressure is 6-12MPa to obtain the artificial stone finished product.
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