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CN114031342B - Colored gravel concrete composition with strong weather resistance and preparation method thereof - Google Patents

Colored gravel concrete composition with strong weather resistance and preparation method thereof Download PDF

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Publication number
CN114031342B
CN114031342B CN202110425979.7A CN202110425979A CN114031342B CN 114031342 B CN114031342 B CN 114031342B CN 202110425979 A CN202110425979 A CN 202110425979A CN 114031342 B CN114031342 B CN 114031342B
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parts
weight
gravel
emulsion
concrete composition
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CN114031342A (en
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程结旺
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Shanghai Yu Zhen Industrial Development Co ltd
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Shanghai Yu Zhen Industrial Development Co ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02Granular materials, e.g. microballoons
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2623Polyvinylalcohols; Polyvinylacetates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/10Lime cements or magnesium oxide cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00008Obtaining or using nanotechnology related materials
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention relates to the field of concrete, in particular to a colored gravel concrete composition with strong weather resistance and a preparation method thereof, wherein the preparation raw materials comprise, by weight, 10-15 parts of modified polyvinyl acetate, 8-13 parts of resin, 40-60 parts of inorganic cementing material, 180-230 parts of crumb-shaped sediment, 10-15 parts of slag and 20-30 parts of inorganic particles. The colored gravel concrete composition has extremely strong weather resistance, can keep stable performance for a long time in outdoor environment, has no bad phenomena of cracking, wrinkling, cracking and the like, has bright color and high saturation, has high color persistence, and is not easy to generate color difference in outdoor environment for a long time.

Description

Colored gravel concrete composition with strong weather resistance and preparation method thereof
Technical Field
The invention relates to the field of concrete, in particular to a colored gravel concrete composition with strong weather resistance and a preparation method thereof.
Background
The colored concrete is a concrete which is added with white and colored cement or white cement and colored pigment according to a specific proportion and is compounded with colored aggregate and white or light-colored aggregate, is widely applied to urban construction in recent years, such as gardens, squares, hotels, office buildings, homes, sidewalks, driveways, parking lots, garages, building outer walls, roofs and various public places or old house decoration and transformation projects, has good plasticity and fluidity of the traditional concrete, has a certain decoration function, and can meet the decoration requirements of numerous occasions without secondary coloring.
The colored concrete inherits the good performance of the traditional concrete, however, the added pigment exposes a plurality of problems along with the prolonging of the outdoor service time, the pigment in the colored concrete has the phenomena of precipitation and fading caused by long-term wind, sunshine and rain, in addition, the addition of the pigment inevitably destroys the compatibility of the original concrete raw materials, the problems of cracking and wrinkling caused by large temperature change are caused, the attractiveness and the use are seriously influenced, and therefore, the development of the colored concrete with strong weather resistance and stable color is necessary.
CN110590285A discloses a colored polymer gravel concrete and a preparation method thereof, which solves the problems of large color difference and poor use feeling, neglects the problem of weather resistance and generates cracks after long-term use.
CN201611217181.9 discloses a colored clear water concrete and a preparation method thereof, which improve the weather resistance of colored concrete, and the poor color persistence can cause the problems of pigment precipitation and fading.
Disclosure of Invention
The first aspect of the present invention provides a colored gravel concrete composition with strong weather resistance, which is prepared from the following raw materials, by weight, 10-15 parts of modified polyvinyl acetate, 8-13 parts of resin, 40-60 parts of an inorganic cementitious material, 180-230 parts of crumb-like sediment, 10-15 parts of slag and 20-30 parts of inorganic particles.
In a preferred embodiment, the modified polyvinyl acetate is acrylate-modified polyvinyl acetate.
As a preferred embodiment, the resin is at least one selected from the group consisting of an epoxy resin, an acrylic resin, a phenol resin, a fluorine resin, a urea resin, a melamine resin, and an unsaturated polyester resin.
As a preferred embodiment, the inorganic gelling material is selected from at least one of cement, gypsum, lime.
As a preferred embodiment, the clastic deposit is selected from at least one of gravel, sand, quartz, feldspar, mica.
In a preferred embodiment, the inorganic particles are nano inorganic particles.
As a preferable embodiment, the preparation raw materials further comprise, by weight, 0.5-3 parts of a water reducing agent, 5-10 parts of a pigment and 30-40 parts of water.
