CN111825371A - Antibacterial additive for high-strength and high-performance concrete and preparation method thereof - Google Patents
Antibacterial additive for high-strength and high-performance concrete and preparation method thereof Download PDFInfo
- Publication number
- CN111825371A CN111825371A CN202010701945.1A CN202010701945A CN111825371A CN 111825371 A CN111825371 A CN 111825371A CN 202010701945 A CN202010701945 A CN 202010701945A CN 111825371 A CN111825371 A CN 111825371A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- parts
- strength
- antibacterial
- oxide composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application relates to the field of concrete, in particular to an antibacterial additive for high-strength and high-performance concrete. The application provides an antibacterial additive for high-strength and high-performance concrete, which is prepared by mixing the following components in parts by mass: polycarboxylic acid water reducing agent, chitosan-copper oxide composite antibacterial agent, fly ash, hydroxypropyl methyl cellulose, bentonite and polyacrylamide. A preparation method of the antibacterial additive for the high-strength and high-performance concrete comprises the step of ultrasonically blending a polycarboxylic acid water reducing agent and a chitosan-copper oxide composite antibacterial agent and the step of blending other components, and the preparation method is simple and convenient. The antibacterial agent has better antibacterial performance and lasting antibacterial effect; the concrete admixture has good water absorption performance, and can greatly improve the strength of concrete under the condition of adding a small amount of the admixture.
Description
Technical Field
The application relates to the field of concrete, in particular to an antibacterial additive for high-strength and high-performance concrete and a preparation method thereof.
Background
The concrete is an artificial stone material, and is generally prepared by mixing and compounding aggregate, portland cement, water and an additive. Concrete can be classified into various types according to its use, such as waterproof impervious concrete, thermal insulation concrete, fire-resistant concrete, marine concrete, road concrete, radiation-proof concrete, and the like. The high-strength high-performance concrete is concrete with excellent mechanical properties, and has high durability, high workability and high volume stability.
The antibacterial additive is an additive for improving the antibacterial performance of the concrete when added into the concrete, so that the concrete block can be applied to scenes with antibacterial requirements. Chinese patent No. CN1307120C discloses an antibacterial agent for concrete, which is prepared from silver compound, copper compound and ion-retaining compound according to the ratio of 1: (0.1-100): (1-80), wherein the silver compound is one or more of silver carbonate, silver oxide and silver phosphate, the copper compound is one or more of copper carbonate, copper oxide, copper phosphate and copper hydroxide, and the ion-retaining compound is one of alumina, iron oxide, silica, hydrous titanium oxide, hydrous tin oxide, hydrous zirconium oxide, hydrous antimony oxide, phosphomolybdate, phosphotungstate, and the like. When the antibacterial admixture is used for manufacturing high-strength high-performance antibacterial concrete, other kinds of admixtures need to be used at the same time, so that the total addition amount of the admixture is large, however, the maximum addition amount of the admixture is always related to the using amount of a gel material, and therefore, the high-strength high-performance antibacterial concrete with excellent performance is difficult to obtain by using the admixture.
In addition, Chinese patent with patent application publication No. CN111153625A discloses a nano-silver loaded antiseptic and antibacterial polycarboxylate water reducer, which is added with a silver compound to obtain antibacterial performance, and the silver compound is loaded in graphene oxide to improve antibacterial stability; the nano-silver-loaded antiseptic antibacterial polycarboxylate superplasticizer is mainly designed for saline-alkali environment, so that the nano-silver-loaded antiseptic antibacterial polycarboxylate superplasticizer is more suitable for ocean engineering concrete or hydraulic concrete, and cannot be well suitable for high-strength and high-performance concrete.
The Chinese patent with patent application publication number CN109650790A discloses a high-strength antibacterial concrete, which is added with scales as powder, and is also added with laurel leaf powder and a surfactant as an additive, the laurel leaf powder and the surfactant are mixed according to the proportion of 1:2, and the surfactant is the equal mixture of lignosulfonate and alkyl sulfonate. The laurel leaf powder removes the unique fishy smell in the scales, adds the fragrance of the concrete, and simultaneously plays roles of purifying air, inhibiting fungal growth, preventing corrosion and the like, so that the admixture used for the high-strength antibacterial concrete has weak antibacterial effect and cannot be well used in some occasions with high antibacterial requirements.
The technical schemes have certain defects, and an antibacterial additive for high-strength and high-performance concrete is needed to overcome the defects in the prior art.
Disclosure of Invention
In order to better meet the requirement of the performance of the high-strength high-performance concrete additive, the application provides the high-strength high-performance concrete antibacterial additive and the preparation method thereof.
In a first aspect, the application provides an antibacterial additive for high-strength and high-performance concrete, which consists of the following materials in percentage by mass:
15-30 parts of a polycarboxylic acid water reducing agent;
25-35 parts of chitosan-copper oxide composite antibacterial agent;
15-20 parts of fly ash;
0-2 parts of hydroxypropyl methyl cellulose;
0-2 parts of bentonite;
0-2 parts of polyacrylamide.
