CN108373303A - A kind of preparation method of antifouling and antibiosis type concrete - Google Patents
A kind of preparation method of antifouling and antibiosis type concrete Download PDFInfo
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- CN108373303A CN108373303A CN201810284139.1A CN201810284139A CN108373303A CN 108373303 A CN108373303 A CN 108373303A CN 201810284139 A CN201810284139 A CN 201810284139A CN 108373303 A CN108373303 A CN 108373303A
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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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- 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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- 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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- 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
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Abstract
The invention discloses a kind of preparation methods of antifouling and antibiosis type concrete, it is to prepare antifouling and antibiosis type polycarboxylate water-reducer, its mother liquor is diluted to the solution that solid content weight ratio is 15%~16% again, incorporation is used to prepare in the gel rubber material of concrete, acquisition is mixed well, incorporation is the 1%~1.5% of gel rubber material total weight.Wherein antifouling and antibiosis type polycarboxylate water-reducer is 3~5 by molar ratio:1:0.05~0.5:0.05~0.5 carboxylic acid monomer, polyether macromonomer, zwitterionic monomer, cationic monomer carry out free radicals copolymerization reaction under redox initiator and chain-transferring agent effect and are made.The concrete of the present invention can meet higher construction requirement, have a good application prospect in hydraulic engineering and ocean engineering.
Description
Technical field
The present invention relates to a kind of preparation methods of antifouling and antibiosis type concrete, belong to building material technical field.
Background technology
Concrete is one of the component being most widely used in infrastructure construction, has high capacity, quick construction, matter
Measure the features such as reliable.The prior art resists sulfate, acid-base property etc. relative maturity in concrete, but for bacterium and micro-
Concrete body is stained and influences appearance, generates peculiar smell caused by the erosion of biology, or even the side such as performance for influencing concrete
Face causes enough concern and attention not yet, also the countermeasure without finding effectively to solve.
It has been reported that and mixes the growth that antiseptic can inhibit microorganism and bacterium in concrete.Chinese patent
CN107663050A discloses a kind of low temperature resistant concrete of antibacterial, and using nano silver self cleaning enamel glaze, Antimicrobial preservative uses the longevity
Life length.Chinese patent CN104058704A discloses a kind of antibacterial water-tight concrete, by using natural colorful jade powder, borosilicate
Hydrochlorate unorganic glass scale increases the impervious and anti-microbial property of concrete.Chinese patent CN104230228A discloses one kind
High-temperature resistant antibacterial concrete, by adding milk thistle extract, hexadecyltrimethylammonium chloride so that concrete has antibacterial
Corrosion resistant characteristic, prolongs the service life.
Polycarboxylate water-reducer is a kind of important concrete admixture, have volume is low, water-reducing rate is high, function of slump protection is good,
The advantages that molecular structure adjustability is strong, high performance potentiality are big.It will be mixed in polycarboxylate water-reducer with antifouling and antibiosis function
Concrete can effectively inhibit the growth of microorganism and bacterium.Drawn in carboxylic acid water reducer by MOLECULE DESIGN means based on this
Enter antifouling and antibiosis functional group, be expected to become the fundamental way to solve the above problems.Chinese patent CN107698721A discloses one
Kind branched chain type antibacterial polycarboxylate water-reducer, branch contain imidazole salts group, and imidazole salts group has stronger antibiotic property and stabilization
Property, make polycarboxylate water-reducer that there is stronger anti-microbial property.Chinese patent CN107265907A discloses a kind of amphoteric antibacterial
Polycarboxylic acid series high efficiency water reducing agent carries the quaternary ammonium salt structure of three polyethers big molecule side chains on side chain, has antibacterial functions.China
Patent CN105621927A discloses a kind of antibiotic antiseptic for poly carboxylic acid series water reducer, by anti-bacterial refreshing monomer and polyoxy
Vinethene is carried out free-radical polymerized and is obtained, and has the molecular structure with poly carboxylic acid series water reducer similar compatibility, has significant anti-
It goes mouldy, bactericidal effect.Chinese patent CN105037645A discloses a kind of environmentally friendly from anti-corrosion type polycarboxylate water-reducer, carboxylic acid list
Body, high molecular weight polyether polymeric monomer carry out free radicals copolymerization reaction with functional guanidine salt monomer and are made, and water-reducing agent itself is made to have
The function of Antimicrobial preservative.
