CN113087437B - Composite air entraining agent, preparation method thereof and cement-based material - Google Patents
Composite air entraining agent, preparation method thereof and cement-based material Download PDFInfo
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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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
- C04B28/02—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 containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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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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- 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
- C04B2111/76—Use at unusual temperatures, e.g. sub-zero
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The application relates to the technical field of building additives, and particularly discloses a composite air entraining agent, a preparation method thereof and a cement-based material, wherein the composite air entraining agent is prepared from a sulfonate air entraining agent and a polyether type cell structure regulator; the polyether type cell structure regulator is obtained by using glycerol as an initiator and copolymerizing any monomers of ethylene oxide, propylene oxide and 1, 2-butylene oxide, wherein the weight average molecular weight of the polyether type cell structure regulator is 1000-3000; the application also discloses a preparation method of the composite air entraining agent, which comprises the steps of uniformly mixing the raw materials to obtain a final product; the application also discloses a cement-based material which comprises the composite air entraining agent. The foam stability of the air entraining agent is improved, the composite air entraining agent with high air entraining efficiency and good air entraining agent stability is obtained, and the composite air entraining agent has better comprehensive performance in the aspects of foam entraining efficiency, strength, frost resistance and the like when being used for the cement-based material.
Description
Technical Field
The application relates to the technical field of concrete mortar, in particular to a composite air entraining agent, a preparation method thereof and a cement-based material.
Background
The air entraining agent is doped into the cement-based material such as mortar or concrete, so that the properties such as frost resistance, impermeability and the like of the cement-based material are improved by regulating and controlling the pore structure of the cement-based material, and the structure and the properties of a cement-based material product are greatly influenced, so that the quality control of the air content and the pore structure of the cement-based material is an important technology for preparing the high-performance cement-based material.
The concrete air entraining agent commonly used in the market comprises three types, namely a polyether air entraining agent, a rosin air entraining agent and an alkyl sulfonate air entraining agent. The polyether air entraining agent and the rosin air entraining agent have low air entraining efficiency, and although the alkyl sulfonate air entraining agent has high air entraining efficiency, the air entraining agent has the problem of poor bubble stability, and the introduced bubbles are not uniform, so that the obtained cement-based material has serious strength loss and low comprehensive performance.
Disclosure of Invention
In order to improve the foam stability of the air entraining agent and obtain the composite air entraining agent with high air entraining efficiency and good air entraining agent stability, the application provides the composite air entraining agent, the preparation method thereof and the cement-based material.
In a first aspect, the present application provides a composite air entraining agent, which adopts the following technical scheme:
the composite air entraining agent is prepared from a sulfonate air entraining agent and a polyether type cell structure regulator, wherein the addition amount of the polyether type cell structure regulator in the composite air entraining agent is 2-10%;
the polyether type cell structure regulator is obtained by using glycerol as an initiator and copolymerizing any several monomers of ethylene oxide, propylene oxide and 1, 2-butylene oxide, wherein the weight average molecular weight of the polyether type cell structure regulator is 1000-3000;
the epoxy resin composition comprises, by weight, 0-30 parts of ethylene oxide, 30-65 parts of propylene oxide and 5-40 parts of 1, 2-butylene oxide.
By adopting the technical scheme, the polyether type cell structure regulator obtained by copolymerizing glycerol serving as an initiator and ethylene oxide, propylene oxide and 1, 2-butylene oxide serving as monomers in the application has a special structure, particularly, a polyether polymer obtained by copolymerizing 1, 2-butylene oxide serving as a monomer has a special structure, and the proportion of 1, 2-butylene oxide in the polyether polymer is controlled, so that the composite air entraining agent obtained by compounding the polyether type cell structure with a specific structure and a small molecular weight and a sulfonate air entraining agent is stable in introduced bubble structure in a cement-based material, the introduced bubbles are fine and uniform, the air entraining efficiency is high, the problem of strength reduction caused when the air entraining agent is used for the cement-based material is solved, and the comprehensive performance of the air entraining agent is better.
Preferably, the sulfonate air entraining agent is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, alpha-alkenyl sodium sulfonate and fatty alcohol-polyoxyethylene ether sodium sulfate, and more preferably is alpha-alkenyl sodium sulfonate.
By adopting the technical scheme, the sulfonate air entraining agent adopts the alpha-alkenyl sodium sulfonate, so that the sulfonate air entraining agent has excellent hard water resistance, and the foam stabilizing effect after being compounded with the polyether type cell structure regulator is better.
Preferably, the polyether cell structure regulator is obtained by block copolymerization.
Preferably, the polyether type cell structure regulator is polymerized by the following method:
mixing glycerol and a catalyst, heating, stirring, heating to 90-120 ℃, sequentially adding propylene oxide, 1, 2-butylene oxide and ethylene oxide, maintaining the temperature at 90-120 ℃ for reaction until a polymer with the weight-average molecular weight of 1000-3000 is obtained by polymerization, and vacuumizing to remove low-boiling-point substances and water to obtain the polyether type cell structure regulator.