By adopting the technical scheme, the polycarboxylate superplasticizer is a high-performance water reducing agent, and the water reducing agent is green and environment-friendly, and is nonflammable and also non-explosive. The chitosan-copper oxide composite antibacterial agent has a wide antibacterial spectrum, and can be applied to high-strength and high-performance concrete to improve the antibacterial performance of the concrete. The fly ash is tiny ash particles discharged in the dye combustion process, and is beneficial to realizing blending of all materials in the formula. The hydroxypropyl methyl cellulose has stronger water-retaining property, can prevent the slurry from cracking caused by too fast drying after being coated, and enhances the strength of the hardened concrete. The bentonite has adsorbability and expansibility, and like a water reducing agent, the bentonite can reduce the content of free water in slurry and enhance the strength of concrete. The polyacrylamide is a linear high molecular polymer, and can increase the consistency of concrete and reduce the slump of the concrete.
Preferably, the fly ash is grade I fly ash.
By adopting the technical scheme, the grade I fly ash has low water demand and high consistency, and is suitable for preparing high-strength and high-performance concrete admixtures.
Preferably, the polyacrylamide is nonionic polyacrylamide.
By adopting the technical scheme, the nonionic polyacrylamide is a high molecular polymer or polyelectrolyte, and the molecular chain of the nonionic polyacrylamide contains a certain amount of polar gene energy solid particles, so that large aggregates are formed by bridging among the particles, and the strength of the concrete can be improved compared with other types of polyacrylamide.
Preferably, the bentonite is organic bentonite.
By adopting the technical scheme, the organic bentonite not only has high adsorbability and high expansibility, but also has certain corrosion resistance, and can improve the antibacterial property of concrete in cooperation with the chitosan-copper oxide composite antibacterial agent.
Preferably, the hydroxypropyl methyl cellulose is instant hydroxypropyl methyl cellulose.
By adopting the technical scheme, the instant hydroxypropyl methyl cellulose has the best water absorption and is most suitable for preparing the admixture of high-strength and high-performance concrete.
Preferably, in the chitosan-copper oxide composite antibacterial agent, the deacetylation degree of chitosan is more than or equal to 92%, and the molecular weight is between 60000-90000.
By adopting the technical scheme, the deacetylation degree of chitosan is positively correlated with the antibacterial performance, and chitosan with the molecular weight of 60000-90000 can be better agglomerated around copper oxide to form the chitosan-copper oxide composite antibacterial agent.
Preferably, the preparation method of the chitosan-copper oxide composite antibacterial agent comprises the following steps: dispersing chitosan powder in distilled water by ultrasonic wave, adjusting pH to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, reacting for 30min under ultrasonic stirring, slowly adding sodium carbonate, adding dropwise within 30min until pH is 10-12, eluting solid matter obtained by filtering with distilled water for 3-5 times, and freeze-drying under vacuum to obtain the chitosan-copper oxide composite antibacterial agent.
By adopting the technical scheme, the chitosan has poor water solubility, the chitosan can be well dispersed in water by using ultrasonic waves, under the condition of adjusting the PH to be weakly acidic, copper elements in copper sulfate are mainly in an ionic state, the copper ions and the chitosan can be mutually attracted and combined by ultrasonic stirring reaction for 30min, the copper ions in the solution can be converted into copper hydroxide with extremely fine granularity by adding sodium carbonate, the copper hydroxide is completely converted when the PH reaches 10-12, the chitosan and the copper hydroxide are simultaneously settled, sodium sulfate in the sediment can be removed by distilled water elution, the structure of the sediment is not damaged while crystal water in the sediment can be removed by vacuum freeze drying, and finally the chitosan-copper oxide composite antibacterial agent can bring strong antibacterial performance to concrete.
Preferably, the preparation method of the chitosan-copper oxide composite antibacterial agent comprises the following steps:
putting chitosan powder and isooctane into a reaction kettle, dispersing chitosan by using ultrasonic dispersion stirring to form a chitosan-isooctane dispersion system, putting terephthaloyl chloride, putting ethylenediamine as Lewis base, carrying out ultrasonic stirring, carrying out water bath heating for 1h, naturally cooling, and carrying out spray drying to obtain modified chitosan powder;
and step two, dispersing modified chitosan powder in distilled water, adjusting the pH value to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, carrying out ultrasonic stirring reaction for 30min, then slowly adding sodium carbonate, completing dropwise adding within 30min, raising the pH value to 10-12, eluting the solid matter obtained by filtering with distilled water for 3-5 times, and carrying out vacuum freeze drying to obtain the chitosan-copper oxide composite antibacterial agent.
According to the technical scheme, through the first step, amino in chitosan and terephthaloyl chloride are subjected to substitution reaction under the catalysis of Lewis base, and as the terephthaloyl chloride and chitosan have steric effect during the substitution reaction, only acyl chloride groups generally participate in the substitution reaction, the terminal part of the finally obtained modified chitosan powder is provided with more acyl chloride groups, the acyl chloride groups form carboxyl groups when meeting water in the second step, and the carboxyl groups have stronger water absorption, so that the chitosan-copper oxide composite antibacterial agent obtained in the second step has certain water absorption, and the chitosan-copper oxide composite antibacterial agent can obtain stronger water absorption performance while having stronger antibacterial spectrum, is beneficial to being applied to high-strength and high-performance concrete, and ensures that the performance of the concrete meets the requirements.
