CN108373303B - Preparation method of antifouling and antibacterial concrete - Google Patents
Preparation method of antifouling and antibacterial concrete Download PDFInfo
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- CN108373303B CN108373303B CN201810284139.1A CN201810284139A CN108373303B CN 108373303 B CN108373303 B CN 108373303B CN 201810284139 A CN201810284139 A CN 201810284139A CN 108373303 B CN108373303 B CN 108373303B
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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
- 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
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/67—Biocides
- C04B2103/69—Fungicides
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2092—Resistance against biological degradation
Abstract
The invention discloses a preparation method of antifouling and antibacterial concrete, which is characterized by preparing an antifouling and antibacterial polycarboxylate superplasticizer, diluting a mother solution of the polycarboxylate superplasticizer into a solution with the solid content of 15-16% by weight, doping the solution into a gel material for preparing the concrete, and fully and uniformly mixing the solution to obtain the concrete, wherein the doping amount is 1-1.5% of the total weight of the gel material. The antifouling and antibacterial polycarboxylate superplasticizer is prepared by carrying out free radical copolymerization on a carboxylate monomer, a polyether macromonomer, a zwitter-ion monomer and a cationic monomer in a molar ratio of 3-5: 1: 0.05-0.5 under the action of a redox initiator and a chain transfer agent. The concrete can meet higher construction requirements and has good application prospect in hydraulic engineering and ocean engineering.
Description
Technical Field
The invention relates to a preparation method of antifouling and antibacterial concrete, belonging to the technical field of building materials.
Background
The concrete is one of the most widely applied members in infrastructure construction, and has the characteristics of high bearing capacity, quickness in construction, reliable quality and the like. The prior art is relatively mature in the aspects of sulfate resistance, acid-base resistance and the like of concrete, but has not attracted sufficient attention and attention in the aspects of influencing appearance and generating peculiar smell due to the dirt of a concrete body caused by the corrosion of bacteria and microorganisms, even influencing the performance of the concrete and the like, and has not found a measure for effectively solving the problem.
Incorporation of antimicrobial agents into concrete has been reported to inhibit the growth of microorganisms and bacteria. Chinese patent CN107663050A discloses an antibacterial low-temperature-resistant concrete, which adopts nano-silver self-cleaning ceramic glaze, and has the advantages of antibacterial property, corrosion resistance and long service life. Chinese patent CN104058704A discloses an antibacterial and impervious concrete, which uses natural colored jade powder and borosilicate inorganic glass flakes to increase the impermeability and antibacterial performance of the concrete. Chinese patent CN104230228A discloses a high-temperature-resistant antibacterial concrete, which has antibacterial and corrosion-resistant characteristics and prolonged service life by adding silybum marianum extract and hexadecyl trimethyl ammonium chloride.
The polycarboxylate superplasticizer is an important concrete admixture and has the advantages of low mixing amount, high water reducing rate, good slump retaining performance, strong molecular structure adjustability, large high-performance potential and the like. The concrete is doped into the polycarboxylate superplasticizer with antifouling and antibacterial functions, so that the breeding of microorganisms and bacteria can be effectively inhibited. Based on the above, introducing antifouling and antibacterial functional groups into the carboxylic acid water reducing agent by a molecular design means is expected to become a fundamental way for solving the above problems. Chinese patent CN107698721A discloses a branched chain type antibacterial polycarboxylate water reducing agent, wherein a branched chain contains an imidazolium salt group, and the imidazolium salt group has strong antibacterial property and stability, so that the polycarboxylate water reducing agent has strong antibacterial property. Chinese patent CN107265907A discloses an amphoteric antibacterial polycarboxylic acid high-efficiency water reducing agent, wherein the side chain of the amphoteric antibacterial polycarboxylic acid high-efficiency water reducing agent is provided with a quaternary ammonium salt structure with three polyether macromolecular branched chains, and the amphoteric antibacterial polycarboxylic acid high-efficiency water reducing agent has an antibacterial function. Chinese patent CN105621927A discloses an antibacterial preservative for a polycarboxylic acid water reducing agent, which is obtained by carrying out free radical copolymerization on an antibacterial fresh-keeping monomer and polyoxyethylene ether, has a molecular structure similar to and compatible with the polycarboxylic acid water reducing agent, and has remarkable anti-mildew and sterilization effects. Chinese patent CN105037645A discloses an environment-friendly self-anticorrosion polycarboxylate water reducer, which is prepared by carrying out free radical copolymerization reaction on a carboxylic acid monomer, a high molecular weight polyether macromonomer and a functional guanidine salt monomer, so that the water reducer has the antibacterial and anticorrosion functions.