Currently, insider has been widely believed that whether antifouling and antibiosis will have a direct impact on its performance and service life to concrete.
Concrete is vulnerable to the erosion of microorganism and bacterium in environment, and configuration of surface is made to be destroyed, and then influences it and use function, because
This specific condition or environment propose requirements at the higher level to the antifouling and antibiosis ability of concrete.For example, water conservancy project or maritime concrete are long
Phase and water or contact with sea water, a large amount of bacteriums and microorganism generate corrosion function to concrete, concrete surface can be caused to occur tight
It is stained and corrodes again.It is expected to realize the antifouling and antibiosis purpose of concrete in consideration of it, preparing a kind of antifouling and antibiosis type concrete, utilize
Preparing, there is antifouling and antibiosis type polycarboxylate water-reducer can get antifouling and antibiosis type concrete, therefore the polycarboxylic acids of various specific functions
Water-reducing agent exploitation is also one of the important directions of the following concrete preparation field development.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preparation methods of antifouling and antibiosis type concrete.
The preparation method of antifouling and antibiosis type concrete of the present invention, step are：
(1) antifouling and antibiosis type polycarboxylate water-reducer is prepared
The mixed aqueous solution of polyether macromonomer, zwitterionic monomer and cationic monomer is placed in reaction kettle, is warming up to
30~40 DEG C, oxidation component is added；2~the 3h of aqueous solution and B solution i.e. chain that the i.e. carboxylic acid monomer of solution A is slowly added dropwise simultaneously turn
2~the 3h of mixed solution for moving agent and reducing agent keeps the temperature 1~3h after being added dropwise to complete；It is down to room temperature after reaction, utilizes hydroxide
Sodium or potassium hydroxide aqueous solution adjust the pH to pH=6-7 of reaction product, obtain antifouling and antibiosis type polycarboxylate water-reducer；
Wherein, carboxylic acid monomer is acrylic or methacrylic acid；Polyether macromonomer is isoamyl alcohol polyoxyethylene ether
(TPEG), one kind in isobutene alcohol polyoxyethylene ether (HPEG), allyl alcohol polyethenoxy ether (APEG)；Zwitterionic monomer is
(methyl) acrylic acid carboxybetaine, (methyl) acrylic acid sulfonic group glycine betaine, (methyl) acrylamide carboxybetaine, (first
Base) one kind in acrylamide sulfonic group glycine betaine；Cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, allyl
One kind in base trimethyl ammonium chloride, acrylamido propyl trimethyl ammonium chloride；And carboxylic acid monomer, polyether macromonomer, both sexes from
Mass concentration when sub- monomer, cationic monomers is 40~60%；The redox initiator be oxidation component and
The composition of reduction components, wherein oxidation component, that is, oxidant are one kind in hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, reduction
Component, that is, reducing agent is one kind in vitamin C, sodium hydrogensulfite, ferrous sulfate, and oxidation component dosage is polyether macromonomer, two
Property ion monomer, the 0.1%~2% of cationic monomer gross mass and oxidation component and the mass ratio of reduction components be 0.5~5:
1；The chain-transferring agent is one kind in 2 mercaptopropionic acid, 3- mercaptopropionic acids, 2- mercaprols, 3- mercaprols；Chain tra nsfer
Agent dosage be carboxylic acid monomer, polyether macromonomer, zwitterionic monomer, cationic monomer gross mass 0.1%~1%；
In above-mentioned antifouling and antibiosis type polycarboxylate water-reducer, the carboxylic acid monomer, polyether macromonomer, zwitterionic monomer and sun
The molar ratio of ion monomer is 3~5:1:0.05~0.5:0.05~0.5；
(2) preparation of antifouling and antibiosis type concrete
The antifouling and antibiosis type polycarboxylate water-reducer of preparation is diluted to the solution that solid content weight ratio is 15%~16%, then
Incorporation is used to prepare in the conventional GPC material of concrete, is mixed well, that is, obtains antifouling and antibiosis type concrete；Wherein, antifouling
The incorporation of antimicrobial form polycarboxylate water-reducer solution is the 1%~1.5% of gel rubber material total weight.The wherein described gel rubber material is excellent
Choosing is cement, miberal powder and flyash.