Preferably, in the preparation method of the chitosan-silver oxide composite antibacterial agent,
the material used in the first step comprises the following components in parts by weight:
8-12 parts of chitosan powder;
450 portions of isooctane and 650 portions of isooctane;
12-15 parts of terephthaloyl chloride;
5-10 parts of ethylenediamine;
the materials used in the step two are as follows in parts by weight:
11-13 parts of modified chitosan powder;
550 portions of deionized water and 650 portions;
3-4 parts of a copper sulfate solution;
15-28 parts of sodium carbonate.
In a second aspect, the present application provides a method for preparing an antibacterial admixture for high-strength high-performance concrete, comprising the following steps: the chitosan-copper oxide composite antibacterial agent is put into the polycarboxylic acid water reducing agent, stirred for 30min by ultrasonic waves, sequentially put into the fly ash, the hydroxymethyl cellulose, the bentonite and the polyacrylamide, and stirred to obtain a uniform mixture, namely the high-strength and high-performance concrete antibacterial additive.
By adopting the technical scheme, the obtained concrete antibacterial admixture has stronger water absorption, and can ensure that the performances of all aspects of concrete meet the requirements when being applied to the concrete.
In summary, the present application includes at least one of the following beneficial technical effects:
firstly, the antibacterial agent has better antibacterial performance and lasting antibacterial effect;
and secondly, the concrete admixture has better water absorption performance, and can greatly improve the strength of concrete under the condition of adding a small amount of the admixture.
Detailed Description
The materials of the examples are commercially available products, and are not limited herein.
Example 1
An antibacterial additive for high-strength and high-performance concrete is prepared by mixing the following components in parts by mass:
25 parts of a polycarboxylic acid water reducing agent;
25 parts of chitosan-copper oxide composite antibacterial agent;
15 parts of fly ash;
2 parts of hydroxypropyl methyl cellulose;
1 part of bentonite;
and 1 part of polyacrylamide.
In this embodiment, class I fly ash is selected as the fly ash.
The polyacrylamide of the embodiment adopts nonionic polyacrylamide.
In this example, organic bentonite was used as bentonite.
In this example, instant hydroxypropyl methylcellulose is used as hydroxypropyl methylcellulose.
In the chitosan-copper oxide composite antibacterial agent of the embodiment, the deacetylation degree of chitosan is 95%, and the molecular weight is 70000.
The preparation method of the chitosan-copper oxide composite antibacterial agent comprises the following steps:
dispersing chitosan powder in distilled water by ultrasonic wave, adjusting pH to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, reacting for 30min under ultrasonic stirring, slowly adding sodium carbonate, adding dropwise within 30min, increasing pH to 12, eluting solid matter obtained by filtering with distilled water for 3 times, and freeze-drying in vacuum to obtain the chitosan-copper oxide composite antibacterial agent.
The chitosan-copper oxide composite antibacterial agent comprises the following materials in parts by weight in the preparation process:
11 parts of chitosan powder;
550 parts of deionized water;
3 parts of copper sulfate solution;
28 parts of sodium carbonate.
The preparation method of the high-strength high-performance concrete antibacterial additive comprises the following steps: the chitosan-copper oxide composite antibacterial agent is put into the polycarboxylic acid water reducing agent, stirred for 30min by ultrasonic waves, sequentially put into the fly ash, the hydroxymethyl cellulose, the bentonite and the polyacrylamide, and stirred to obtain a uniform mixture, namely the high-strength and high-performance concrete antibacterial additive.
Example 2
The formulation and preparation method of this example are substantially the same as those of example 1, except that in the chitosan-copper oxide composite antibacterial agent of this example, the degree of deacetylation of chitosan is 90%, and the molecular weight is 50000.
Example 3
The formulation and preparation method of this example are substantially the same as those of example 1, except that in the chitosan-copper oxide composite antibacterial agent of this example, the degree of deacetylation of chitosan is 88%, and the molecular weight is 100000.
Example 4
The preparation method of this example is substantially the same as that of example 1 except that the recipe is different. Specifically, the high-strength high-performance concrete antibacterial admixture of the embodiment is prepared by mixing the following components in parts by mass:
15 parts of a polycarboxylic acid water reducing agent;
35 parts of chitosan-copper oxide composite antibacterial agent;
18 parts of fly ash;
1 part of hydroxypropyl methyl cellulose;
2 parts of bentonite;
in this embodiment, class I fly ash is selected as the fly ash.
In this example, organic bentonite was used as bentonite.
In this example, instant hydroxypropyl methylcellulose is used as hydroxypropyl methylcellulose.
In the chitosan-copper oxide composite antibacterial agent of the present example, the degree of deacetylation of chitosan was 92%, and the molecular weight was 90000.
The preparation method of the chitosan-copper oxide composite antibacterial agent comprises the following steps:
dispersing chitosan powder in distilled water by ultrasonic wave, adjusting pH to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, reacting for 30min under ultrasonic stirring, slowly adding sodium carbonate, adding dropwise within 30min, increasing pH to 11, eluting solid matter obtained by filtering with distilled water for 3-5 times, and freeze-drying under vacuum to obtain the chitosan-copper oxide composite antibacterial agent.
The chitosan-copper oxide composite antibacterial agent comprises the following materials in parts by weight in the preparation process:
12 parts of chitosan powder;
600 parts of deionized water;
3 parts of copper sulfate solution;
and 24 parts of sodium carbonate.
