CN109133701B - Micro-nano bubble air entraining agent for concrete and preparation method thereof - Google Patents
Micro-nano bubble air entraining agent for concrete and preparation method thereof Download PDFInfo
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- CN109133701B CN109133701B CN201810841260.XA CN201810841260A CN109133701B CN 109133701 B CN109133701 B CN 109133701B CN 201810841260 A CN201810841260 A CN 201810841260A CN 109133701 B CN109133701 B CN 109133701B
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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
- 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
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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
- C04B2103/304—Air-entrainers
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a micro-nano bubble air entraining agent for concrete and a preparation method thereof, wherein the micro-nano bubble air entraining agent for concrete comprises a main air entraining agent, a nonionic air entraining agent and a surfactant, the air entraining agent is added in the concrete stirring process, bubbles with the average particle size of less than 50 mu m can be generated, the bubbles are stable, and the change of the gas content of the concrete is less than 1% within 4 hours after water is added; the preparation method of the micro-nano bubble air entraining agent for the concrete comprises the following steps of (1) heating a surfactant and stirring at the same time, heating to 40-60 ℃, and (2) adding a nonionic air entraining agent, stirring uniformly, and cooling to normal temperature; (3) and adding the main air entraining agent, and stirring for 20-40min to obtain the air entraining agent.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a micro-nano bubble air entraining agent for concrete and a preparation method thereof.
Background
Micro-nano bubbles are introduced into the concrete, so that the workability, cohesiveness and durability of the low-grade concrete can be improved. The traditional air entraining agents comprise rosin air entraining agents, anionic air entraining agents, nonionic air entraining agents and combinations thereof, the rosin air entraining agents have insufficient air entraining amount, air bubbles introduced into concrete are unstable, the average particle size of the air bubbles is increased rapidly along with the extension of concrete mixing time in the distribution process of the concrete, and the rosin air entraining agents cannot be compatible with polycarboxylic acid water reducing agents, so that the practical application of the rosin air entraining agents is greatly limited; the anion air entraining agent is traditional K12, AOS and the like, the bubble structure is generally larger than 200 mu m, the bubbles larger than 200 mu m account for more than 80 percent of the whole bubbles, and a large amount of harmful bubbles are introduced into the concrete; although the nonionic air entraining agent can effectively introduce air bubbles, the average particle size of the air bubbles is more than 200 mu m and is larger than that of the air bubbles of the anionic air entraining agent, and the content of the introduced air bubbles is higher along with the longer concrete stirring time, so that the quality control in the actual production of the concrete is very unfavorable; there are combinations of anionic and non-ionic air entraining agents on the market, but achieving average particle sizes below 200 μm is still not possible or difficult to achieve.
Patent 201510507538.6 discloses a concrete air-entraining agent, which uses polyether as a hydrophilic chain segment, aliphatic hydrocarbon as a hydrophobic chain segment, and alkoxy silicon-based concrete air-entraining agent molecules are modified on the hydrophobic chain segment, so that the size distribution of air bubbles is improved, the beneficial air bubbles with the size of 20-200 μm are increased, and the size of the air bubbles still cannot meet the requirements of the workability, cohesiveness and durability of low-grade concrete.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the micro-nano bubble air entraining agent for the concrete, and the air entraining agent can introduce bubbles with the average particle size of below 50 microns into the concrete, so that the cohesiveness, the workability and the durability of the concrete are greatly improved; the invention also aims to provide a preparation method of the micro-nano bubble air entraining agent for concrete, which has the advantages of simple process, easy control and low production cost.
The purpose of the invention is realized by the following technical scheme: a micro-nano bubble air entraining agent for concrete comprises a main air entraining agent, a non-ionic air entraining agent and a surfactant for adjusting the molecular arrangement of a gas-liquid interface, wherein the structural formula of the main air entraining agent is shown as follows,
wherein R is1、R2Is straight-chain or isomeric alkanyl, R3、R4、R5、R6、R7、R8、R9、R10Is H or-SO3Z, Z are alkali metal ions, alkaline earth metal ions or-NH4 +。
The air entraining agent prepared by mutually matching the main air entraining agent, the nonionic air entraining agent and the surfactant is added in the concrete stirring process, so that air bubbles with the average particle size of less than 50 mu m can be generated, the air bubbles are stable, and the air content of the concrete is changed by less than 1% within 4 hours after water is added.