By adopting the technical scheme, the reaction rate of the polymerization reaction is controlled by controlling the temperature, the reaction is faster when the temperature is higher, but if the reaction temperature is too high, the implosion is easy to generate, the unsaturation degree of the obtained polymer is increased, and the safe operation is not facilitated.
Preferably, the catalyst is one or two of sodium hydroxide and potassium hydroxide, and the addition amount of the catalyst is 0.3-0.7% of the sum of the mass of the monomers.
By adopting the technical scheme, the polymerization reaction time is adjusted by controlling the addition amount of the catalyst, the addition of the catalyst is beneficial to improving the polymerization reaction speed, but if the addition amount of the catalyst is too high, the reaction speed can be greatly improved, but the unsaturation degree of the obtained polymerization product is obviously increased, and when the composite air entraining agent is applied to sulfonate air entraining agents, the air entraining efficiency, the strength and the frost resistance of the obtained composite air entraining agent are all reduced.
Preferably, after mixing the glycerol and the catalyst, the temperature is firstly raised to 80-100 ℃, and then the temperature is continuously raised to 90-120 ℃ after vacuumizing.
By adopting the technical scheme, in the polymerization process, the glycerin reacts with the catalyst such as sodium hydroxide and the like to generate water, and the polymerization of ethylene oxide, propylene oxide and 1, 2-butylene oxide is influenced, so that the water generated in the reaction process of the glycerin and the catalyst can be removed by heating to a certain temperature and then vacuumizing. In addition, the reaction of the epoxy compound and the glycerol begins to have an induction period, the polymerization reaction can be carried out at a lower temperature at the beginning, and the temperature is increased along with the reaction, so that the polymerization reaction is more favorably carried out.
Preferably, after the polymer with the weight-average molecular weight of 1000-3000 is obtained by polymerization, acid is added to neutralize the catalyst, and then the low-boiling-point substance and the water are removed by vacuum pumping, so as to prepare the polyether type cell structure regulator.
By adopting the technical scheme, the catalyst is alkaline substances such as sodium hydroxide and the like, acid is added to neutralize the catalyst, and then the catalyst is vacuumized to remove low-boiling-point substances and water to obtain the final product.
In a second aspect, the application provides a preparation method of a composite air entraining agent, which adopts the following technical scheme:
a preparation method of the composite air entraining agent comprises the following steps:
and uniformly mixing the sulfonate air entraining agent and the polyether type cell structure regulator to obtain the composite air entraining agent.
By adopting the technical scheme, the preparation method is simple and convenient, and industrialization is easy to realize.
In a third aspect, the present application provides a cement-based material, which adopts the following technical scheme:
the cement-based material is concrete or mortar, and comprises the composite air entraining agent, wherein the addition amount of the composite air entraining agent in the cement-based material is 0.05-0.08kg/m3。
By adopting the technical scheme, the obtained cement-based material has excellent frost resistance, workability and construction pumping performance by controlling the addition amount of the air entraining agent, and the strength of the cement-based material is prevented from being greatly reduced due to the fact that the addition amount of the air entraining agent is not appropriate.
In summary, the present application has the following beneficial effects:
1. when the polyether type cell structure regulator with a specific structure is obtained by polymerizing a monomer polymer comprising a 1, 2-butylene oxide monomer, and the composite air entraining agent obtained by compounding the polymer and the sulfonate air entraining agent is applied to a cement-based material, the air entraining efficiency is high, introduced bubbles are fine and uniform, the structure is stable, good frost resistance is achieved, and the phenomenon of strength reduction in the application of the existing sulfonate air entraining agent is improved;
2. the composite air entraining agent obtained in the application is applied to the cement-based material, and has high air entraining efficiency, excellent frost resistance, low strength loss rate of 50 times of freeze thawing and low quality loss rate of 50 times of freeze thawing, and small strength reduction amplitude.
Detailed Description
The present application is described in further detail below with reference to preparation examples, in which: the following preparation examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer, and the raw materials used in the following preparation examples can be obtained from ordinary commercial sources unless otherwise specified.
The air entraining agent is a surfactant which can introduce a large amount of evenly distributed micro-bubbles in the stirring process of a cement-based material (such as mortar or concrete) and can be kept in the air entraining agent after hardening, so that the performances of frost resistance, impermeability, workability and the like of the cement-based material can be obviously improved. The commonly used air entraining agents at present mainly comprise three types, namely a polyether air entraining agent, a rosin air entraining agent and a sulfonate air entraining agent.
The polyether air entraining agent and the rosin air entraining agent have low air entraining efficiency, and the sulfonate air entraining agent has relatively high air entraining efficiency and relatively low mixing amount, but the air entraining agent is mainly of a single-chain structure, one end of the air entraining agent is a hydrophobic group, and the other end of the air entraining agent is an ionic hydrophilic group.
The development of a composite initiator with high air entraining efficiency and good foam stability is urgently needed, when the composite initiator is applied to a cement-based material, the obtained cement-based material has good frost resistance, and the phenomenon of strength reduction of the existing sulfonate air entraining agent in application can be improved.