The preparation method of the high-strength high-performance concrete antibacterial additive comprises the following steps: the chitosan-copper oxide composite antibacterial agent is put into the polycarboxylic acid water reducing agent, stirred for 30min by ultrasonic waves, and then sequentially put into the fly ash, the hydroxymethyl cellulose and the bentonite, and stirred to obtain a uniform mixture, namely the high-strength and high-performance concrete antibacterial additive.
Example 5
The preparation method of this example is substantially the same as that of example 1 except that the recipe is different. Specifically, the high-strength high-performance concrete antibacterial admixture of the embodiment is prepared by mixing the following components in parts by mass:
24 parts of a polycarboxylic acid water reducing agent;
31 parts of a chitosan-copper oxide composite antibacterial agent;
17 parts of fly ash;
1 part of hydroxypropyl methyl cellulose;
and 1 part of polyacrylamide.
In this embodiment, class I fly ash is selected as the fly ash.
The polyacrylamide of the embodiment adopts nonionic polyacrylamide.
In the chitosan-copper oxide composite antibacterial agent of the embodiment, the deacetylation degree of chitosan is 96%, and the molecular weight is 65000.
The preparation method of the chitosan-copper oxide composite antibacterial agent comprises the following steps:
dispersing chitosan powder in distilled water by ultrasonic wave, adjusting pH to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, reacting for 30min under ultrasonic stirring, slowly adding sodium carbonate, adding dropwise within 30min, increasing pH to 10, eluting solid matter obtained by filtering with distilled water for 5 times, and freeze-drying under vacuum to obtain the chitosan-copper oxide composite antibacterial agent.
The chitosan-copper oxide composite antibacterial agent comprises the following materials in parts by weight in the preparation process:
11 parts of chitosan powder;
560 parts of deionized water;
3 parts of copper sulfate solution;
15 parts of sodium carbonate.
In the preparation method of the high-strength high-performance concrete antibacterial additive, the chitosan-copper oxide composite antibacterial agent is added into the polycarboxylic acid water reducing agent, the mixture is stirred for 30min by ultrasonic waves, the fly ash, the hydroxymethyl cellulose and the polyacrylamide are sequentially added, and the uniform mixture is obtained by stirring, namely the high-strength high-performance concrete antibacterial additive.
Example 6
The preparation method of this example is substantially the same as that of example 1 except that the recipe is different. Specifically, the high-strength high-performance concrete antibacterial admixture of the embodiment is prepared by mixing the following components in parts by mass:
26 parts of a polycarboxylic acid water reducing agent;
29 parts of chitosan-copper oxide composite antibacterial agent;
19 parts of fly ash;
in this embodiment, class I fly ash is selected as the fly ash.
In the chitosan-copper oxide composite antibacterial agent of the present example, the degree of deacetylation of chitosan was 93%, and the molecular weight was 75000.
The preparation method of the chitosan-copper oxide composite antibacterial agent comprises the following steps:
dispersing chitosan powder in distilled water by ultrasonic wave, adjusting pH to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, reacting for 30min under ultrasonic stirring, slowly adding sodium carbonate, adding dropwise within 30min until pH is raised to 11, eluting solid matter obtained by filtering with distilled water for 5 times, and freeze-drying in vacuum to obtain the chitosan-copper oxide composite antibacterial agent.
The chitosan-copper oxide composite antibacterial agent comprises the following materials in parts by weight in the preparation process:
12 parts of chitosan powder;
560 parts of deionized water;
4 parts of copper sulfate solution;
and 21 parts of sodium carbonate.
The preparation method of the high-strength high-performance concrete antibacterial additive comprises the following steps: and (3) putting the chitosan-copper oxide composite antibacterial agent into the polycarboxylic acid water reducing agent, performing ultrasonic stirring for 30min, putting the fly ash, and stirring to obtain a uniform mixture, namely the high-strength and high-performance concrete antibacterial additive.
Example 7
The preparation method of this example is substantially the same as that of example 1, except that the formulation is different and the preparation method of the chitosan-copper oxide composite antibacterial agent is different. Specifically, the high-strength high-performance concrete antibacterial admixture of the embodiment is prepared by mixing the following components in parts by mass:
16 parts of a polycarboxylic acid water reducing agent;
32 parts of a chitosan-copper oxide composite antibacterial agent;
16 parts of fly ash;
2 parts of hydroxypropyl methyl cellulose;
2 parts of bentonite;
and 2 parts of polyacrylamide.
In this embodiment, class I fly ash is selected as the fly ash.
The polyacrylamide of the embodiment adopts nonionic polyacrylamide.
In this example, organic bentonite was used as bentonite.
In this example, instant hydroxypropyl methylcellulose is used as hydroxypropyl methylcellulose.
In the chitosan-copper oxide composite antibacterial agent of this example, the degree of deacetylation of chitosan was 95%, and the molecule was 80000.