Further, the main air entraining agent, the nonionic air entraining agent and the surfactant respectively account for 1-98%, 1-98% and 1-98% of the air entraining agent by mass.
Further, the nonionic air entraining agent is one or a mixture of more of alkylphenol polyoxyethylene ether, alkyl alcohol polyoxyethylene ether and alkyl glucoside.
The nonionic air entraining agent disclosed by the invention is prepared by mutually matching one or more mixtures of alkylphenol polyoxyethylene ether, alkyl alcohol polyoxyethylene ether and alkyl glucoside, so that generated bubbles are rich and fine, the surface activity of the whole molecule can be increased, the concrete seal is easy to pump and not easy to bleed, and the cohesiveness and the durability are better.
Further, the proportions of the alkylphenol polyoxyethylene ether, the alkyl alcohol polyoxyethylene ether and the alkyl glycoside in the nonionic air entraining agent are respectively 1-98%, 1-98% and 1-98%.
Further, the surfactant is a propylene oxide and ethylene oxide block copolymer.
According to the invention, the propylene oxide and ethylene oxide block copolymer is used as the surfactant, so that the air entraining agent enables the concrete to have good fluidity and not easy to bleed when used in the concrete.
Furthermore, the molecular structure of the surfactant is simply shown in the specification,
further, wherein, 0.001<n1/n2<100,n1+n2≤500。
The invention adjusts the chain length relation of the block copolymer of propylene oxide and ethylene oxide to be 0.001<n1/n2<100,n1+n2Less than or equal to 500, so that the air entraining agent enables the concrete to have better fluidity and less bleeding when used in the concrete.
A preparation method of a micro-nano bubble air entraining agent for concrete comprises the following steps of (1) heating a surfactant and stirring at the same time, heating to 40-60 ℃, and (2) adding a nonionic air entraining agent, stirring uniformly, and cooling to normal temperature; (3) adding the main air entraining agent, and stirring for 20-40min to obtain the micro-nano bubble air entraining agent for concrete.
The preparation method has the advantages of simple process, easy control and good consistency of the prepared air entraining agent, and can introduce air bubbles with the average grain diameter of less than 50 mu m into the concrete during the adding of the air entraining agent, and the air bubbles are stable.
The invention has the beneficial effects that: (1) compared with the prior art, the grain diameter of the bubbles introduced into the cement is lower than 50 microns, so that the gas content is more stable in the production and distribution processes of the concrete, and the strength of the concrete is promoted; (2) the air entraining agent is used to ensure that concrete is easier to pump, is not easy to bleed, and has good cohesiveness, good fluidity and good durability; (3) the preparation method has the advantages of simple process, easy operation and low production cost.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Embodiment 1, a micro-nano bubble air entraining agent for concrete, comprising a main air entraining agent, a nonionic air entraining agent and a surfactant for adjusting the molecular arrangement of a gas-liquid interface, wherein the structural formula of the main air entraining agent is shown as follows,
wherein R is1、R2Is an isomeric alkanyl radical, R3、R4、R5、R6、R7、R8、R9、R10Is H.
Further, the mass fractions of the main air-entraining agent, the nonionic air-entraining agent and the surfactant in the air-entraining agent are respectively 98%, 1% and 1%.
Further, the nonionic air entraining agent is alkyl alcohol polyvinyl ether.
Further, the proportions of the alkylphenol polyoxyethylene ether, the alkyl alcohol polyoxyethylene ether and the alkyl glycoside in the nonionic air entraining agent are respectively 1%, 1% and 98%.
Further, the surfactant is a propylene oxide-ethylene oxide block copolymer.
Furthermore, the molecular structure of the surfactant is simply shown in the specification,
further, wherein n1/n2＝50,n1+n2＝500。
A preparation method of a micro-nano bubble air entraining agent for concrete comprises the following steps of (1) heating a surfactant while stirring, heating to 40 ℃, and (2) adding a nonionic air entraining agent, stirring uniformly, and cooling to normal temperature; (3) and adding the main air entraining agent, and stirring for 20min to obtain the micro-nano bubble air entraining agent for concrete.