In the preparation method of above-mentioned antifouling and antibiosis type concrete：The carboxylic acid monomer, polyether macromonomer, zwitterionic monomer
With the molar ratio preferably 4~5 of cationic monomer:1:0.1~0.4:0.1~0.4；The wherein preferred acrylic acid of carboxylic acid monomer；Polyethers
The preferred isoamyl alcohol polyoxyethylene ether of polymeric monomer (TPEG)；Zwitterionic monomer preferably (methyl) acrylic acid sulfonic group glycine betaine；
The preferred MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of cationic monomer；The preferred hydrogen peroxide of oxidation component, reduction components are excellent
Select vitamin C；The preferred 3- mercaptopropionic acids of the chain-transferring agent.
Further, the molar ratio of the carboxylic acid monomer, polyether macromonomer, zwitterionic monomer and cationic monomer is preferred
4.2:1:0.3:0.2；And the molar ratio of zwitterionic monomer and cationic monomer is 1~3:2.Wherein, the amphoteric ion list
The molar ratio of body and cationic monomer most preferably 1.5:1.
The present invention is free-radical polymerized by the unsaturated monomer progress of antifouling and antibiosis functional group and composition water-reducing agent, makes poly- carboxylic
Sour water-reducing agent itself has the function of antifouling and antibiosis, then is spiked into cement concrete, can assign concrete surface to thin
The inhibition of bacterium and microorganism and killing effect keep its good appearance and performance, and expansion polycarboxylate water-reducer is contributed to exist
Application in water conservancy project or maritime concrete field, antifouling and antibiosis type concrete obtained can meet higher construction requirement, have
Good application prospect.
The beneficial effects of the invention are as follows：
1. introducing the group with antifouling and antibiosis function in polycarboxylate water-reducer molecule structure, poly- carboxylic can be not only improved
Sour water-reducing agent subjective antisepsis effect, uses as additive, can assign concrete antifouling and antibiosis function；
2. in antifouling and antibiosis type polycarboxylate water-reducer, amphoteric ion functional group can inhibit bacterium and microorganism attachment and
It grows, quaternary ammonium salt cationic can effectively kill the bacterium and microorganism of attachment, and the synergistic effect of the two can be to bacterium and micro- life
" suppression is killed " of object is carried out at the same time, and improves and inhibits and kill efficiency；
3. by antifouling and antibiosis type polycarboxylate water-reducer mix concrete, make its surface keep cleaning, can prevent bacterium and
Microbial attack is particularly suitable for extra large work or the surface soiling antibacterial of concrete for hydraulic structure.
Specific implementation mode
Below by the specific embodiment provided it will be further appreciated that the present invention, but following embodiments are not to this hair
The restriction of bright protection domain.
Embodiment 1：
(1) preparation of antifouling and antibiosis type polycarboxylate water-reducer
Into the four-hole boiling flask equipped with thermometer, blender and dropping funel be added 40g (16.7mmol) TPEG2400,
The methacrylic sulfonic acids base glycine betaine of 1.4g (5mol), 1.4g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (75wt%,
5mmol), the distilled water of 35g, control initial temperature are 30 DEG C -35 DEG C, and after polymeric monomer dissolving, the hydrogen peroxide of 0.46g is added
(30wt%).After stirring 15min, while A, B liquid (acrylic acid and the preparation of 3.5g distilled water that A liquid is 5.0g (70mmol) is added dropwise
Aqueous solution；B liquid is the 3- mercaptopropionic acids of 0.24g (2.3mmol), the vitamin C (1.65mmol) and 8.1g distilled water of 0.29g
The aqueous solution being configured to).A drops add 2.5h, B drops to add 3.0h, and 1.5h is kept the temperature after being added dropwise to complete.It is down to room after reaction
Temperature, the NaOH solution that 30wt% is added are neutralized to pH=6-7, are diluted with water to 40% solid content to get to antifouling and antibiosis type
Polycarboxylate water-reducer AFB-1.
(2) preparation of antifouling and antibiosis type concrete
Antifouling and antibiosis type polycarboxylate superplasticizer mother liquor AFB-1 is diluted to the solution that solid content is 15%, by gel rubber material
The 1% of (cement and flyash etc.) dosage adds.Using concrete benchmark match ratio：The matter of cement, flyash, yellow sand, rubble
Amount is than being 320:80:900:920, concrete standard test block (15cm*15cm*15cm) is prepared, is conserved 7 days at 25 DEG C.
Embodiment 2：
(1) preparation of antifouling and antibiosis type polycarboxylate water-reducer
With embodiment 1.
(2) preparation of antifouling and antibiosis type concrete
Antifouling and antibiosis type polycarboxylate superplasticizer mother liquor AFB-1 is diluted to the solution that solid content is 15%, by gel rubber material
The 1.25% of (cement and flyash etc.) dosage adds.Using concrete benchmark match ratio：Cement, flyash, yellow sand, rubble
Mass ratio is 320:80:900:920, concrete standard test block (15cm*15cm*15cm) is prepared, is conserved 7 days at 25 DEG C.
Embodiment 3：
(1) preparation of antifouling and antibiosis type polycarboxylate water-reducer
With embodiment 1.
(2) preparation of antifouling and antibiosis type concrete
Antifouling and antibiosis type polycarboxylate superplasticizer mother liquor AFB-1 is diluted to the solution that solid content is 15%, by gel rubber material
The 1.5% of (cement and flyash etc.) dosage adds.Using concrete benchmark match ratio：Cement, flyash, yellow sand, rubble
Mass ratio is 320:80:900:920, concrete standard test block (15cm*15cm*15cm) is prepared, is conserved 7 days at 25 DEG C.
Embodiment 4：
(1) preparation of antifouling and antibiosis type polycarboxylate water-reducer
Into the four-hole boiling flask equipped with thermometer, blender and dropping funel be added 40g (16.7mmol) TPEG2400,
The methacrylic sulfonic acids base glycine betaine of 1.4g (5mol), 0.9g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (75wt%,
3.3mmol), the distilled water of 35g, control initial temperature are 30 DEG C -35 DEG C, and after polymeric monomer dissolving, the hydrogen peroxide of 0.46g is added
(30wt%).After stirring 15min, while A, B liquid (acrylic acid and the preparation of 3.5g distilled water that A liquid is 5.0g (70mmol) is added dropwise
Aqueous solution；B liquid is the 3- mercaptopropionic acids of 0.24g (2.3mmol), the vitamin C (1.65mmol) and 8.1g distilled water of 0.29g
The aqueous solution being configured to).A drops add 2.5h, B drops to add 3.0h, and 1.5h is kept the temperature after being added dropwise to complete.It is down to room after reaction
Temperature, the NaOH solution that 30wt% is added are neutralized to pH=6-7, are diluted with water to 40% solid content to get to antifouling and antibiosis type
Polycarboxylate water-reducer AFB-2.
(2) preparation of antifouling and antibiosis type concrete
Antifouling and antibiosis type polycarboxylate superplasticizer mother liquor AFB-2 is diluted to the solution that solid content is 15%, by gel rubber material
The 1% of (cement and flyash etc.) dosage adds.Using concrete benchmark match ratio：The matter of cement, flyash, yellow sand, rubble
Amount is than being 320:80:900:920, concrete standard test block (15cm*15cm*15cm) is prepared, is conserved 7 days at 25 DEG C.