The preparation method of the chitosan-copper oxide composite antibacterial agent comprises the following steps:
putting chitosan powder and isooctane into a reaction kettle, dispersing chitosan by using ultrasonic dispersion stirring to form a chitosan-isooctane dispersion system, putting terephthaloyl chloride, putting ethylenediamine as Lewis base, carrying out ultrasonic stirring, carrying out water bath heating for 1h, naturally cooling, and carrying out spray drying to obtain modified chitosan powder;
and step two, dispersing modified chitosan powder in distilled water, adjusting the pH value to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, carrying out ultrasonic stirring reaction for 30min, then slowly adding sodium carbonate, after dropwise addition is completed within 30min, raising the pH value to 10, eluting the solid matter obtained by filtering with distilled water for 3 times, and carrying out vacuum freeze drying to obtain the chitosan-copper oxide composite antibacterial agent.
In the preparation method of the chitosan-silver oxide composite antibacterial agent of the embodiment,
the material used in the first step comprises the following components in parts by weight:
8 parts of chitosan powder;
450 parts of isooctane;
12 parts of terephthaloyl chloride;
5 parts of ethylenediamine;
the materials used in the step two are as follows in parts by weight:
13 parts of modified chitosan powder;
550 parts of deionized water;
4 parts of copper sulfate solution;
and 18 parts of sodium carbonate.
Example 8
The preparation method of this example is substantially the same as that of example 7 except that the recipe is different. Specifically, the high-strength high-performance concrete antibacterial admixture of the embodiment is prepared by mixing the following components in parts by mass:
30 parts of a polycarboxylic acid water reducing agent;
35 parts of chitosan-copper oxide composite antibacterial agent;
20 parts of fly ash;
2 parts of hydroxypropyl methyl cellulose;
and 2 parts of polyacrylamide.
In this embodiment, class I fly ash is selected as the fly ash.
The polyacrylamide of the embodiment adopts nonionic polyacrylamide.
In this example, instant hydroxypropyl methylcellulose is used as hydroxypropyl methylcellulose.
In the chitosan-copper oxide composite antibacterial agent of the present example, the deacetylation degree of chitosan was 92%, and the molecular weight was 60000.
The preparation method of the chitosan-copper oxide composite antibacterial agent comprises the following steps:
putting chitosan powder and isooctane into a reaction kettle, dispersing chitosan by using ultrasonic dispersion stirring to form a chitosan-isooctane dispersion system, putting terephthaloyl chloride, putting ethylenediamine as Lewis base, carrying out ultrasonic stirring, carrying out water bath heating for 1h, naturally cooling, and carrying out spray drying to obtain modified chitosan powder;
and step two, dispersing modified chitosan powder in distilled water, adjusting the pH value to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, carrying out ultrasonic stirring reaction for 30min, then slowly adding sodium carbonate, after dropwise addition is completed within 30min, raising the pH value to 12, eluting the solid matter obtained by filtering with distilled water for 5 times, and carrying out vacuum freeze drying to obtain the chitosan-copper oxide composite antibacterial agent.
In the preparation method of the chitosan-silver oxide composite antibacterial agent of the embodiment,
the material used in the first step comprises the following components in parts by weight:
12 parts of chitosan powder;
650 parts of isooctane;
13 parts of terephthaloyl chloride;
7 parts of ethylenediamine;
the materials used in the step two are as follows in parts by weight:
13 parts of modified chitosan powder;
590 parts of deionized water;
4 parts of copper sulfate solution;
28 parts of sodium carbonate.
Example 9
The preparation method of this example is substantially the same as that of example 7 except that the recipe is different. Specifically, the high-strength high-performance concrete antibacterial admixture of the embodiment is prepared by mixing the following components in parts by mass:
26 parts of a polycarboxylic acid water reducing agent;
33 parts of chitosan-copper oxide composite antibacterial agent;
15 parts of fly ash;
1 part of bentonite;
in this embodiment, class I fly ash is selected as the fly ash.
In this example, organic bentonite was used as bentonite.
In the chitosan-copper oxide composite antibacterial agent of the embodiment, the deacetylation degree of chitosan is 92%, and the molecular weight is 70000.
The preparation method of the chitosan-copper oxide composite antibacterial agent comprises the following steps:
putting chitosan powder and isooctane into a reaction kettle, dispersing chitosan by using ultrasonic dispersion stirring to form a chitosan-isooctane dispersion system, putting terephthaloyl chloride, putting ethylenediamine as Lewis base, carrying out ultrasonic stirring, carrying out water bath heating for 1h, naturally cooling, and carrying out spray drying to obtain modified chitosan powder;
and step two, dispersing modified chitosan powder in distilled water, adjusting the pH value to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, carrying out ultrasonic stirring reaction for 30min, then slowly adding sodium carbonate, after dropwise addition is completed within 30min, raising the pH value to 11, eluting the solid matter obtained by filtering with distilled water for 5 times, and carrying out vacuum freeze drying to obtain the chitosan-copper oxide composite antibacterial agent.
In the preparation method of the chitosan-silver oxide composite antibacterial agent of the embodiment,
the material used in the first step comprises the following components in parts by weight:
12 parts of chitosan powder;
450 parts of isooctane;
15 parts of terephthaloyl chloride;
10 parts of ethylenediamine;
the materials used in the step two are as follows in parts by weight:
11 parts of modified chitosan powder;
550 parts of deionized water;
3 parts of copper sulfate solution;
and 18 parts of sodium carbonate.