Example 2
The difference between the embodiment 2 and the embodiment 1 is that the micro-nano bubble air entraining agent for concrete comprises a main air entraining agent, a nonionic air entraining agent and a surfactant for adjusting the molecular arrangement of a gas-liquid interface, wherein the structural formula of the main air entraining agent is shown as follows,
wherein R is1、R2Is a straight chain alkyl radical, R3、R4、R5、R6、R7、R8、R9、R10is-SO3Z and Z are alkali metal ions.
Further, the mass fractions of the main air-entraining agent, the nonionic air-entraining agent and the surfactant in the air-entraining agent are respectively 1%, 98% and 1%.
Further, the nonionic air entraining agent is alkylphenol polyoxyethylene ether.
Furthermore, the proportions of the alkylphenol polyoxyethylene ether, the alkyl alcohol polyoxyethylene ether and the alkyl glycoside in the nonionic air entraining agent are respectively 50%, 49% and 1%.
Further, the surfactant is a propylene oxide-ethylene oxide block copolymer.
Furthermore, the molecular structure of the surfactant is simply shown in the specification,
further, wherein n1/n2＝1,n1+n2＝250。
A preparation method of a micro-nano bubble air entraining agent for concrete comprises the following steps of (1) heating a surfactant while stirring, heating to 40 ℃, and (2) adding a nonionic air entraining agent, stirring uniformly, and cooling to normal temperature; (3) and adding the main air entraining agent, and stirring for 20min to obtain the micro-nano bubble air entraining agent for concrete.
Example 3
Example 3 differs from example 1 in that: a micro-nano bubble air entraining agent for concrete comprises a main air entraining agent, a non-ionic air entraining agent and a surfactant for adjusting the molecular arrangement of a gas-liquid interface, wherein the structural formula of the main air entraining agent is shown as follows,
wherein R is1、R2Is an isomeric alkanyl radical, R3、R4、R5、R6、R7、R8、R9、R10is-SO3Z and Z are alkaline earth metal ions.
Further, the mass fractions of the main air-entraining agent, the nonionic air-entraining agent and the surfactant in the air-entraining agent are respectively 25%, 50% and 25%.
Further, the nonionic air entraining agent is a mixture of alkyl alcohol polyvinyl ether and alkyl glycoside.
Furthermore, the proportions of the alkylphenol polyoxyethylene ether, the alkyl alcohol polyoxyethylene ether and the alkyl glycoside in the nonionic air entraining agent are respectively 25%, 25% and 50%.
Further, the surfactant is a propylene oxide-ethylene oxide block copolymer.
Furthermore, the molecular structure of the surfactant is simply shown in the specification,
further, wherein n1/n2＝0.001,n1+n2＝200。
A preparation method of a micro-nano bubble air entraining agent for concrete comprises the following steps of (1) heating a surfactant and stirring at the same time, heating to 60 ℃, and (2) adding a nonionic air entraining agent, stirring uniformly, and cooling to normal temperature; (3) and adding the main air entraining agent, and stirring for 40min to obtain the micro-nano bubble air entraining agent for concrete.
Example 4
Example 4 differs from example 1 in that: a micro-nano bubble air entraining agent for concrete comprises a main air entraining agent, a non-ionic air entraining agent and a surfactant for adjusting the molecular arrangement of a gas-liquid interface, wherein the structural formula of the main air entraining agent is shown as follows,
wherein R is1、R2Is a straight chain alkyl radical, R3、R4、R5、R6、R7、R8、R9、R10is-SO3Z, Z are-NH4 +。
Further, the mass fractions of the main air-entraining agent, the nonionic air-entraining agent and the surfactant in the air-entraining agent are respectively 1%, 1% and 98%.
Further, the nonionic air entraining agent is a mixture of alkylphenol polyoxyethylene ether, alkyl alcohol polyoxyethylene ether and alkyl glycoside.
Furthermore, the proportions of the alkylphenol polyoxyethylene ether, the alkyl alcohol polyoxyethylene ether and the alkyl glycoside in the nonionic air entraining agent are respectively 25%, 25% and 50%.
Further, the surfactant is a propylene oxide-ethylene oxide block copolymer.
Furthermore, the molecular structure of the surfactant is simply shown in the specification,
further, wherein n1/n2＝0.1,n1+n2＝100。
A preparation method of a micro-nano bubble air entraining agent for concrete comprises the following steps of (1) heating a surfactant and stirring at the same time, heating to 50 ℃, and (2) adding a nonionic air entraining agent, stirring uniformly, and cooling to normal temperature; (3) and adding the main air entraining agent, and stirring for 30min to obtain the micro-nano bubble air entraining agent for concrete.
After the concrete is solidified and sliced, the concrete is photographed and contrastively analyzed under a high power microscope, the average particle size of bubbles introduced into the concrete by using the micro-nano bubble air entraining agent for the concrete in the embodiment is less than 50 mu m, the bubbles are stable, and through testing, the gas content of the concrete changes by less than 1 percent within 4 hours after water is added.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (8)
1. A micro-nano bubble air entraining agent for concrete is characterized by comprising a main air entraining agent, a nonionic air entraining agent and a surfactant for adjusting the molecular arrangement of a gas-liquid interface, wherein the structural formula of the main air entraining agent is shown as follows,
wherein R is1、R2Is straight-chain or isomeric alkanyl, R3、R4、R5、R6、R7、R8、R9、R10Is H or-SO3Z, Z are alkali metal ions, alkaline earth metal ions or-NH4 +。
2. The micro-nano bubble air entraining agent for concrete according to claim 1, which is characterized in that: the main air entraining agent, the nonionic air entraining agent and the surfactant respectively account for 1-98 percent, 1-98 percent and 1-98 percent of the air entraining agent by mass.
3. The micro-nano bubble air entraining agent for concrete according to claim 1, which is characterized in that: the nonionic air entraining agent is one or a mixture of more of alkylphenol polyoxyethylene ether, alkyl alcohol polyoxyethylene ether and alkyl glucoside.
4. The micro-nano bubble air entraining agent for concrete according to claim 3, which is characterized in that: the proportions of the alkylphenol polyoxyethylene ether, the alkyl alcohol polyvinyl ether and the alkyl glycoside in the nonionic air entraining agent are respectively 1-98%, 1-98% and 1-98%.
5. The micro-nano bubble air entraining agent for concrete according to claim 1, which is characterized in that: the surfactant is a propylene oxide-ethylene oxide block copolymer.
6. The micro-nano bubble air entraining agent for concrete according to claim 5, which is characterized in that: the molecular structure of the surfactant is simply shown in the specification,
7. the micro-nano bubble air entraining agent for concrete according to claim 6, which is characterized in that: wherein, 0.001<n1/n2<100,n1+n2≤500。
8. The preparation method of the micro-nano bubble air entraining agent for concrete according to any one of claims 1 to 7, characterized by comprising the following steps: the method comprises the following steps of (1) heating a surfactant to 40-60 ℃ while stirring, and (2) adding a nonionic air entraining agent, stirring uniformly, and cooling to normal temperature; (3) adding the main air entraining agent, and stirring for 20-40min to obtain the micro-nano bubble air entraining agent for concrete.
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| CN112645631A (en) * | 2020-12-28 | 2021-04-13 | 江苏开放大学（江苏城市职业学院） | Antifreezing concrete composite water reducing agent and preparation method thereof |
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| JPS5313218B2 (en) * | 1973-06-26 | 1978-05-09 | ||
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| KR900002752B1 (en) * | 1986-06-11 | 1990-04-28 | 쌍용양회공업 주식회사 | Method for producing cement-additives |
| JP2001019517A (en) * | 1999-07-05 | 2001-01-23 | Toho Chem Ind Co Ltd | Admixture for concrete and mortar |
| JP5092214B2 (en) * | 2005-07-28 | 2012-12-05 | 日油株式会社 | Additive for cement |
| KR20130075334A (en) * | 2011-12-27 | 2013-07-05 | 재단법인 포항산업과학연구원 | Amorphous steel fiber cement composites and mortar products using the same |
| US9546110B2 (en) * | 2015-06-15 | 2017-01-17 | Gcp Applied Technologies Inc. | Superplasticizing admixture for cementitious compositions |
| CN106116230A (en) * | 2016-06-24 | 2016-11-16 | 桂林华越环保科技有限公司 | Concrete composite air entraining agent |
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