At present, the industry has widely considered that whether the concrete is antifouling and antibacterial directly influences the service performance and the service life of the concrete. The concrete is easy to be corroded by microorganisms and bacteria in the environment, so that the surface form is damaged, and the use function of the concrete is further influenced, and therefore, the special conditions or the environment have higher requirements on the antifouling and antibacterial capacity of the concrete. For example, when hydraulic or marine concrete is in contact with water or seawater for a long time, a large amount of bacteria and microorganisms attack the concrete, which may cause serious fouling and corrosion of the concrete surface. Therefore, the prepared antifouling and antibacterial concrete is expected to achieve the antifouling and antibacterial purposes of the concrete, and the antifouling and antibacterial concrete can be obtained by preparing the polycarboxylate superplasticizer with the antifouling and antibacterial functions, so the development of the polycarboxylate superplasticizer with various specific functions is one of the important directions for the development of the concrete preparation field in the future.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of antifouling and antibacterial concrete.
The preparation method of the antifouling and antibacterial concrete comprises the following steps:
(1) preparation of antifouling and antibacterial polycarboxylic acid water reducing agent
Placing a mixed aqueous solution of a polyether macromonomer, a zwitterionic monomer and a cationic monomer into a reaction kettle, heating to 30-40 ℃, and adding an oxidation component; meanwhile, slowly dropwise adding the solution A, namely the aqueous solution of the carboxylic acid monomer, for 2-3 hours, and the solution B, namely the mixed solution of the chain transfer agent and the reducing agent, for 2-3 hours, and preserving heat for 1-3 hours after dropwise adding; after the reaction is finished, cooling to room temperature, and adjusting the pH of the reaction product to 6-7 by using a sodium hydroxide or potassium hydroxide aqueous solution to obtain the antifouling and antibacterial polycarboxylate superplasticizer;
wherein, the carboxylic acid monomer is acrylic acid or methacrylic acid; the polyether macromonomer is one of prenyl polyoxyethylene ether (TPEG), isobutenol polyoxyethylene ether (HPEG) and allyl Alcohol Polyoxyethylene Ether (APEG); the zwitterionic monomer is one of (methyl) acrylic acid carboxyl betaine, (methyl) acrylic acid sulfobetaine, (methyl) acrylamide carboxyl betaine and (methyl) acrylamide sulfobetaine; the cationic monomer is one of methacryloyloxyethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride and acrylamide propyl trimethyl ammonium chloride; the mass concentration of the carboxylic acid monomer, the polyether macromonomer, the zwitterion monomer and the cationic monomer during polymerization is 40-60%; the redox initiator is a composition of an oxidizing component and a reducing component, wherein the oxidizing component is one of hydrogen peroxide, ammonium persulfate and potassium persulfate, the reducing component is one of vitamin C, sodium bisulfite and ferrous sulfate, the using amount of the oxidizing component is 0.1-2% of the total mass of the polyether macromonomer, the zwitterionic monomer and the cationic monomer, and the mass ratio of the oxidizing component to the reducing component is 0.5-5: 1; the chain transfer agent is one of 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptopropanol and 3-mercaptopropanol; the dosage of the chain transfer agent is 0.1 to 1 percent of the total mass of the carboxylic acid monomer, the polyether macromonomer, the zwitterion monomer and the cation monomer;
in the antifouling and antibacterial polycarboxylate superplasticizer, the molar ratio of the carboxylic acid monomer, the polyether macromonomer, the zwitterion monomer and the cationic monomer is 3-5: 1: 0.05-0.5;
(2) preparation of antifouling antibacterial concrete
Diluting the prepared antifouling and antibacterial polycarboxylate superplasticizer into a solution with the solid content of 15-16% by weight, then doping the solution into a conventional gel material for preparing concrete, and fully and uniformly mixing to obtain the antifouling and antibacterial concrete; wherein the doping amount of the antifouling and antibacterial polycarboxylate superplasticizer solution is 1-1.5 percent of the total weight of the gel material. Wherein the gel material is preferably cement, mineral powder and fly ash.