Embodiment 5：
(1) preparation of antifouling and antibiosis type polycarboxylate water-reducer
With embodiment 4.
(2) preparation of antifouling and antibiosis type concrete
Antifouling and antibiosis type polycarboxylate superplasticizer mother liquor AFB-2 is diluted to the solution that solid content is 15%, by gel rubber material
The 1.25% of (cement and flyash etc.) dosage adds.Using concrete benchmark match ratio：Cement, flyash, yellow sand, rubble
Mass ratio is 320:80:900:920, concrete standard test block (15cm*15cm*15cm) is prepared, is conserved 7 days at 25 DEG C.
Embodiment 6：
(1) preparation of antifouling and antibiosis type polycarboxylate water-reducer
With embodiment 4.
(2) preparation of antifouling and antibiosis type concrete
Antifouling and antibiosis type polycarboxylate superplasticizer mother liquor AFB-2 is diluted to the solution that solid content is 15%, by gel rubber material
The 1.5% of (cement and flyash etc.) dosage adds.Using concrete benchmark match ratio：Cement, flyash, yellow sand, rubble
Mass ratio is 320:80:900:920, concrete standard test block (15cm*15cm*15cm) is prepared, is conserved 7 days at 25 DEG C.
Comparative example 1：
(1) preparation of anti-fouling type polycarboxylate water-reducer
Into the four-hole boiling flask equipped with thermometer, blender and dropping funel be added 40g (16.7mmol) TPEG2400,
The methacrylic sulfonic acids base glycine betaine of 1.4g (5mol), the distilled water of 35g, control initial temperature is 30 DEG C -35 DEG C, waits for big list
After body dissolving, the hydrogen peroxide (30wt%) of 0.46g is added.Stir 15min after, while be added dropwise A, B liquid (A liquid be 5.0g
The aqueous solution that the acrylic acid of (70mmol) is prepared with 3.5g distilled water；B liquid is the 3- mercaptopropionic acids of 0.24g (2.3mmol),
The aqueous solution that the vitamin C (1.65mmol) and 8.1g distilled water of 0.29g is configured to).A drops add 2.5h, B drops to add 3.0h,
1.5h is kept the temperature after being added dropwise to complete.It is down to room temperature after reaction, the NaOH solution that 30wt% is added is neutralized to pH=6-7, adds water
40% solid content is diluted to get to anti-fouling type polycarboxylate water-reducer AF-1.
(2) preparation of anti-fouling type concrete
Anti-fouling type polycarboxylate superplasticizer mother liquor AF-1 is diluted to the solution that solid content is 15%, by gel rubber material (cement
With flyash etc.) dosage 1.25% adds.Using concrete benchmark match ratio：The quality of cement, flyash, yellow sand, rubble
Than being 320:80:900:920, concrete standard test block (15cm*15cm*15cm) is prepared, is conserved 7 days at 25 DEG C.
Comparative example 2：
(1) preparation of antimicrobial form polycarboxylate water-reducer
Into the four-hole boiling flask equipped with thermometer, blender and dropping funel be added 40g (16.7mmol) TPEG2400,
The MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (75wt%, 5mmol) of 1.4g, the distilled water of 35g, control initial temperature are 30
DEG C -35 DEG C, after polymeric monomer dissolving, the hydrogen peroxide (30wt%) of 0.46g is added.After stirring 15min, while A, B liquid (A is added dropwise
The aqueous solution that the acrylic acid that liquid is 5.0g (70mmol) is prepared with 3.5g distilled water；B liquid is the 3- sulfydryls of 0.24g (2.3mmol)
Propionic acid, the aqueous solution that the vitamin C (1.65mmol) and 8.1g distilled water of 0.29g are configured to).A drops add 2.5h, B drops to add
3.0h keeping the temperature 1.5h after being added dropwise to complete.It is down to room temperature after reaction, the NaOH solution that 30wt% is added is neutralized to pH=6-7,
40% solid content is diluted with water to get to antimicrobial form polycarboxylate water-reducer AB-1.