Example 10
The preparation method of this example is substantially the same as that of example 7, except that the formulation is different and the preparation method of the chitosan-copper oxide composite antibacterial agent is different. Specifically, the high-strength high-performance concrete antibacterial admixture of the embodiment is prepared by mixing the following components in parts by mass:
30 parts of a polycarboxylic acid water reducing agent;
35 parts of chitosan-copper oxide composite antibacterial agent;
20 parts of fly ash;
in this embodiment, class I fly ash is selected as the fly ash.
In the chitosan-copper oxide composite antibacterial agent of the embodiment, the deacetylation degree of chitosan is 94%, and the molecular weight is 90000.
The preparation method of the chitosan-copper oxide composite antibacterial agent comprises the following steps:
putting chitosan powder and isooctane into a reaction kettle, dispersing chitosan by using ultrasonic dispersion stirring to form a chitosan-isooctane dispersion system, putting terephthaloyl chloride, putting ethylenediamine as Lewis base, carrying out ultrasonic stirring, carrying out water bath heating for 1h, naturally cooling, and carrying out spray drying to obtain modified chitosan powder;
and step two, dispersing modified chitosan powder in distilled water, adjusting the pH value to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, carrying out ultrasonic stirring reaction for 30min, then slowly adding sodium carbonate, completing dropwise adding within 30min, raising the pH value to 10-12, eluting the solid matter obtained by filtering with distilled water for 3-5 times, and carrying out vacuum freeze drying to obtain the chitosan-copper oxide composite antibacterial agent.
In the preparation method of the chitosan-silver oxide composite antibacterial agent of the embodiment,
the material used in the first step comprises the following components in parts by weight:
10 parts of chitosan powder;
510 parts of isooctane;
14 parts of terephthaloyl chloride;
9 parts of ethylenediamine;
the materials used in the step two are as follows in parts by weight:
11 parts of modified chitosan powder;
550 parts of deionized water;
4 parts of copper sulfate solution;
and 21 parts of sodium carbonate.
Comparative example 1
The present comparative example used only the chitosan-copper oxide composite antibacterial agent as an additive, and the preparation method of the chitosan-copper oxide composite antibacterial agent of the present comparative example was identical to example 7.
Comparative example 2
In the additive of the comparative example, the chitosan-copper oxide composite antibacterial agent is not added, other ingredients are consistent with those in example 1, and the preparation method of the comparative example only needs to simply mix all the ingredients.
Comparative example 3
The comparative example used only a polycarboxylic acid water reducing agent as an admixture for concrete.
Preparation of a test sample:
the admixtures of examples 1 to 10 and comparative examples 1 to 3 were prepared as concrete test samples, and the formulation table included 100 parts of portland cement, 200 parts of sand, 50 parts of water, and 5 parts of an admixture, and the concrete test samples were prepared by thoroughly mixing and stirring the admixture with a mortar mixer.
The test of the test sample includes an antibacterial property test and a strength test, in which,
the antibacterial performance test is carried out by adopting a method of a microbial corrosion test in a patent authorization publication No. CN1307120C, and the size of a sample block is selected from a specification of 4cm by 10 cm.
The strength test comprises the compression strength and the cleavage strength, and the test method of the strength test is carried out according to GB/T50081-2002.
The results of the above tests are recorded in the following table:
from the above table the following conclusions can be drawn:
from the comparison of the antibacterial performances of examples 1 to 10 and comparative examples 1 to 3, it can be seen that the chitosan-copper oxide composite antibacterial agent of the present application has a better antibacterial effect;
from the comparison of the strength properties of examples 1-10 and comparative examples 1-3, it can be seen that the admixture obtained by the formulation of the present application can be used for making high-strength and high-performance concrete.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (10)
1. The antibacterial additive for the high-strength and high-performance concrete is characterized by being prepared by mixing the following components in parts by mass:
15-30 parts of a polycarboxylic acid water reducing agent;
25-35 parts of chitosan-copper oxide composite antibacterial agent;
15-20 parts of fly ash;
0-2 parts of hydroxypropyl methyl cellulose;
0-2 parts of bentonite;
0-2 parts of polyacrylamide.
2. The antibacterial admixture for high-strength high-performance concrete according to claim 1, which is characterized in that: the fly ash is I-grade fly ash.
3. The antibacterial admixture for high-strength high-performance concrete according to claim 1, which is characterized in that: the polyacrylamide is nonionic polyacrylamide.
4. The antibacterial admixture for high-strength high-performance concrete according to claim 1, which is characterized in that: the bentonite is organic bentonite.
5. The antibacterial admixture for high-strength high-performance concrete according to claim 1, which is characterized in that: the hydroxypropyl methyl cellulose is instant hydroxypropyl methyl cellulose.
6. The antibacterial admixture for high-strength high-performance concrete according to claim 1, which is characterized in that: in the chitosan-copper oxide composite antibacterial agent, the deacetylation degree of chitosan is more than or equal to 92%, and the molecular weight is between 60000 and 90000.
7. The antibacterial additive for high-strength and high-performance concrete according to claim 6, wherein the preparation method of the chitosan-copper oxide composite antibacterial agent is as follows:
dispersing chitosan powder in distilled water by ultrasonic wave, adjusting pH to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, reacting for 30min under ultrasonic stirring, adding sodium carbonate, adding dropwise within 30min, increasing pH to 10-12, eluting solid matter obtained by filtering with distilled water for 3-5 times, and freeze-drying under vacuum to obtain the chitosan-copper oxide composite antibacterial agent.