The preparation method of the antifouling and antibacterial concrete comprises the following steps: the mole ratio of the carboxylic acid monomer, the polyether macromonomer, the zwitterion monomer and the cationic monomer is preferably 4-5: 1: 0.1-0.4; wherein the carboxylic acid monomer is preferably acrylic acid; the polyether macromonomer is preferably isopentenol polyoxyethylene ether (TPEG); the zwitterionic monomer is preferably sulfobetaine (methyl) acrylate; the cationic monomer is preferably methacryloyloxyethyl trimethyl ammonium chloride; the oxidizing component is preferably hydrogen peroxide, and the reducing component is preferably vitamin C; the chain transfer agent is preferably 3-mercaptopropionic acid.
Further, the molar ratio of the carboxylic acid monomer, the polyether macromonomer, the zwitterionic monomer and the cationic monomer is preferably 4.2:1:0.3: 0.2; and the molar ratio of the zwitterion monomer to the cationic monomer is 1-3: 2. Wherein the molar ratio of zwitterionic monomer to cationic monomer is most preferably 1.5: 1.
According to the invention, the antifouling and antibacterial functional groups and the unsaturated monomers forming the water reducing agent are subjected to free radical copolymerization, so that the polycarboxylate water reducing agent has an antifouling and antibacterial function, and then the polycarboxylate water reducing agent is added into cement concrete, so that the inhibition and killing effects on bacteria and microorganisms on the surface of the concrete can be given, the good appearance and the good service performance of the polycarboxylate water reducing agent can be maintained, the application of the polycarboxylate water reducing agent in the field of hydraulic or marine concrete can be expanded, and the prepared antifouling and antibacterial concrete can meet higher construction requirements and has a good application prospect.
The invention has the beneficial effects that:
1. the group with antifouling and antibacterial functions is introduced into the molecular structure of the polycarboxylic acid water reducing agent, so that the self antibacterial effect of the polycarboxylic acid water reducing agent can be improved, and the polycarboxylic acid water reducing agent can be used as an additive to endow concrete with antifouling and antibacterial functions;
2. in the antifouling and antibacterial polycarboxylate superplasticizer, the zwitterion functional groups can inhibit the attachment and breeding of bacteria and microorganisms, the quaternary ammonium salt cations can effectively kill the attached bacteria and microorganisms, the synergistic effect of the bacteria and the microorganisms can simultaneously inhibit and kill the bacteria and the microorganisms, and the inhibition and killing efficiency is improved;
3. the antifouling and antibacterial polycarboxylate superplasticizer is doped into concrete, so that the surface of the concrete is kept clean, the corrosion of bacteria and microorganisms can be prevented, and the concrete is particularly suitable for the surface antifouling and antibacterial of marine or hydraulic concrete.
Detailed Description
The present invention will be further understood from the following specific examples, which should not be construed as limiting the scope of the invention.