In a preferred embodiment, the water reducing agent is at least one selected from the group consisting of lignosulfonate, naphthalene sulfonate, melamine-based water reducing agent, sulfamate-based high-efficiency water reducing agent, fatty acid-based high-efficiency water reducing agent, powdery polycarboxylate, casein and polycarboxylic acid-based high-performance water reducing agent.
In a preferred embodiment, the pigment is at least one selected from the group consisting of iron blue, iron oxide red, chromium oxide green, carbon black, titanium white, chromium oxide yellow, cadmium red, cadmium yellow, lithopone, and iron oxide yellow.
In a second aspect, the present invention provides a method for preparing a colored gravel concrete composition with high weather resistance, comprising the steps of:
1. putting 180-230 parts of crumb-shaped sediment, 10-15 parts of slag, 20-30 parts of inorganic particles and 5-10 parts of pigment into a stirrer, and uniformly stirring to prepare a premix;
2. adding 40-60 parts of inorganic cementing material into the premix, and continuously stirring uniformly to prepare a mixture;
3. and (2) putting 10-15 parts of modified polyvinyl acetate, 8-13 parts of resin, 0.5-3 parts of water reducing agent and 30-40 parts of water into the mixture, and uniformly stirring to obtain the modified polyvinyl acetate.
Compared with the prior art, the invention has the following beneficial effects:
1. the colored gravel concrete composition has extremely strong weather resistance, can keep stable performance for a long time in an outdoor environment, and does not have the bad phenomena of cracking, wrinkling, cracking and the like.
2. The colored gravel concrete composition has the advantages of bright color, high saturation and high color persistence, and is not easy to generate color difference in outdoor environment for a long time.
3. By compounding gravels with different grain diameters and adding reinforcing agents and nano particles with different grain diameters, the colored gravel concrete composition has compact and compact structure, and is not easy to have the bad phenomena of sinking and collapse when being applied to strong stress environments such as ground and the like.
4. The acrylate modified polyvinyl acetate solves the problems of poor performance, ultraviolet ray resistance and high and low temperature resistance of the color concrete adhesive in the prior art, so that the prepared color gravel concrete composition is tightly and firmly crosslinked, water-resistant, high and low temperature resistant, has good stability, and is particularly suitable for outdoor decoration in areas with high illumination intensity and high temperature difference.
Detailed Description
In order to solve the above technical problems, the first aspect of the present invention provides a colored gravel concrete composition with strong weather resistance, which is prepared from, by weight, 10-15 parts of modified polyvinyl acetate, 8-13 parts of resin, 40-60 parts of inorganic cementitious material, 180-230 parts of crumb-like sediment, 10-15 parts of slag and 20-30 parts of inorganic particles.
In a preferred embodiment, the modified polyvinyl acetate is acrylate-modified polyvinyl acetate.
The preparation method of the acrylate modified polyvinyl acetate comprises the following steps:
1. according to the weight portion, evenly mixing 20-120 portions of vinyl acetate monomer, 20-40 portions of butyl acrylate and 13-18 portions of acrylic acid to obtain the seed emulsion.
2. Adding 50-80 parts of water and 0.02-1 part of first emulsifier by weight into a first triangular flask, slowly adding 20-120 parts of vinyl acetate monomer and 0.2-3 parts of butyl acrylate, and uniformly mixing to obtain the outer core pre-emulsion.
3. Adding 50-80 parts of water and 0.02-1 part of a second emulsifier into a second triangular flask, slowly adding 90-110 parts of vinyl acetate monomer, 0.1-4 parts of butyl acrylate and 110-130 parts of isooctyl acrylate, and uniformly mixing to obtain the shell pre-emulsion.
4. Adding 50-80 parts of water and 8-15 parts of polyvinyl alcohol into a third triangular flask, heating and dissolving at 90 ℃, cooling to 60 ℃, adding 0.5-5 parts of a third emulsifier and 1-5 parts of sodium bicarbonate, stirring, adding 20-70 parts of a seed emulsion and 5-10 parts of a first initiator, heating to 75 ℃, adding 10-50 parts of an outer core pre-emulsion and 5-10 parts of a second initiator, stirring, adding 30-80 parts of a shell pre-emulsion and 5-10 parts of a third initiator, standing for 1h, heating to 90 ℃, keeping the temperature for 1h, cooling to 40 ℃, vacuumizing for 1h, and discharging.
Preferably, the weight ratio of the vinyl acetate monomer to the butyl acrylate in the seed emulsion is (2-12): (2-4).
Preferably, the weight percentage of acrylic acid in the seed emulsion is 0.05-0.35wt%.
Preferably, the weight percentage of isooctyl acrylate in the shell pre-emulsion is not less than 0.38wt%.
Preferably, in step 4, the weight ratio of the seed emulsion, the outer core pre-emulsion and the shell pre-emulsion is (2-7): (1-5): (3-8).
Although the vinyl acetate monomer has better adhesive force, the freeze-thaw resistance stability, the flexibility and the water resistance of the vinyl acetate monomer are not good, and the polyvinyl acetate monomer cannot cope with low-temperature environment in concrete.
The applicant finds that when the prepared seed emulsion, the prepared outer core pre-emulsion and the prepared shell pre-emulsion are mixed according to a specific proportion, agglomeration and precipitation phenomena are easy to occur, the applicant thinks that the phenomena are likely to occur because the viscosity of the seed emulsion, the prepared outer core pre-emulsion and the prepared shell pre-emulsion is low due to the fact that water is used as a solvent, the seed emulsion, the prepared outer core pre-emulsion and the prepared shell pre-emulsion cannot be well dispersed in a system, and the problem of precipitation is well solved after polyvinyl alcohol is added as a protective agent, the polyvinyl alcohol is likely to be a high-molecular compound, the viscosity of the solvent can be improved after the polyvinyl alcohol is completely dissolved in water, a stable protective layer can be formed on the surfaces of the seed emulsion, the prepared outer core pre-emulsion and the prepared shell pre-emulsion, and the stability of the solution is improved through a hydration layer and steric hindrance. The polyvinyl alcohol has hydroxyl groups, so that the water resistance of the emulsion is poor, and therefore, the control of the using amount of the polyvinyl alcohol becomes critical, and the applicant finds that when the weight of the polyvinyl alcohol is 8-15 parts, the aim of protecting molecules from sedimentation can be achieved, and the maximum affinity to water can be maintained.
Preferably, the first emulsifier, the second emulsifier and the third emulsifier are sodium dodecyl sulfate.
Preferably, the first initiator, the second initiator and the third initiator are all potassium persulfate and sodium bisulfite in a weight ratio of 1: (7-9) compounding.
The applicant finds that potassium persulfate and sodium bisulfite are compounded in a specific proportion, so that the tail end of a molecular chain of the generated polymer is provided with sulfate radicals and sulfonate radicals with good hydrophilicity, the polymer can be endowed with certain self-emulsifying property, and the polymer is further endowed with good compatibility and stability.
As a preferred embodiment, the resin is at least one selected from the group consisting of an epoxy resin, an acrylic resin, a phenol resin, a fluorine resin, a urea resin, a melamine resin, and an unsaturated polyester resin.
Preferably, the resin is selected from at least one of bisphenol a epoxy resin, glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, thermoplastic acrylic resin, thermosetting acrylic resin, hydroxyacrylic resin, thermoplastic phenol resin, thermosetting phenol resin, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoroethylene-vinylidene fluoride copolymer, tetrafluoroethylene-hexafluoropropylene-trifluoroethylene copolymer, bisphenol a unsaturated polyester, and halogenated unsaturated polyester.
Preferably, the resin is selected from bisphenol a type epoxy resins.
Preferably, the epoxy value of the bisphenol A epoxy resin is not less than 0.4eq/100g (the epoxy value is the amount of epoxy groups contained in 100g of the epoxy resin).
The epoxy value is an important performance parameter of the epoxy resin, when the epoxy resin is used as an adhesive, the epoxy resin with a lower epoxy value can achieve a good bonding effect and is beneficial to stripping, when the epoxy value is too low, the prepared raw materials cannot be well adhered together, and phenomena of loosening, material falling, poor mechanical strength, raw material precipitation and the like are easy to occur, so that the applicant selects the epoxy value of not less than 0.4eq/100g to endow the prepared concrete composition with good mechanical strength and use quality.
As a preferred embodiment, the inorganic cementing material is selected from at least one of cement, gypsum and lime.
Preferably, the inorganic gelling material is selected from cement.
Preferably, the cement is selected from the group consisting of portland cement, aluminate cement, sulphoaluminate cement, ferro-aluminate cement, fluoroaluminate cement, phosphate cement.
Preferably, the cement is selected from portland cements.
Preferably, the strength grade of the portland cement is not less than 52.5 (the strength grade value of the cement is the value of 28d compressive strength (MPa) of a cement standard test block).
The strength of the cement is an important index for evaluating the quality of the cement, and is a basis for dividing the strength grade of the cement, the strength is continuously increased in the forming process of the cement and finally forms a fixed value, and the portland cement has the characteristics of high hardness improvement and early strength formation compared with other cements.
As a preferred embodiment, the clastic deposit is selected from at least one of gravel, sand, quartz, feldspar, mica.
Preferably, the clastic sediment is selected from gravel.
Preferably, the gravel is a mixture of fine gravel and coarse gravel.
Preferably, the particle size of the fine gravel is 3-10mm, and the particle size of the coarse gravel is 11-99mm.
Preferably, the weight ratio of the fine gravel to the coarse gravel is (7-10): 3.
when the gravels in the composition are all fine gravels, agglomeration and caking are easy to occur in the stirring process, so that the finished product has poor quality and even cannot be used, and when the gravels are all coarse gravels, a plurality of cavities are easy to form among the coarse gravels due to overlarge particle size, and the concrete composition can be locally sunken after being used for a period of time outdoors, so that the problems of water accumulation, water seepage and the like are caused. The applicant found that when the weight ratio of the fine gravel to the coarse gravel is (7-10): 3, this problem can be solved well because the fine gravels having a specific particle size can fill the cavities between the coarse gravels, thereby reducing the occurrence of collapse in use and effectively reducing the penetration of rainwater.
As a preferred embodiment, the slag is an alkaline slag having a M value greater than 1 (M value is the ratio of alkaline oxide to acidic oxide in the slag).
In a preferred embodiment, the inorganic particles are nano inorganic particles.
Preferably, the nano inorganic particles are at least one selected from nano silicon dioxide, nano titanium carbide, nano carbonate, nano zinc oxide, nano silicon nitride, nano barium sulfate, nano montmorillonite and nano glass fiber.
Preferably, the nano inorganic particles are selected from nano silica.
Preferably, the particle size of the nano silicon dioxide is 15-25nm.
The applicant relieves the problem of cavities in the concrete composition by adding the thick and thin gravels with specific proportion and particle size, but in actual use, the raw materials in the concrete composition slightly expand along with the increase of temperature, and then shrink along with the decrease of temperature, so that the thick gravels and the thin gravels are displaced and the cavities are generated again.
As a preferable embodiment, the preparation raw materials further comprise 0.5-3 parts of a water reducing agent, 5-10 parts of a pigment and 30-40 parts of water by weight.
The invention does not specially limit the water reducing agent, and all the water reducing agents can disperse cement particles, improve the workability of the water reducing agent, reduce the unit water consumption and improve the fluidity of concrete mixtures; the water reducing agent can be at least one selected from lignosulfonate, naphthalene sulfonate, melamine water reducing agent, sulfamate high-efficiency water reducing agent, fatty acid high-efficiency water reducing agent, powdery polycarboxylate, casein and polycarboxylic acid high-performance water reducing agent.
The invention does not specially limit the pigment, and all the pigments which can provide color-enhancing pigment for the gravel concrete composition can be used; the pigment may be at least one selected from iron blue, iron oxide red, chromium oxide green, carbon black, titanium white, chromium oxide yellow, cadmium red, cadmium yellow, lithopone, and iron oxide yellow.
In a second aspect, the present invention provides a method for preparing a colored gravel concrete composition with high weather resistance, comprising the steps of:
1. putting 180-230 parts of crumb-shaped sediment, 10-15 parts of slag, 20-30 parts of inorganic particles and 5-10 parts of pigment into a stirrer, and uniformly stirring to prepare premix;
2. adding 40-60 parts of inorganic cementing material into the premix, and continuously stirring uniformly to prepare a mixture;
3. and (2) putting 10-15 parts of modified polyvinyl acetate, 8-13 parts of resin, 0.5-3 parts of water reducing agent and 30-40 parts of water into the mixture, and uniformly stirring to obtain the modified polyvinyl acetate.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Vinyl acetate monomer purchased from Togaku chemical industry and development Co., ltd
Butyl acrylate CAS # 141-32-2
Acrylic acid CAS #:79-10-7
2386-53-0 CAS # of sodium dodecyl sulfate
Isooctyl acrylate CAS # 103-11-7
Polyvinyl alcohol purchased from Taishiai (Shanghai) chemical industry development Co., ltd
CAS # 7727-21-1 potassium persulfate
Bisphenol A epoxy resin was purchased from Monni environmental protection science Hebei Ltd
Portland cement is purchased from Chengming building materials Co., ltd, jinhua City
Fine gravel bought from Yongshui mineral processing plant in Lingshou county
Coarse gravel purchase from Yongshun mineral processing plant in Lingshou county
The acid slag and the alkaline slag are purchased from Tangshan Industrial and building materials Co., ltd
Nano silicon dioxide purchased from Hangzhou Wanjing New Material Co Ltd
Sodium lignosulfonate CAS # 8061-51-6
Iron oxide Red was purchased from WULIAN county Licai Industrial trade Co Ltd
Polyvinyl acetate was purchased from Wanhong New Material Co., ltd, changzhou city
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Example 1 in a first aspect, there is provided a colored gravel concrete composition with high weather resistance, which is prepared from, by weight, 10 parts of modified polyvinyl acetate, 8 parts of bisphenol a type epoxy resin (epoxy value of 0.6eq/100 g), 40 parts of portland cement (strength grade of 52.5), 180 parts of gravel, 10 parts of alkaline slag, 20 parts of nano-silica (particle size of 15 nm), 0.5 part of sodium lignosulfonate, 5 parts of iron oxide red, and 30 parts of water.
The preparation method of the modified polyvinyl acetate comprises the following steps:
1. according to the weight portion, evenly mixing 20 portions of vinyl acetate monomer, 30 portions of butyl acrylate and 13 portions of acrylic acid to obtain the seed emulsion.
2. According to the weight parts, 50 parts of water and 0.02 part of sodium dodecyl sulfate are added into a first triangular flask, 20 parts of vinyl acetate monomer and 0.2 part of butyl acrylate are slowly added, and the mixture is uniformly mixed to obtain the external core pre-emulsion.
3. Adding 50 parts of water and 0.02 part of sodium dodecyl sulfate into a second triangular flask, slowly adding 90 parts of vinyl acetate monomer, 0.1 part of butyl acrylate and 110 parts of isooctyl acrylate, and uniformly mixing to obtain the shell pre-emulsion.
4. Adding 50 parts by weight of water and 8 parts by weight of polyvinyl alcohol into a third triangular flask, heating to 90 ℃ for dissolving, cooling to 60 ℃, adding 0.5 part by weight of sodium dodecyl sulfate and 1 part by weight of sodium bicarbonate, stirring, adding 20 parts by weight of seed emulsion and 5 parts by weight of first initiator, heating to 75 ℃, adding 10 parts by weight of outer core pre-emulsion and 5 parts by weight of second initiator, stirring, adding 30 parts by weight of shell pre-emulsion and 5 parts by weight of third initiator, standing for 1 hour, heating to 90 ℃, and keeping warm for 1 hour. Cooling to 40 ℃, vacuumizing for 1h, and discharging.
The first initiator, the second initiator and the third initiator are respectively potassium persulfate and sodium bisulfite in a weight ratio of 1:7, compounding.
The gravel is a mixture of fine gravel and coarse gravel, the particle size of the fine gravel is 3mm, and the particle size of the coarse gravel is 11mm; the weight ratio of the fine gravel to the coarse gravel is 7:3.
example 1 in a second aspect there is provided a strong weatherable colored gravel concrete composition comprising the steps of:
1. putting the gravel, the alkaline slag, the nano-silica and the iron oxide red into a stirrer, and uniformly stirring to prepare a premix;
2. adding the silicate cement into the premix, and continuously stirring uniformly to prepare a mixture;
3. and adding the modified polyvinyl acetate, the bisphenol A epoxy resin, the sodium lignin sulfonate and the water into the mixture, and uniformly stirring to obtain the modified polyvinyl acetate.
Example 2
Example 2 in a first aspect, there is provided a colored gravel concrete composition having high weather resistance, which is prepared from, by weight, 15 parts of modified polyvinyl acetate, 13 parts of bisphenol a type epoxy resin (epoxy value of 0.9eq/100 g), 60 parts of portland cement (strength grade of 52.5), 230 parts of gravel, 15 parts of alkaline slag, 30 parts of nano-silica (particle size of 25 nm), 3 parts of sodium lignosulfonate, 10 parts of iron blue, and 40 parts of water.
The preparation method of the modified polyvinyl acetate comprises the following steps:
1. according to the weight portion, evenly mixing 110 portions of vinyl acetate monomer, 40 portions of butyl acrylate and 18 portions of acrylic acid to obtain the seed emulsion.
2. According to the weight parts, 80 parts of water and 1 part of sodium dodecyl sulfate are added into a first triangular flask, 120 parts of vinyl acetate monomer and 3 parts of butyl acrylate are slowly added, and the mixture is uniformly mixed to obtain the external core pre-emulsion.
3. According to the weight parts, 80 parts of water and 1 part of sodium dodecyl sulfate are added into a second triangular flask, 110 parts of vinyl acetate monomer, 4 parts of butyl acrylate and 130 parts of isooctyl acrylate are slowly added, and the mixture is uniformly mixed to obtain the shell pre-emulsion.
4. Adding 80 parts by weight of water and 15 parts by weight of polyvinyl alcohol into a third triangular flask, heating to 90 ℃ for dissolution, cooling to 60 ℃, adding 5 parts by weight of sodium dodecyl sulfate and 5 parts by weight of sodium bicarbonate, stirring, adding 70 parts by weight of seed emulsion and 10 parts by weight of first initiator, heating to 75 ℃, adding 50 parts by weight of outer core pre-emulsion and 10 parts by weight of second initiator, stirring, adding 80 parts by weight of shell pre-emulsion and 10 parts by weight of third initiator, standing for 1h, heating to 90 ℃, and keeping warm for 1h. Cooling to 40 ℃, vacuumizing for 1h, and discharging.
The first initiator, the second initiator and the third initiator are respectively potassium persulfate and sodium bisulfite in a weight ratio of 1:9 and (4) compounding.
The gravel is a mixture of fine gravel and coarse gravel, the particle size of the fine gravel is 10mm, and the particle size of the coarse gravel is 99mm; the weight ratio of the fine gravel to the coarse gravel is 10:3.
example 2 in a second aspect, a colored gravel concrete composition having enhanced weatherability is provided, as in example 1.
Example 3
Example 3 in a first aspect, there is provided a colored gravel concrete composition with high weather resistance, which is prepared from, by weight, 13 parts of modified polyvinyl acetate, 10 parts of bisphenol a type epoxy resin (epoxy value of 0.7eq/100 g), 50 parts of portland cement (strength grade of 52.5), 200 parts of gravel, 13 parts of alkaline slag, 25 parts of nano-silica (particle size of 20 nm), 2 parts of sodium lignosulfonate, 7 parts of carbon black and 35 parts of water.
The preparation method of the modified polyvinyl acetate comprises the following steps:
1. according to the weight portion, 80 portions of vinyl acetate monomer, 30 portions of butyl acrylate and 15 portions of acrylic acid are evenly mixed to obtain the seed emulsion.
2. According to the weight parts, 60 parts of water and 0.5 part of sodium dodecyl sulfate are added into a first triangular flask, 80 parts of vinyl acetate monomer and 1.5 parts of butyl acrylate are slowly added, and the materials are uniformly mixed to obtain the external core pre-emulsion.
3. Adding 70 parts of water and 0.5 part of sodium dodecyl sulfate into a second triangular flask, slowly adding 100 parts of vinyl acetate monomer, 2 parts of butyl acrylate and 120 parts of isooctyl acrylate, and uniformly mixing to obtain the shell pre-emulsion.
4. Adding 70 parts of water and 12 parts of polyvinyl alcohol into a third triangular flask, heating and dissolving at 90 ℃, cooling to 60 ℃, adding 4 parts of sodium dodecyl sulfate and 3 parts of sodium bicarbonate, stirring, adding 50 parts of seed emulsion and 7 parts of first initiator, heating to 75 ℃, adding 30 parts of outer core pre-emulsion and 7 parts of second initiator, stirring, adding 60 parts of shell pre-emulsion and 7 parts of third initiator, standing for 1h, heating to 90 ℃, and keeping the temperature for 1h. Cooling to 40 ℃, vacuumizing for 1h, and discharging.
The first initiator, the second initiator and the third initiator are respectively potassium persulfate and sodium bisulfite in a weight ratio of 1:8, compounding.
The gravel is a mixture of fine gravel and coarse gravel, the particle size of the fine gravel is 7mm, and the particle size of the coarse gravel is 50mm; the weight ratio of the fine gravel to the coarse gravel is 8:3.
example 3 in a second aspect, a colored gravel concrete composition having enhanced weatherability is provided, as in example 1.
Comparative example 1
Comparative example 1 in a first aspect, a colored gravel concrete composition having high weather resistance is prepared in the same manner as in example 3 except that polyvinyl acetate is used instead of modified polyvinyl acetate.
Comparative example 1 in a second aspect, a colored gravel concrete composition having high weather resistance is provided, as in example 1.
Comparative example 2
Comparative example 2 the first aspect provides a strong weather-resistant colored gravel concrete composition, which is prepared in the same manner as in example 3, except that the seed emulsion is prepared by: according to the weight portion, 80 portions of vinyl acetate monomer, 50 portions of butyl acrylate and 15 portions of acrylic acid are evenly mixed to obtain the seed emulsion.
Comparative example 2 in a second aspect, a colored gravel concrete composition having high weather resistance is provided, as in example 1.
Comparative example 3
Comparative example 3 the first aspect provides a colored gravel concrete composition with strong weather resistance, which is prepared in the same manner as in example 3, except that 70 parts by weight of water and 12 parts by weight of polyvinyl alcohol are added to a third flask, dissolved by heating at 90 ℃, cooled to 60 ℃, added with 4 parts by weight of sodium dodecyl sulfonate and 3 parts by weight of sodium bicarbonate, stirred, added with 50 parts by weight of seed emulsion and 7 parts by weight of potassium persulfate, heated to 75 ℃, added with 50 parts by weight of outer core pre-emulsion and 7 parts by weight of potassium persulfate, stirred, added with 50 parts by weight of shell pre-emulsion and 7 parts by weight of potassium persulfate, left to stand for 1 hour, heated to 90 ℃ and kept warm for 1 hour. Cooling to 40 ℃, vacuumizing for 1h, and discharging.
Comparative example 3 in a second aspect, a colored gravel concrete composition having high weather resistance is provided, as in example 1.
Comparative example 4
Comparative example 4 the first aspect provides a colored gravel concrete composition having high weather resistance, which is carried out in the same manner as in example 3 except that the epoxy value of the bisphenol a type epoxy resin is 0.25eq/100g.
Comparative example 4 in a second aspect, a colored gravel concrete composition having high weather resistance was prepared in the same manner as in example 1
Comparative example 5
Comparative example 5 the first aspect provides a colored gravel concrete composition with high weather resistance, which is embodied in the same manner as in example 3 except that the nano-silica has a particle size of 5nm.
Comparative example 5 in a second aspect, a colored gravel concrete composition having high weather resistance was prepared in the same manner as in example 1
Comparative example 6
Comparative example 6 the first aspect provides a colored gravel concrete composition with high weather resistance, which is carried out in the same manner as in example 3, except that the gravel is fine gravel having a particle size of 10mm.
Comparative example 6 in a second aspect, a colored gravel concrete composition having high weather resistance is provided by the same method as in example 1.
Comparative example 7
Comparative example 7 the first aspect provides a strong weather-resistant colored gravel concrete composition, which is carried out in the same manner as in example 3, except that the weight ratio of the fine gravel to the coarse gravel is 1:3.
comparative example 7 in a second aspect, a colored gravel concrete composition having high weather resistance is provided by the same method as in example 1.
Comparative example 8
Comparative example 8 the first aspect provides a colored gravel concrete composition with high weather resistance, which is embodied in the same manner as in example 3 except that acid slag is used instead of alkali slag.
Comparative example 8 in a second aspect, a colored gravel concrete composition having high weather resistance is provided by the same method as in example 1.
Comparative example 9
Comparative example 9 in a first aspect, a high weatherability colored gravel concrete composition is provided and is embodied in the same manner as in example 3 except that the strength grade of the portland cement is 42.5.
Comparative example 9 in a second aspect, a colored gravel concrete composition having high weather resistance is provided in the same manner as in example 1.
Performance test
The above examples and comparative examples were subjected to performance tests, and the results are shown in the following table.
Standard for 500 day colour difference test: the prepared strong weather-resistant colored gravel concrete composition was placed in an outdoor environment for 500 days, and the weight ratio of the composition was measured before and after the placement with the same camera in the morning of 9:00 photograph record color.
Weather resistance test standard: the prepared colored gravel concrete composition with strong weather resistance is placed in an outdoor environment for 500 days, and the surface change condition of the composition is recorded after 500 days.
And (4) testing the compressive strength: GB/T50107-2010
Figure BDA0003029470850000121
Figure BDA0003029470850000131
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.

Claims (4)

1. The colored gravel concrete composition with strong weather resistance is characterized by comprising, by weight, 10-15 parts of modified polyvinyl acetate, 8-13 parts of resin, 40-60 parts of inorganic cementing material, 180-230 parts of crumb-shaped sediment, 10-15 parts of slag and 20-30 parts of inorganic particles; the preparation raw materials also comprise 0.5-3 parts of water reducing agent, 5-10 parts of pigment and 30-40 parts of water; the modified polyvinyl acetate is acrylate modified polyvinyl acetate; the resin is epoxy resin, the resin is bisphenol A type epoxy resin, and the epoxy value of the bisphenol A type epoxy resin is not less than 0.4eq/100g; the inorganic cementing material is Portland cement, and the strength grade of the inorganic cementing material is not less than 52.5; the detritus-shaped sediment is a mixture of fine gravel and coarse gravel, and the weight ratio of the fine gravel to the coarse gravel is (7-10): 3, the particle size of the fine gravel is 3-10mm, and the particle size of the coarse gravel is 11-99mm; the inorganic particles are nano silicon dioxide, and the particle size of the nano silicon dioxide is 15-25nm; the slag is alkaline slag with M value more than 1;
the preparation method of the acrylate modified polyvinyl acetate comprises the following steps:
(1) Uniformly mixing 20-120 parts of vinyl acetate monomer, 20-40 parts of butyl acrylate and 13-18 parts of acrylic acid in parts by weight to obtain seed emulsion;
(2) Adding 50-80 parts of water and 0.02-1 part of first emulsifier by weight into a first triangular flask, slowly adding 20-120 parts of vinyl acetate monomer and 0.2-3 parts of butyl acrylate, and uniformly mixing to obtain an outer core pre-emulsion;
(3) Adding 50-80 parts of water and 0.02-1 part of a second emulsifier by weight into a second triangular flask, slowly adding 90-110 parts of vinyl acetate monomer, 0.1-4 parts of butyl acrylate and 110-130 parts of isooctyl acrylate, and uniformly mixing to obtain a shell pre-emulsion;
(4) Adding 50-80 parts by weight of water and 8-15 parts by weight of polyvinyl alcohol into a third triangular flask, heating to 90 ℃ for dissolution, cooling to 60 ℃, adding 0.5-5 parts by weight of a third emulsifier and 1-5 parts by weight of sodium bicarbonate, stirring, adding 20-70 parts by weight of seed emulsion and 5-10 parts by weight of a first initiator, heating to 75 ℃, adding 10-50 parts by weight of an outer core pre-emulsion and 5-10 parts by weight of a second initiator, stirring, adding 30-80 parts by weight of a shell pre-emulsion and 5-10 parts by weight of a third initiator, standing for 1h, heating to 90 ℃, keeping the temperature for 1h, cooling to 40 ℃, vacuumizing for 1h, and discharging;
the weight ratio of the seed emulsion to the outer core pre-emulsion to the shell pre-emulsion is (2-7): (1-5): (3-8).
2. A highly weatherable colored gravel concrete composition according to claim 1, wherein the water reducing agent is at least one selected from the group consisting of lignosulfonate, naphthalenesulfonate, melamine-based water reducing agents, sulfamate-based superplasticizers, fatty acid-based superplasticizers, powdery polycarboxylates, casein, and polycarboxylic acid-based high performance water reducing agents.
3. A strong weatherable colored gravel concrete composition according to claim 1, wherein the pigment is selected from at least one of iron blue, iron oxide red, chromium oxide green, carbon black, titanium white, chromium oxide yellow, cadmium red, cadmium yellow, lithopone, and iron oxide yellow.
4. A method of making a highly weatherable colored gravel concrete composition of claim 1 comprising the steps of:
1. putting 180-230 parts of crumb-shaped sediment, 10-15 parts of slag, 20-30 parts of inorganic particles and 5-10 parts of pigment into a stirrer, and uniformly stirring to prepare premix;
2. adding 40-60 parts of inorganic cementing material into the premix, and continuously stirring uniformly to prepare a mixture;
3. and (2) putting 10-15 parts of modified polyvinyl acetate, 8-13 parts of resin, 0.5-3 parts of water reducing agent and 30-40 parts of water into the mixture, and uniformly stirring to obtain the modified polyvinyl acetate.
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