8. The antibacterial additive for high-strength and high-performance concrete according to claim 6, wherein the preparation method of the chitosan-copper oxide composite antibacterial agent is as follows:
putting chitosan powder and isooctane into a reaction kettle, dispersing chitosan by using ultrasonic dispersion stirring to form a chitosan-isooctane dispersion system, putting terephthaloyl chloride, putting ethylenediamine as Lewis base, carrying out ultrasonic stirring, carrying out water bath heating for 1h, naturally cooling, and carrying out spray drying to obtain modified chitosan powder;
and step two, dispersing modified chitosan powder in distilled water, adjusting the pH value to 5, adding 0.5mol/L copper sulfate solution under magnetic stirring, carrying out ultrasonic stirring reaction for 30min, then slowly adding sodium carbonate, completing dropwise adding within 30min, raising the pH value to 10-12, eluting the solid matter obtained by filtering with distilled water for 3-5 times, and carrying out vacuum freeze drying to obtain the chitosan-copper oxide composite antibacterial agent.
9. The antibacterial admixture for high-strength high-performance concrete according to claim 8, wherein: in the preparation method of the chitosan-silver oxide composite antibacterial agent,
the materials used in the step one are as follows in parts by weight:
8-12 parts of chitosan powder;
450 portions of isooctane and 650 portions of isooctane;
12-15 parts of terephthaloyl chloride;
5-10 parts of ethylenediamine;
the materials used in the step two are as follows in parts by weight:
11-13 parts of modified chitosan powder;
550 portions of deionized water and 650 portions;
3-4 parts of a copper sulfate solution;
15-28 parts of sodium carbonate.
10. The method for preparing the antibacterial additive for high-strength and high-performance concrete of any one of claims 1 to 9, which is characterized by comprising the following steps: the chitosan-copper oxide composite antibacterial agent is put into the polycarboxylic acid water reducing agent, stirred for 30min by ultrasonic waves, sequentially put into the fly ash, the hydroxymethyl cellulose, the bentonite and the polyacrylamide, and stirred to obtain a uniform mixture, namely the high-strength and high-performance concrete antibacterial additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010701945.1A CN111825371B (en) | 2020-07-20 | 2020-07-20 | Antibacterial additive for high-strength and high-performance concrete and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010701945.1A CN111825371B (en) | 2020-07-20 | 2020-07-20 | Antibacterial additive for high-strength and high-performance concrete and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111825371A true CN111825371A (en) | 2020-10-27 |
| CN111825371B CN111825371B (en) | 2022-07-22 |
Family
ID=72923721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010701945.1A Active CN111825371B (en) | 2020-07-20 | 2020-07-20 | Antibacterial additive for high-strength and high-performance concrete and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111825371B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608108A (en) * | 2020-12-31 | 2021-04-06 | 冀东水泥重庆混凝土有限公司 | High-performance concrete and preparation method thereof |
| CN112760266A (en) * | 2021-02-09 | 2021-05-07 | 黑龙江大学 | Bacillus preparation for hydraulic concrete and preparation method and application thereof |
| CN115746169A (en) * | 2022-12-13 | 2023-03-07 | 贵阳绿洲苑新材料有限公司 | Three-dimensional modified chitosan polymer and preparation method thereof |
| CN115785302A (en) * | 2022-12-23 | 2023-03-14 | 科之杰新材料集团有限公司 | Antiseptic for antibacterial monomer and concrete admixture and preparation method thereof |
| CN116496023A (en) * | 2023-04-23 | 2023-07-28 | 唐山冀东水泥外加剂有限责任公司 | Polycarboxylate superplasticizer and preparation method thereof |
| CN116573894A (en) * | 2023-05-27 | 2023-08-11 | 威海万佳源新型建材有限公司 | Granite concrete and preparation method thereof |
| CN116813238A (en) * | 2023-08-25 | 2023-09-29 | 邢台天泉商品混凝土有限责任公司 | Preparation process of organic fiber additive for concrete |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2012152257A (en) * | 2012-12-05 | 2014-06-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный строительный университет" (МГСУ) | DRY BUILDING MIX |
| CN105174799A (en) * | 2015-08-24 | 2015-12-23 | 湖州华仑助剂科技有限公司 | Roof concrete additive |
| CN105384463A (en) * | 2015-11-10 | 2016-03-09 | 当涂县科辉商贸有限公司 | Fireproof, antibacterial and mothproof autoclaved aerated concrete block and production method thereof |
| CN106007544A (en) * | 2016-06-02 | 2016-10-12 | 耿云花 | Antibacterial building concrete production process |
| CN106587855A (en) * | 2017-01-05 | 2017-04-26 | 蔡中元 | Anti-microbial and anti-corrosion concrete material for marine ecological engineering and preparation method for concrete material |
| CN109796146A (en) * | 2019-03-04 | 2019-05-24 | 东南大学 | A kind of hydrated cementitious controlled material and its preparation method and application |
-
2020