(2) preparation of antimicrobial form concrete
Antimicrobial form polycarboxylate superplasticizer mother liquor AB-1 is diluted to the solution that solid content is 15%, by gel rubber material (cement
With flyash etc.) dosage 1.25% adds.Using concrete benchmark match ratio：The quality of cement, flyash, yellow sand, rubble
Than being 320:80:900:920, concrete standard test block (15cm*15cm*15cm) is prepared, is conserved 7 days at 25 DEG C.
Comparative example 3：
(1) preparation of common polycarboxylate water-reducer
The TPEG2400 of 40g (16.7mmol) is added into the four-hole boiling flask equipped with thermometer, blender and dropping funel,
The distilled water of 35g, control initial temperature are 30 DEG C -35 DEG C, and after polymeric monomer dissolving, the hydrogen peroxide (30wt%) of 0.46g is added.
After stirring 15min, while A, B liquid (aqueous solution that the acrylic acid that A liquid is 5.0g (70mmol) is prepared with 3.5g distilled water is added dropwise；B
Liquid is the 3- mercaptopropionic acids of 0.24g (2.3mmol), the water that the vitamin C (1.65mmol) and 8.1g distilled water of 0.29g are configured to
Solution).A drops add 2.5h, B drops to add 3.0h, and 1.5h is kept the temperature after being added dropwise to complete.It is down to room temperature after reaction, is added
The NaOH solution of 30wt% is neutralized to pH=6-7, is diluted with water to 40% solid content to get to common polycarboxylate water-reducer
PC-1。
(2) preparation of normal concrete
By common polycarboxylate superplasticizer mother liquor PC-1 be diluted to solid content be 15% solution, by gel rubber material (cement with
Flyash etc.) dosage 1.25% add.Using concrete benchmark match ratio：The mass ratio of cement, flyash, yellow sand, rubble
It is 320:80:900:920, concrete standard test block (15cm*15cm*15cm) is prepared, is conserved 7 days at 25 DEG C.
Concrete test block antifouling and antibiosis performance test：
The concrete test block that embodiment 1-6 and comparative example 1-3 are obtained immerses in culture solution, the constant temperature training being placed at 40 DEG C
Case is supported, regular sample detection the results are shown in Table 1.
Concrete test block antifouling and antibiosis the performance test results under the different embodiment states of table 1
As it can be seen from table 1 the concrete test block surface prepared using common polycarboxylate water-reducer (PC-1) is 3 at 40 DEG C
Just there are within a month green paint or mycelia to occur.Anti-pollution type polycarboxylate water-reducer (AF-1) containing amphoteric ion group and containing quaternary ammonium sun
The test block surface of the antimicrobial form polycarboxylate water-reducer (AB-1) of ionic group occurred green paint or mycelia at 6 months.And containing antifouling anti-
The test block of bacterial type polycarboxylate water-reducer AFB-1 and AFB-2 occurred green paint or mycelia at 9 months, or kept original state.Illustrate to utilize
The antifouling and antibiosis type polycarboxylate water-reducer of group containing amphoteric ion and quaternary ammonium cationic groups prepare concrete have it is antifouling and
Antibacterial acts synergistically, and can effectively improve " suppression is killed " effect to bacterium, microorganism, and effect and its content in concrete
It is proportionate.
Claims (5)
1. a kind of preparation method of antifouling and antibiosis type concrete, step are：
(1) antifouling and antibiosis type polycarboxylate water-reducer is prepared
The mixed aqueous solution of polyether macromonomer, zwitterionic monomer and cationic monomer is placed in reaction kettle, it is warming up to 30~
40 DEG C, oxidation component is added；2~the 3h of aqueous solution and B solution i.e. chain-transferring agent of the i.e. carboxylic acid monomer of solution A are slowly added dropwise simultaneously
With 2~3h of mixed solution of reducing agent, 1~3h is kept the temperature after being added dropwise to complete；Be down to room temperature after reaction, using sodium hydroxide or
Potassium hydroxide aqueous solution adjusts the pH to pH=6-7 of reaction product, obtains antifouling and antibiosis type polycarboxylate water-reducer；
Wherein, carboxylic acid monomer is acrylic or methacrylic acid；Polyether macromonomer is isoamyl alcohol polyoxyethylene ether (TPEG), different
One kind in butenol polyoxyethylene ether (HPEG), allyl alcohol polyethenoxy ether (APEG)；Zwitterionic monomer is (methyl) third
Olefin(e) acid carboxybetaine, (methyl) acrylic acid sulfonic group glycine betaine, (methyl) acrylamide carboxybetaine, (methyl) acryloyl
One kind in amine sulfonic group glycine betaine；Cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, allyl trimethyl
One kind in ammonium chloride, acrylamido propyl trimethyl ammonium chloride；And carboxylic acid monomer, polyether macromonomer, zwitterionic monomer, sun
Mass concentration when ion monomer polymerize is 40~60%；The redox initiator is oxidation component and reduction components
Composition, wherein oxidation component, that is, oxidant are one kind in hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, and reduction components restore
Agent is one kind in vitamin C, sodium hydrogensulfite, ferrous sulfate, and oxidation component dosage is polyether macromonomer, amphoteric ion list
Body, the 0.1%~2% of cationic monomer gross mass and oxidation component and the mass ratio of reduction components are 0.5~5:1；Described
Chain-transferring agent is one kind in 2 mercaptopropionic acid, 3- mercaptopropionic acids, 2- mercaprols, 3- mercaprols；Chain-transferring agent dosage is
Carboxylic acid monomer, polyether macromonomer, zwitterionic monomer, cationic monomer gross mass 0.1%~1%；
In above-mentioned antifouling and antibiosis type polycarboxylate water-reducer, the carboxylic acid monomer, polyether macromonomer, zwitterionic monomer and cation
The molar ratio of monomer is 3~5:1:0.05~0.5:0.05~0.5；
(2) preparation of antifouling and antibiosis type concrete
The antifouling and antibiosis type polycarboxylate water-reducer of preparation is diluted to solid content weight ratio and is 15%~16% solution, then is mixed
It is used to prepare in the conventional GPC material of concrete, mixes well, that is, obtain antifouling and antibiosis type concrete；Wherein, antifouling and antibiosis
The incorporation of type polycarboxylate water-reducer solution is the 1%~1.5% of gel rubber material total weight.
2. the preparation method of antifouling and antibiosis type concrete according to claim 1, it is characterised in that：The carboxylic acid monomer gathers
The molar ratio of ether polymeric monomer, zwitterionic monomer and cationic monomer is 4~5:1:0.1~0.4:0.1~0.4；Wherein carboxylic acid
Monomer is acrylic acid；Polyether macromonomer is isoamyl alcohol polyoxyethylene ether (TPEG)；Zwitterionic monomer is (methyl) acrylic acid
Sulfonic group glycine betaine；Cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride；The oxidation component is hydrogen peroxide, also
Stock blend is vitamin C；The chain-transferring agent is 3- mercaptopropionic acids.
3. the preparation method of antifouling and antibiosis type concrete according to claim 2, it is characterised in that：The carboxylic acid monomer gathers
The molar ratio of ether polymeric monomer, zwitterionic monomer and cationic monomer is 4.2:1:0.3:0.2；And zwitterionic monomer with sun from
The molar ratio of sub- monomer is 1~3:2.
4. the preparation method of antifouling and antibiosis type concrete according to claim 3, it is characterised in that：The zwitterionic monomer
Molar ratio with cationic monomer is 1.5:1.
5. the preparation method of antifouling and antibiosis type concrete according to claim 1, it is characterised in that：Step (2) described gel
Material is cement, miberal powder and flyash.
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