Example 1:
(1) preparation of antifouling antibacterial polycarboxylate superplasticizer
Into a four-necked flask equipped with a thermometer, a stirrer and a dropping funnel were charged 40g (16.7mmol) of TPEG2400, 1.4g (5mol) of sulfobetaine methacrylate, 1.4g of methacryloyloxyethyltrimethylammonium chloride (75 wt%, 5mmol), 35g of distilled water, the initial temperature was controlled to 30 ℃ to 35 ℃, and after dissolution of the macromonomer, 0.46g of hydrogen peroxide (30 wt%) was added. After stirring for 15min, A, B liquid (liquid A is an aqueous solution of 5.0g (70mmol) of acrylic acid and 3.5g of distilled water; liquid B is an aqueous solution of 0.24g (2.3mmol) of 3-mercaptopropionic acid, 0.29g of vitamin C (1.65mmol) and 8.1g of distilled water) was added dropwise at the same time. Dropwise adding the solution A for 2.5h, dropwise adding the solution B for 3.0h, and preserving heat for 1.5h after dropwise adding. And (3) cooling to room temperature after the reaction is finished, adding 30 wt% of NaOH solution to neutralize until the pH value is 6-7, and adding water to dilute to 40% of solid content to obtain the antifouling and antibacterial polycarboxylate superplasticizer AFB-1.
(2) Preparation of antifouling antibacterial concrete
Diluting the antifouling and antibacterial polycarboxylate superplasticizer mother liquor AFB-1 into a solution with the solid content of 15%, and adding the solution according to 1% of the dosage of gel materials (cement, fly ash and the like). Adopting concrete reference mixing ratio: preparing a standard concrete test block (15cm by 15cm) with the mass ratio of the cement to the fly ash to the yellow sand to the broken stone being 320:80:900:920, and curing for 7 days at 25 ℃.
Example 2:
(1) preparation of antifouling antibacterial polycarboxylate superplasticizer
The same as in example 1.
(2) Preparation of antifouling antibacterial concrete
Diluting the antifouling and antibacterial polycarboxylate superplasticizer mother liquor AFB-1 into a solution with the solid content of 15%, and adding the solution according to 1.25% of the dosage of gel materials (cement, fly ash and the like). Adopting concrete reference mixing ratio: preparing a standard concrete test block (15cm by 15cm) with the mass ratio of the cement to the fly ash to the yellow sand to the broken stone being 320:80:900:920, and curing for 7 days at 25 ℃.
Example 3:
(1) preparation of antifouling antibacterial polycarboxylate superplasticizer
The same as in example 1.
(2) Preparation of antifouling antibacterial concrete
Diluting the antifouling and antibacterial polycarboxylate superplasticizer mother liquor AFB-1 into a solution with the solid content of 15%, and adding the solution according to 1.5% of the dosage of gel materials (cement, fly ash and the like). Adopting concrete reference mixing ratio: preparing a standard concrete test block (15cm by 15cm) with the mass ratio of the cement to the fly ash to the yellow sand to the broken stone being 320:80:900:920, and curing for 7 days at 25 ℃.
Example 4:
(1) preparation of antifouling antibacterial polycarboxylate superplasticizer
Into a four-necked flask equipped with a thermometer, a stirrer and a dropping funnel were charged 40g (16.7mmol) of TPEG2400, 1.4g (5mol) of sulfobetaine methacrylate, 0.9g of methacryloyloxyethyltrimethylammonium chloride (75 wt%, 3.3mmol), 35g of distilled water, the starting temperature was controlled to 30 ℃ to 35 ℃, and after dissolution of the macromonomer, 0.46g of hydrogen peroxide (30 wt%) was added. After stirring for 15min, A, B liquid (liquid A is an aqueous solution of 5.0g (70mmol) of acrylic acid and 3.5g of distilled water; liquid B is an aqueous solution of 0.24g (2.3mmol) of 3-mercaptopropionic acid, 0.29g of vitamin C (1.65mmol) and 8.1g of distilled water) was added dropwise at the same time. Dropwise adding the solution A for 2.5h, dropwise adding the solution B for 3.0h, and preserving heat for 1.5h after dropwise adding. And (3) cooling to room temperature after the reaction is finished, adding 30 wt% of NaOH solution to neutralize until the pH value is 6-7, and adding water to dilute to 40% of solid content to obtain the antifouling and antibacterial polycarboxylate superplasticizer AFB-2.
(2) Preparation of antifouling antibacterial concrete
Diluting the antifouling and antibacterial polycarboxylate superplasticizer mother liquor AFB-2 into a solution with the solid content of 15%, and adding the solution according to 1% of the dosage of gel materials (cement, fly ash and the like). Adopting concrete reference mixing ratio: preparing a standard concrete test block (15cm by 15cm) with the mass ratio of the cement to the fly ash to the yellow sand to the broken stone being 320:80:900:920, and curing for 7 days at 25 ℃.
Example 5:
(1) preparation of antifouling antibacterial polycarboxylate superplasticizer
The same as in example 4.
(2) Preparation of antifouling antibacterial concrete
Diluting the antifouling and antibacterial polycarboxylate superplasticizer mother liquor AFB-2 into a solution with the solid content of 15%, and adding the solution according to 1.25% of the dosage of gel materials (cement, fly ash and the like). Adopting concrete reference mixing ratio: preparing a standard concrete test block (15cm by 15cm) with the mass ratio of the cement to the fly ash to the yellow sand to the broken stone being 320:80:900:920, and curing for 7 days at 25 ℃.
Example 6:
(1) preparation of antifouling antibacterial polycarboxylate superplasticizer
The same as in example 4.
(2) Preparation of antifouling antibacterial concrete
Diluting the antifouling and antibacterial polycarboxylate superplasticizer mother liquor AFB-2 into a solution with the solid content of 15%, and adding the solution according to 1.5% of the dosage of gel materials (cement, fly ash and the like). Adopting concrete reference mixing ratio: preparing a standard concrete test block (15cm by 15cm) with the mass ratio of the cement to the fly ash to the yellow sand to the broken stone being 320:80:900:920, and curing for 7 days at 25 ℃.
Comparative example 1:
(1) preparation of antifouling polycarboxylate superplasticizer
Into a four-necked flask equipped with a thermometer, a stirrer and a dropping funnel were charged 40g (16.7mmol) of TPEG2400, 1.4g (5mol) of sulfobetaine methacrylate, and 35g of distilled water, the starting temperature was controlled to 30 ℃ to 35 ℃, and after dissolution of the macromonomer, 0.46g of hydrogen peroxide (30 wt%) was added. After stirring for 15min, A, B liquid (liquid A is an aqueous solution of 5.0g (70mmol) of acrylic acid and 3.5g of distilled water; liquid B is an aqueous solution of 0.24g (2.3mmol) of 3-mercaptopropionic acid, 0.29g of vitamin C (1.65mmol) and 8.1g of distilled water) was added dropwise at the same time. Dropwise adding the solution A for 2.5h, dropwise adding the solution B for 3.0h, and preserving heat for 1.5h after dropwise adding. And (3) cooling to room temperature after the reaction is finished, adding 30 wt% of NaOH solution to neutralize until the pH value is 6-7, and adding water to dilute to 40% of solid content to obtain the antifouling polycarboxylate superplasticizer AF-1.
(2) Preparation of antifouling concrete
Diluting the antifouling polycarboxylate superplasticizer mother liquor AF-1 into a solution with the solid content of 15%, and adding the solution according to 1.25% of the dosage of gel materials (cement, fly ash and the like). Adopting concrete reference mixing ratio: preparing a standard concrete test block (15cm by 15cm) with the mass ratio of the cement to the fly ash to the yellow sand to the broken stone being 320:80:900:920, and curing for 7 days at 25 ℃.
Comparative example 2:
(1) preparation of antibacterial polycarboxylic acid water reducing agent
Into a four-necked flask equipped with a thermometer, a stirrer and a dropping funnel were charged 40g (16.7mmol) of TPEG2400, 1.4g of methacryloyloxyethyl trimethyl ammonium chloride (75 wt%, 5mmol) and 35g of distilled water, the starting temperature was controlled to 30 ℃ to 35 ℃, and after dissolution of the macromonomer, 0.46g of hydrogen peroxide (30 wt%) was added. After stirring for 15min, A, B liquid (liquid A is an aqueous solution of 5.0g (70mmol) of acrylic acid and 3.5g of distilled water; liquid B is an aqueous solution of 0.24g (2.3mmol) of 3-mercaptopropionic acid, 0.29g of vitamin C (1.65mmol) and 8.1g of distilled water) was added dropwise at the same time. Dropwise adding the solution A for 2.5h, dropwise adding the solution B for 3.0h, and preserving heat for 1.5h after dropwise adding. And (3) cooling to room temperature after the reaction is finished, adding 30 wt% of NaOH solution to neutralize until the pH value is 6-7, and adding water to dilute to 40% of solid content to obtain the antibacterial polycarboxylate superplasticizer AB-1.
(2) Preparation of antibacterial concrete
The antibacterial polycarboxylate superplasticizer mother liquor AB-1 is diluted into a solution with the solid content of 15%, and the solution is added according to 1.25% of the dosage of gel materials (cement, fly ash and the like). Adopting concrete reference mixing ratio: preparing a standard concrete test block (15cm by 15cm) with the mass ratio of the cement to the fly ash to the yellow sand to the broken stone being 320:80:900:920, and curing for 7 days at 25 ℃.
Comparative example 3:
(1) preparation of common polycarboxylic acid water reducing agent
A four-necked flask equipped with a thermometer, stirrer and dropping funnel was charged with 40g (16.7mmol) of TPEG2400, 35g of distilled water, controlled to have an initial temperature of 30 ℃ to 35 ℃, and after dissolution of the macromonomer, 0.46g of hydrogen peroxide (30 wt%) was added. After stirring for 15min, A, B liquid (liquid A is an aqueous solution of 5.0g (70mmol) of acrylic acid and 3.5g of distilled water; liquid B is an aqueous solution of 0.24g (2.3mmol) of 3-mercaptopropionic acid, 0.29g of vitamin C (1.65mmol) and 8.1g of distilled water) was added dropwise at the same time. Dropwise adding the solution A for 2.5h, dropwise adding the solution B for 3.0h, and preserving heat for 1.5h after dropwise adding. And (3) cooling to room temperature after the reaction is finished, adding 30 wt% of NaOH solution to neutralize until the pH value is 6-7, and adding water to dilute until the solid content is 40% to obtain the common polycarboxylic acid water reducing agent PC-1.
(2) Preparation of ordinary concrete
Diluting the common polycarboxylate superplasticizer mother liquor PC-1 into a solution with the solid content of 15%, and adding the diluted solution according to 1.25% of the dosage of gel materials (cement, fly ash and the like). Adopting concrete reference mixing ratio: preparing a standard concrete test block (15cm by 15cm) with the mass ratio of the cement to the fly ash to the yellow sand to the broken stone being 320:80:900:920, and curing for 7 days at 25 ℃.
And (3) testing the antifouling and antibacterial performances of the concrete test block:
the concrete test pieces obtained in examples 1 to 6 and comparative examples 1 to 3 were immersed in the culture solution, placed in a constant temperature incubator at 40 ℃ and periodically sampled and examined, and the results are shown in Table 1.
TABLE 1 antifouling and antibacterial property test results of concrete test blocks in different example states
As can be seen from Table 1, the surface of the concrete test block prepared by using the common polycarboxylate superplasticizer (PC-1) has green moss or hypha at 40 ℃ for 3 months. Green moss or hyphae appear on the surface of a test block of the anti-fouling polycarboxylate superplasticizer (AF-1) containing the zwitterion group and the antibacterial polycarboxylate superplasticizer (AB-1) containing the quaternary ammonium cation group within 6 months. And the test block containing the antifouling antibacterial polycarboxylate superplasticizers AFB-1 and AFB-2 has green moss or hypha in 9 months or keeps the original shape. The concrete prepared by the antifouling and antibacterial polycarboxylate superplasticizer containing the zwitter-ion group and the quaternary ammonium cation group has the antifouling and antibacterial synergistic effects, can effectively improve the inhibiting and killing effects on bacteria and microorganisms, and has positive correlation with the content of the effect in the concrete.
Claims (1)
1. A preparation method of antifouling and antibacterial concrete comprises the following steps:
(1) preparation of antifouling and antibacterial polycarboxylic acid water reducing agent
Placing a mixed aqueous solution of a polyether macromonomer, a zwitterionic monomer and a cationic monomer into a reaction kettle, heating to 30-40 ℃, and adding an oxidation component; meanwhile, slowly dropwise adding the solution A, namely the aqueous solution of the carboxylic acid monomer, for 2-3 hours, and the solution B, namely the mixed solution of the chain transfer agent and the reducing component, for 2-3 hours, and preserving heat for 1-3 hours after dropwise adding; after the reaction is finished, cooling to room temperature, and adjusting the pH of the reaction product to be 6-7 by using a sodium hydroxide or potassium hydroxide aqueous solution to obtain the antifouling and antibacterial polycarboxylate superplasticizer;
wherein the carboxylic acid monomer is acrylic acid; the polyether macromonomer is isopentenol polyoxyethylene ether; the zwitterionic monomer is (methyl) acrylic acid sulfobetaine; the cationic monomer is methacryloyloxyethyl trimethyl ammonium chloride; the mass concentration of the carboxylic acid monomer, the polyether macromonomer, the zwitterion monomer and the cationic monomer during polymerization is 40-60%; the redox initiator is a composition of an oxidation component and a reduction component, wherein the oxidation component is hydrogen peroxide, the reduction component is vitamin C, the dosage of the oxidation component is 0.1-2% of the total mass of the polyether macromonomer, the zwitterion monomer and the cationic monomer, and the mass ratio of the oxidation component to the reduction component is 0.5-5: 1; the chain transfer agent is 3-mercaptopropionic acid; the dosage of the chain transfer agent is 0.1-1% of the total mass of the carboxylic acid monomer, the polyether macromonomer, the zwitterion monomer and the cationic monomer;
(2) preparation of antifouling antibacterial concrete
Diluting the prepared antifouling and antibacterial polycarboxylate superplasticizer into a solution with the solid content of 15-16% by weight, doping the solution into a conventional gel material for preparing concrete, and fully and uniformly mixing to obtain the antifouling and antibacterial concrete; wherein the doping amount of the antifouling and antibacterial polycarboxylate superplasticizer solution is 1-1.5% of the total weight of the gel material;
the method is characterized in that:
in the antifouling and antibacterial polycarboxylate superplasticizer, the molar ratio of a carboxylic acid monomer, a polyether macromonomer, a zwitterion monomer and a cationic monomer is 4.2:1:0.3: 0.2; and the molar ratio of zwitterionic monomer to cationic monomer is 1.5: 1.
Priority Applications (1)
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| CN111153625B (en) * | 2020-02-18 | 2021-08-06 | 广东汇强外加剂有限公司 | Nano-silver-loaded anticorrosion antibacterial polycarboxylate superplasticizer and preparation method thereof |
| CN111515124B (en) * | 2020-06-05 | 2022-04-22 | 江苏拜富科技股份有限公司 | Matt ceramic glaze with strong anti-pollution capability and strong color development |
| CN112195706B (en) * | 2020-08-14 | 2022-03-25 | 江苏固迈新材料技术有限公司 | Comfortable type permeable pavement of elasticity |
| CN112500074A (en) * | 2020-12-08 | 2021-03-16 | 陕西恒盛混凝土有限公司 | Microorganism self-repairing concrete and preparation method thereof |
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