- 2020-07-20 CN CN202010701945.1A patent/CN111825371B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2012152257A (en) * | 2012-12-05 | 2014-06-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный строительный университет" (МГСУ) | DRY BUILDING MIX |
| CN105174799A (en) * | 2015-08-24 | 2015-12-23 | 湖州华仑助剂科技有限公司 | Roof concrete additive |
| CN105384463A (en) * | 2015-11-10 | 2016-03-09 | 当涂县科辉商贸有限公司 | Fireproof, antibacterial and mothproof autoclaved aerated concrete block and production method thereof |
| CN106007544A (en) * | 2016-06-02 | 2016-10-12 | 耿云花 | Antibacterial building concrete production process |
| CN106587855A (en) * | 2017-01-05 | 2017-04-26 | 蔡中元 | Anti-microbial and anti-corrosion concrete material for marine ecological engineering and preparation method for concrete material |
| CN109796146A (en) * | 2019-03-04 | 2019-05-24 | 东南大学 | A kind of hydrated cementitious controlled material and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| 张柏林: "《生物技术与食品加工》", 31 March 2005, 化学工业出版社 * |
| 李凤竹: "纳米氧化铜壳聚糖复合物处理后大青杨的耐腐性能", 《第三届中国林业学术大会论文集》 * |
| 蒋建新: "《功能性多糖胶开发与应用》", 31 January 2013, 中国轻工业出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608108A (en) * | 2020-12-31 | 2021-04-06 | 冀东水泥重庆混凝土有限公司 | High-performance concrete and preparation method thereof |
| CN112760266A (en) * | 2021-02-09 | 2021-05-07 | 黑龙江大学 | Bacillus preparation for hydraulic concrete and preparation method and application thereof |
| CN115746169A (en) * | 2022-12-13 | 2023-03-07 | 贵阳绿洲苑新材料有限公司 | Three-dimensional modified chitosan polymer and preparation method thereof |
| CN115746169B (en) * | 2022-12-13 | 2024-05-10 | 贵阳绿洲苑新材料有限公司 | Three-dimensional modified chitosan polymer and preparation method thereof |
| CN115785302A (en) * | 2022-12-23 | 2023-03-14 | 科之杰新材料集团有限公司 | Antiseptic for antibacterial monomer and concrete admixture and preparation method thereof |
| CN115785302B (en) * | 2022-12-23 | 2024-04-16 | 科之杰新材料集团有限公司 | Antiseptic for antibacterial monomer and concrete additive and preparation method thereof |
| CN116496023A (en) * | 2023-04-23 | 2023-07-28 | 唐山冀东水泥外加剂有限责任公司 | Polycarboxylate superplasticizer and preparation method thereof |
| CN116573894A (en) * | 2023-05-27 | 2023-08-11 | 威海万佳源新型建材有限公司 | Granite concrete and preparation method thereof |
| CN116573894B (en) * | 2023-05-27 | 2024-06-07 | 威海万佳源新型建材有限公司 | Granite concrete and preparation method thereof |
| CN116813238A (en) * | 2023-08-25 | 2023-09-29 | 邢台天泉商品混凝土有限责任公司 | Preparation process of organic fiber additive for concrete |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111825371B (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111825371B (en) | Antibacterial additive for high-strength and high-performance concrete and preparation method thereof | |
| CN109574538B (en) | Concrete glue reducing agent and preparation process and application method thereof | |
| CN103951330B (en) | A kind of bridge High-performance clean water concrete and preparation method thereof | |
| CN111072870A (en) | High-adaptability polycarboxylate superplasticizer and preparation method thereof | |
| CN103613307B (en) | Slump type polycarboxylate superplasticizer and preparation method thereof | |
| CN111153627A (en) | Anti-mud additive suitable for machine-made sand concrete and compounding method thereof | |
| CN115536307A (en) | Admixture for high-impermeability marine concrete and preparation method thereof | |
| CN111574105A (en) | Environment-friendly composite early strength water reducing agent and preparation method thereof | |
| CN110156398B (en) | High-strength concrete and preparation method thereof | |
| CN108218284A (en) | Cement water reducing agent composition | |
| JP4056828B2 (en) | Hydraulic composition | |
| CN104478285B (en) | A kind of it is applied to the activation reinforcing agent of cement concrete, purposes and preparation method thereof | |
| CN105601154A (en) | Graphene enhancer and preparation method thereof | |
| CN114920890B (en) | Viscosity-reducing additive and preparation method and application thereof | |
| CN106746948A (en) | A kind of premixing mortar of high-efficiency corrosion-resistant | |
| CN113912343B (en) | Building plastering mortar suitable for robot and preparation method thereof | |
| CN114149214A (en) | Early strength concrete and preparation method and application thereof | |
| CN107434386A (en) | A kind of antidetonation high-strength corrosion-resistant anti-dropout mortar | |
| CN112358228B (en) | Concrete glue reducing agent and preparation method thereof | |
| CN108863150B (en) | Composite additive for mechanical spraying plastering mortar | |
| CN114835433B (en) | Stone powder concrete regulator based on modified particles | |
| CN115521121B (en) | Corrosion-resistant cement mortar and preparation method thereof | |
| CN118184210B (en) | Efficient concrete crack-resistant additive and preparation method thereof | |
| CN116023062B (en) | Water-based synergist for concrete and preparation method thereof | |
| CN116589252A (en) | Composite efficient water-reducing concrete and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |