CN114015300B - Concrete protective coating capable of sterilizing and adsorbing sulfate ions and preparation method thereof - Google Patents
Concrete protective coating capable of sterilizing and adsorbing sulfate ions and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
Abstract
The raw materials of the concrete protective coating comprise a permeable film forming substance, a sterilizing adsorbent, a defoaming agent, a leveling agent, a curing agent, a permeation preventing agent and water, wherein the sterilizing adsorbent is one of chitosan coated cuprous oxide, modified chitosan coated cuprous oxide, polyacrylamide and coated cuprous oxide thereof. The chitosan and the modified chitosan and the polyacrylamide coated cuprous oxide in the concrete protective coating provided by the application have very high sterilization adsorption performance as sterilization adsorbents, and especially the polyacrylamide coated cuprous oxide; the sterilizing adsorbent disclosed by the application utilizes chitosan and polyacrylamide macromolecules to electrostatically adsorb sulfate radicals and simultaneously release copper, so that the released copper kills bacteria such as Sulfate Reducing Bacteria (SRB), thiobacillus and the like, and thus the microbial corrosion is stopped or weakened.
Description
Technical Field
The application relates to the technical field of concrete corrosion prevention and sterilization, in particular to a sterilization and sulfate ion adsorption concrete permeation prevention coating and a preparation method thereof.
Background
One of the main factors affecting the durability of concrete is sulfate attack, and not only the external environment such as sea water, groundwater, etc. mostly contains sulfate, but also the concrete component itself may possibly contain sulfate. And SO 4 2- Can react with calcium hydroxide and calcium aluminate hydrate in the concrete to produce ettringite and gypsum, damage the concrete structure and cause the concrete to expand and crack. Meanwhile, calcium Silicate Hydrate (CSH) in the concrete can be decomposed to produce insoluble and non-cementing colloid, so that the performance of the concrete is further reduced.
Biological sulfuric acid generated by Sulfate Reducing Bacteria (SRB), thiobacillus and the like reacting with sulfate ions and metabolites thereof is a main cause of microbial corrosion of concrete, and the action mechanism is as follows: SRB will SO under anaerobic conditions 4 2- Reduction to S 2- Release H 2 S, reducing the pH value of the environment; under acidic conditions H 2 S is oxidized into biological sulfuric acid by thiobacillus; biological sulfuric acid reacts with alkaline substances of concrete to generate gypsum and ettringite, which damage the concrete structure and cause the concrete to expand and crack, thus reducing the service life of the concrete.
Besides bacteria such as SRB and thiobacillus, organic acids such as acetic acid and glucuronic acid generated by fungus metabolism can react with concrete or hypha stretches into the concrete to accelerate the destruction of the concrete structure.
The method is a simple, economical, practical and effective anti-corrosion protection measure for protecting the concrete surface coating, and the pollution of microorganisms can cause the performance failure of the coating and affect the protection effect. This is because microorganisms can survive and multiply in the coating, causing an increase in the viscosity of the coating, resulting in a failure of the coating properties.
In order to reduce damage of sulfate and microorganisms to concrete and protection thereof, the prior art mainly uses modes of improving the pore structure of the concrete, changing the cement-water ratio (sulfate-resistant cement) of the concrete, adding bactericides and the like. The effect is poor when the components are singly used, and the working procedures are increased when the components are mixed.
Disclosure of Invention
In view of this, the application provides a concrete permeation-preventing coating for sterilizing and adsorbing sulfate ions.
The technical scheme of the application is realized as follows:
the raw materials of the concrete protective coating comprise a permeable film forming substance, a sterilizing adsorbent, a defoaming agent, a leveling agent, a curing agent, a permeation preventing agent and water, wherein the sterilizing adsorbent is one of chitosan coated cuprous oxide, modified chitosan coated cuprous oxide, polyacrylamide and coated cuprous oxide thereof.
The further technical scheme is that the modified chitosan comprises one of formaldehyde crosslinked chitosan and glutaraldehyde crosslinked chitosan.
The further technical scheme is that the anti-seepage agent is basalt flakes activated by a silane coupling agent.
The further technical proposal is that the permeable film forming substance is organosilicon modified acrylic acid aqueous resin; the defoaming agent comprises one of an organic silicon defoaming agent and a polyether modified polysiloxane defoaming agent; the leveling agent is one of polyacrylate leveling agent, fluorine modified polyacrylate leveling agent or polyether modified organosilicon leveling agent; the curing agent is triethylene tetramine.
The concrete protective coating comprises, by weight, 45-60 parts of a penetrating film forming substance, 5-10 parts of a sterilizing adsorbent, 0.05-0.2 part of a defoaming agent, 0.05-0.2 part of a leveling agent, 3-5 parts of a curing agent, 8-12 parts of an anti-penetrating agent and 50-60 parts of water.
A preparation method of the concrete protective coating capable of sterilizing and adsorbing sulfate ions comprises the steps of adding a permeable film forming substance into water at a stirring speed of 1500-2500rpm, then adding a defoaming agent and a leveling agent, continuously stirring for 10-15min, and then adding an impermeable agent and a sterilizing adsorbent, and stirring for 30-40min to obtain emulsion; and adding a curing agent into the emulsion, stirring and mixing to prepare the concrete protective coating.
The further technical scheme is that the preparation method of the sterilizing adsorbent comprises the steps of adding 0.6-0.8 part of chitosan, modified chitosan or polyacrylamide into 80-90 parts of acetic acid aqueous solution with the mass fraction of 1-2% to obtain chitosan solution; mixing 300-320 parts of copper chloride solution with the mass fraction of 20-25% with chitosan solution, heating to 90-95 ℃, adjusting the pH to 8-9, adding 200-220 parts of sodium sulfite solution with the mass fraction of 5-10%, stirring for 20-30min, and separating out a precipitate, wherein the precipitate is a sterilizing adsorbent.
The further technical scheme is that after the copper chloride solution and the chitosan solution are mixed, 0.5-0.7 part of silane coupling agent with the mass fraction of 1-3% is added, and the mixture is stirred for 5-10min and then heated.
The specific activation method of basalt flake activated by the impermeable agent through the silane coupling agent comprises the following steps: adding basalt flakes into a silane coupling agent with the mass fraction of 1-3%, ultrasonically mixing for 5-10min, and then washing and drying by using an alcohol solution to prepare basalt flakes activated by the silane coupling agent.
The adsorption of the sterilizing adsorbent to sulfate radical is mainly the electrostatic attraction of protonated amino radical to sulfate radical, and the adsorption of chitosan and polyacrylamide to sulfate radical is the swelling process of small sulfate radical molecule in water solution entering the gap of large chitosan molecule. The chitosan amino nitrogen atom has nucleophilic activity, can combine hydrogen ions and copper ions in aqueous solution to become protonized amino groups, and can generate electrostatic attraction adsorption on hydrogen sulfate ionized by sulfate radicals. Meanwhile, the cuprous oxide is disproportionated into bivalent copper and copper simple substance in an acid solution, and the reaction formula is as follows: cu (Cu) 2 O+H 2 SO 4 →CuSO 4 +Cu+H 2 The copper released by the sterilizing adsorbent has strong sterilizing effect, and further kills bacteria such as Sulfate Reducing Bacteria (SRB) and thiobacillus, thereby stopping or weakening the microbial corrosion.
Compared with the prior art, the application has the beneficial effects that:
(1) The chitosan and the modified chitosan and the polyacrylamide coated cuprous oxide in the concrete protective coating provided by the application have very high sterilization adsorption performance as sterilization adsorbents, and especially the polyacrylamide coated cuprous oxide; the sterilizing adsorbent disclosed by the application utilizes chitosan and polyacrylamide macromolecules to electrostatically adsorb sulfate radicals and simultaneously release copper, so that the released copper kills bacteria such as Sulfate Reducing Bacteria (SRB), thiobacillus and the like, and thus the microbial corrosion is stopped or weakened.
(2) According to the preparation method of the bactericidal adsorbent, the silane coupling agent is added, so that the adsorptivity of the concrete protective coating to sulfate ions can be greatly improved.
(3) According to the application, the activated basalt flakes are added, so that the physical shielding effect of the concrete protective coating is increased, and the protective capability of the concrete protective coating is further improved.
(4) The concrete protective coating provided by the application has good antibacterial performance, so that the concrete protective coating is not easy to be polluted by microorganisms, the coating performance can be kept for a long time, and the service life of concrete is prolonged.
Detailed Description
In order to better understand the technical content of the present application, the following provides specific examples to further illustrate the present application.
Example 1
The concrete protective coating capable of sterilizing and adsorbing sulfate ions comprises the following raw materials in parts by weight: 45 parts of permeable film forming material, 5 parts of sterilizing adsorbent, 0.05 part of defoamer, 0.05 part of flatting agent, 3 parts of curing agent, 8 parts of anti-permeable agent and 50 parts of water.
The sterilizing adsorbent is cuprous oxide coated by chitosan; the anti-seepage agent is basalt flakes activated by a silane coupling agent. The permeable film forming material is organic silicon modified acrylic acid aqueous resin; the defoaming agent is an organosilicon defoaming agent; the leveling agent is polyacrylate leveling agent; the curing agent is triethylene tetramine.
The preparation method of the concrete protective coating capable of sterilizing and adsorbing sulfate ions comprises the steps of adding a permeable film forming substance into water at a stirring speed of 1500rpm, then adding a defoaming agent and a leveling agent, continuously stirring for 10min, and then adding an anti-permeable agent and a sterilizing adsorbent, and stirring for 30min to obtain emulsion; and adding a curing agent into the emulsion, stirring and mixing to prepare the concrete protective coating.
The preparation method of the sterilizing adsorbent comprises the steps of adding 0.6 part of chitosan into 80 parts of acetic acid aqueous solution with the mass fraction of 1% to obtain chitosan solution; 300 parts of copper chloride solution with the mass fraction of 20% and chitosan solution are mixed, heated to 90 ℃, the pH value is adjusted to 8, 200 parts of sodium sulfite solution with the mass fraction of 5% are added, stirring is carried out for 20min, and precipitation is separated out, wherein the precipitation is a sterilizing adsorbent. After the copper chloride solution and the chitosan solution are mixed, 0.5 part of silane coupling agent with the mass fraction of 1% is added, and the mixture is stirred for 5 minutes and then heated.
The specific activation method of basalt flake activated by the impermeable agent through the silane coupling agent comprises the following steps: adding basalt flakes into a silane coupling agent with the mass fraction of 1%, ultrasonically mixing for 5min, and then cleaning and drying by using an alcohol solution to prepare basalt flakes activated by the silane coupling agent.
Example 2
The concrete protective coating capable of sterilizing and adsorbing sulfate ions comprises the following raw materials in parts by weight: 60 parts of permeable film forming material, 10 parts of sterilizing adsorbent, 0.2 part of defoamer, 0.2 part of flatting agent, 5 parts of curing agent, 12 parts of anti-permeable agent and 60 parts of water.
The sterilizing adsorbent is formaldehyde crosslinked chitosan coated cuprous oxide; the anti-seepage agent is basalt flakes activated by a silane coupling agent; the permeable film forming material is organic silicon modified acrylic acid aqueous resin; the defoaming agent is polyether modified polysiloxane defoaming agent; the leveling agent is a fluorine modified polyacrylate leveling agent; the curing agent is triethylene tetramine.
The preparation method of the concrete protective coating capable of sterilizing and adsorbing sulfate ions comprises the steps of adding a permeable film forming substance into water at a stirring speed of 2500rpm, then adding a defoaming agent and a leveling agent, continuously stirring for 15min, and then adding an anti-permeable agent and a sterilizing adsorbent, and stirring for 40min to obtain emulsion; and adding a curing agent into the emulsion, stirring and mixing to prepare the concrete protective coating.
The preparation method of the sterilizing adsorbent comprises the steps of adding 0.8 part of formaldehyde crosslinked chitosan into 90 parts of acetic acid aqueous solution with the mass fraction of 2% to obtain chitosan solution; 320 parts of copper chloride solution with the mass fraction of 25% and chitosan solution are mixed, heated to 95 ℃, the pH value is adjusted to 9, 220 parts of sodium sulfite solution with the mass fraction of 10% are added, stirring is carried out for 30min, and precipitation is separated out, wherein the precipitation is a sterilizing adsorbent.
After the copper chloride solution and the chitosan solution are mixed, 0.7 part of silane coupling agent with the mass fraction of 3% is added, and the mixture is stirred for 10 minutes and then heated.
The specific activation method of basalt flake activated by the impermeable agent through the silane coupling agent comprises the following steps: adding basalt flakes into a silane coupling agent with the mass fraction of 3%, ultrasonically mixing for 5min, and then cleaning and drying by using an alcohol solution to prepare basalt flakes activated by the silane coupling agent.
Example 3
The concrete protective coating capable of sterilizing and adsorbing sulfate ions comprises the following raw materials in parts by weight: 50 parts of permeable film forming material, 8 parts of sterilizing adsorbent, 0.1 part of defoamer, 0.1 part of flatting agent, 4 parts of curing agent, 10 parts of anti-permeable agent and 55 parts of water.
The sterilization adsorbent is polyacrylamide coated cuprous oxide; the anti-seepage agent is basalt flakes activated by a silane coupling agent; the permeable film forming material is organic silicon modified acrylic acid aqueous resin; the defoaming agent is an organosilicon defoaming agent; the leveling agent is a polyether modified organic silicon leveling agent; the curing agent is triethylene tetramine.
The preparation method of the concrete protective coating capable of sterilizing and adsorbing sulfate ions comprises the steps of adding a permeable film forming substance into water at a stirring speed of 2000rpm, then adding a defoaming agent and a leveling agent, continuously stirring for 15min, and then adding an anti-permeable agent and a sterilizing adsorbent, and stirring for 35min to obtain emulsion; and adding a curing agent into the emulsion, stirring and mixing to prepare the concrete protective coating.
The preparation method of the sterilizing adsorbent comprises the steps of adding 0.7 part of polyacrylamide into 85 parts of acetic acid aqueous solution with the mass fraction of 2% to obtain chitosan solution; 320 parts of copper chloride solution with the mass fraction of 20 percent is mixed with chitosan solution, the mixture is heated to 90 ℃, the pH value is regulated to 8, 210 parts of sodium sulfite solution with the mass fraction of 8 percent is added, the mixture is stirred for 25 minutes, and a precipitate is separated out, wherein the precipitate is a sterilizing adsorbent.
After the copper chloride solution and the chitosan solution are mixed, 0.6 part of silane coupling agent with the mass fraction of 2% is added, and the mixture is stirred for 7min and then heated.
The specific activation method of basalt flake activated by the impermeable agent through the silane coupling agent comprises the following steps: adding basalt flakes into a silane coupling agent with the mass fraction of 2%, ultrasonically mixing for 8min, and then cleaning and drying by using an alcohol solution to prepare basalt flakes activated by the silane coupling agent.
Example 4
The sterilizing adsorbent was polyacrylamide, and the other was the same as in example 3.
Comparative example 1
The sterilizing adsorbent is chitosan, and the other components are the same as those in example 1.
Comparative example 2
The sterilizing adsorbent is formaldehyde crosslinked chitosan, and the other steps are the same as those in the embodiment 2.
Comparative example 3
In the method for preparing the sterilizing and sulfate ion-adsorbing concrete protective coating of example 1, the silane coupling agent is not added after the copper chloride solution and the chitosan solution are mixed. The method comprises the following steps: adding 0.6 part of chitosan into 80 parts of acetic acid aqueous solution with the mass fraction of 1% to obtain chitosan solution; 300 parts of copper chloride solution with the mass fraction of 20% and chitosan solution are mixed, heated to 90 ℃, the pH value is adjusted to 8, 200 parts of sodium sulfite solution with the mass fraction of 5% are added, stirring is carried out for 20min, and precipitation is separated out, wherein the precipitation is a sterilizing adsorbent.
Bacteriostasis test and results thereof
Bacteriostasis test: taking clean pollution-free filter paper sheets, punching the filter paper sheets into filter paper sheets with the diameter of 4mm by using a puncher, placing the filter paper sheets into a test tube, autoclaving the filter paper sheets at 121 ℃ for 15min, taking out the filter paper sheets, and drying the filter paper sheets in a drying oven at 80 ℃; then 50mg of concrete protective paint is added on each filter paper piece, and the filter paper pieces are naturally dried in an incubator (37 ℃) for 5 minutes for standby.
Uniformly smearing and inoculating activated Sulfate Reducing Bacteria (SRB) and thiobacillus on a nutrient agar culture dish plate, and then attaching concrete protective coating filter paper sheets of different test groups on the inoculated nutrient agar culture dish plate, wherein the distance between the centers of the concrete protective coating filter paper sheets is not less than 20mm, and the distance between the centers of the concrete protective coating filter paper sheets and the periphery of a culture medium plate is not less than 15mm. The media were divided into two groups, one group (SRB group) being: each culture medium is respectively stuck with 1 distilled water negative control, 3 filter paper sheets of the concrete protective coating of the same test group, and the total number of the culture mediums is 9; two groups (thiobacillus group) are: each culture medium is respectively stuck with 1 distilled water negative control, 3 filter paper sheets of the concrete protective coating of the same test group, and the total number of the culture mediums is 9;
the dishes were covered, and the results were observed after culturing in two groups of incubators at 37℃for 24 hours. One set of growth observations was placed in an anaerobic bag at 37 ℃. Measuring the size of the inhibition zone includes the diameter and size of the negative patch.
TABLE 1
As can be seen from Table 1, examples 1 to 4 and comparative examples 1 to 3 all have a better antibacterial effect on SRB and thiobacillus than the control group, wherein, as can be seen from examples 1 and comparative example 3, whether the silane coupling agent is added in the preparation method of the bactericidal adsorbent has little influence on the antibacterial effect of the protective coating of the concrete. It is clear from example 1 and comparative example 1 that the antibacterial effect of the chitosan-coated cuprous oxide as a sterilizing adsorbent is stronger than that of chitosan. From example 2 and comparative example 2, it is known that the antibacterial effect of formaldehyde-crosslinked chitosan coated cuprous oxide as a sterilizing adsorbent is greater than that of formaldehyde-crosslinked chitosan. As can be seen from the comparison of examples 1-4, the antibacterial effect of the polyacrylamide coated cuprous oxide of example 3 as a sterilizing adsorbent is superior to that of other sterilizing adsorbents.
Adsorptivity test and results thereof
The concrete protective coating of each test group was weighed into a 250mL conical flask, to which was added 50mL of an initial concentration of 300 mg.L －1 SO of (2) 4 2－ The solution is oscillated and adsorbed for 3 hours at the constant temperature of 35 ℃ and the oscillation speed is controlled to be 180 r.min －1 After adsorption equilibrium, centrifugal filtration is carried out. Measurement of SO in filtrate by ion chromatograph 4 2－ Concentration.
Adsorption rate: η= (C 0 -C e )/C 0 ×100％
Adsorption amount: q= (C 0 -C e )×V/W
In the formula C 0 Is SO 4 2－ The initial concentration (mg/L) of the solution and Ce are SO after adsorption 4 2－ The concentration (mg/L) of the solution, V is the adsorbed SO 4 2－ The volume (L) of the solution and W is the dosage (g) of the concrete protective coating.
TABLE 2
As can be seen from Table 2, the adsorption capacity and adsorption rate of example 3 are both greater than those of other test groups, and it can be seen that the polyacrylamide coated cuprous oxide can maximally adsorb SO as a sterilizing adsorbent for concrete protective coating 4 2－ The method comprises the steps of carrying out a first treatment on the surface of the As can be seen from example 1 and comparative example 1, the adsorption performance of the sterilizing adsorbent of the concrete protective coating prepared by the chitosan coated with cuprous oxide is stronger than that of the concrete protective coating prepared by the chitosan; from example 2 and comparative example 2, it is known that the cuprous oxide coated with formaldehyde crosslinked chitosan has stronger adsorption performance than the sterilizing adsorbent of the concrete protective coating prepared from formaldehyde crosslinked chitosan; as is clear from example 1 and comparative example 3, the addition of the silane coupling agent in the preparation method of the bactericidal adsorbent greatly improves the adsorption performance of the protective coating of concrete.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (7)
1. The utility model provides a concrete protective coating of sterilization, absorption sulfate ion, concrete protective coating raw materials includes infiltration formula film forming material, sterilization adsorbent, defoamer, flatting agent, curing agent, prevention of seepage agent and water, its characterized in that: the sterilizing adsorbent is one of chitosan coated cuprous oxide, modified chitosan coated cuprous oxide and polyacrylamide coated cuprous oxide; the preparation method of the sterilizing adsorbent comprises the steps of adding 0.6-0.8 part of chitosan, modified chitosan or polyacrylamide into 80-90 parts of acetic acid aqueous solution with the mass fraction of 1-2% to obtain chitosan or polyacrylamide solution; mixing 300-320 parts of copper chloride solution with the mass fraction of 20-25% with chitosan or polyacrylamide solution, adding 0.5-0.7 part of silane coupling agent with the mass fraction of 1-3% into the mixture, stirring the mixture for 5-10min, heating the mixture again, heating the mixture to 90-95 ℃, adjusting the pH value to 8-9, adding 200-220 parts of sodium sulfite solution with the mass fraction of 5-10% into the mixture, stirring the mixture for 20-30min, and separating out precipitates, wherein the precipitates are sterilizing adsorbents.
2. The bactericidal, sulfate ion-adsorbing concrete protective coating according to claim 1, wherein: the modified chitosan comprises one of formaldehyde crosslinked chitosan and glutaraldehyde crosslinked chitosan.
3. The bactericidal, sulfate ion-adsorbing concrete protective coating according to claim 1, wherein: the anti-seepage agent is basalt flakes activated by a silane coupling agent.
4. The bactericidal, sulfate ion-adsorbing concrete protective coating according to claim 1, wherein: the permeable film forming material is organic silicon modified acrylic acid aqueous resin; the defoaming agent comprises one of an organic silicon defoaming agent and a polyether modified polysiloxane defoaming agent; the leveling agent is one of polyacrylate leveling agent, fluorine modified polyacrylate leveling agent or polyether modified organosilicon leveling agent; the curing agent is triethylene tetramine.
5. A bactericidal, sulfate ion adsorbing concrete protective coating according to any of claims 1-4, characterized in that: the concrete protective coating comprises the following raw materials in parts by weight: 45-60 parts of permeable film forming substance, 5-10 parts of sterilizing adsorbent, 0.05-0.2 part of defoamer, 0.05-0.2 part of flatting agent, 3-5 parts of curing agent, 8-12 parts of anti-permeable agent and 50-60 parts of water.
6. A method for preparing a bactericidal and sulfate ion-adsorbing concrete protective coating as set forth in claim 5, characterized in that: adding the permeable film forming material into water at a stirring speed of 1500-2500rpm, then adding the defoamer and the flatting agent, continuously stirring for 10-15min, and then adding the anti-permeable agent and the bactericidal adsorbent, and stirring for 30-40min to obtain emulsion; and adding a curing agent into the emulsion, stirring and mixing to prepare the concrete protective coating.
7. The method for preparing the bactericidal and sulfate ion-adsorbing concrete protective coating according to claim 6, which is characterized in that: the impermeable agent is a specific activation method of basalt flakes activated by a silane coupling agent: adding basalt flakes into a silane coupling agent with the mass fraction of 1-3%, ultrasonically mixing for 5-10min, and then washing and drying by using an alcohol solution to prepare basalt flakes activated by the silane coupling agent.
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