On the other hand, glycerin is used as an initiator, copolyether obtained by block copolymerization of ethylene oxide and propylene oxide can be used as a defoaming agent, and the inventor finds that the monomer is changed, the glycerin is used as the initiator, the ethylene oxide, the propylene oxide and the 1, 2-butylene oxide are added, particularly the copolyether obtained by copolymerization of the 1, 2-butylene oxide added into the monomer is compounded with the air entraining agent, so that large air bubbles introduced by the air entraining agent can be eliminated, and the introduced air bubble structure is adjusted, thereby improving the problem of strength reduction of a cement-based material caused by the addition of the air entraining agent, leading the cement-based material to have good anti-freezing effect, and improving the mechanical property of the cement-based material.
Compared with other air entraining agents such as rosin air entraining agents and the like, the sulfonate air entraining agent has high air entraining efficiency and small mixing amount, and the composite air entraining agent obtained by adding the obtained polyether type cell structure regulator and the sulfonate air entraining agent according to a certain proportion not only exerts the advantage of high air entraining efficiency, but also further improves the frost resistance when the polyether type cell structure regulator and the sulfonate air entraining agent are used in cement-based materials, and has better comprehensive performance.
Therefore, the following technical scheme is provided:
a composite air entraining agent is prepared by mixing a sulfonate air entraining agent and a polyether type cell structure regulator, considering that the sulfonate air entraining agent is in a powder state, the polyether type cell structure regulator is in a liquid state, and in order to better mix the sulfonate air entraining agent and the polyether type cell structure regulator, the composite air entraining agent with better performance is obtained, preferably, the mixture of the sulfonate air entraining agent and the polyether type cell structure regulator is prepared by mixing in a high-speed mixer, and the rotating speed of the high-speed mixer can be 200-800r/min, such as 200-500 r/min, 800r/min, more preferably 600-800r/min, such as 600-700 r/min, and 700r/min is taken as an example in the following embodiments.
The polyether cell structure regulator is added in the composite air entraining agent in an amount of 2 to 10 wt%, such as 2 wt%, such as 5 wt%, such as 10 wt%; more preferably from 5 to 8% by weight, for example 5% by weight, for example 6% by weight, for example 8% by weight, the combined properties of the composite air-entraining agent being better in this range.
The polyether type cell structure regulator takes glycerol as an initiator, is obtained by copolymerizing any monomers of ethylene oxide, propylene oxide and 1, 2-butylene oxide, and is preferably obtained by block copolymerization, the weight average molecular weight of the polyether type cell structure regulator is 1000-3000, more preferably 1500-2500, and the cement-based material applied by the composite air entraining agent with the weight average molecular weight is better in comprehensive performance.
And ethylene oxide is used in amounts of 0 to 30 parts, such as 0 part, for example 10 parts, such as 15 parts, for example 20 parts, such as 30 parts, calculated as parts by weight; propylene oxide is used in amounts of 30 to 65 parts, such as 30 parts, such as 40 parts, such as 50 parts, such as 60 parts, such as 65 parts; the 1, 2-butylene oxide is used in amounts of 5 to 40 parts, such as 5 parts, for example 15 parts, such as 20 parts, for example 30 parts, for example 40 parts.
More preferably, the ethylene oxide is used in an amount of 8 to 18 parts, such as 8 parts, for example 12 parts, such as 18 parts; the propylene oxide is used in an amount of 45 to 56 parts, such as 45 parts, such as 50 parts, such as 56 parts; the 1, 2-butylene oxide is used in an amount of 22 to 33 parts, such as 22 parts, such as 25 parts, such as 33 parts.
Specifically, the modified polyether type cell structure regulator is obtained by polymerizing the following methods:
mixing glycerol and a catalyst, heating, stirring, heating to 80-100 ℃ such as 80 ℃ such as 90 ℃ such as 100 ℃, vacuumizing, heating to 90-120 ℃ such as 90 ℃ such as 110 ℃ such as 120 ℃, sequentially adding propylene oxide, 1, 2-butylene oxide and ethylene oxide monomers, maintaining the temperature at 90-120 ℃ for reaction until a polymer with the weight-average molecular weight of 1000-3000 is obtained by polymerization, adding acid to neutralize the catalyst, and vacuumizing to remove low-boiling-point substances and water.
The catalyst is sodium hydroxide or potassium hydroxide, and the addition amount of the catalyst is 0.3-0.7%, such as 0.3%, such as 0.5%, such as 0.7% of the mass sum of the monomers; the propylene oxide, 1, 2-butylene oxide and ethylene oxide monomers are introduced in sequence; when the weight average molecular weight of the objective polymer product, polyether type cell structure regulator, is determined and the quality to be prepared is determined, the amount of the initiator glycerin is also determined.
The molecular formula of the polyether type cell structure regulator obtained by adopting the monomers and the polymerization method in the proportion is shown as the following formula I:
in the formula I, R is H or CH3Or CH2CH3X, y, z are each independently 1 to 15, and m, n, p are each independently 0 to 5.
When the composite air entraining agent is used in cement-based materials, particularly mortar or concrete, the addition amount is 0.05-0.08kg/m3For example 0.05kg/m3For example 0.06kg/m3For example 0.08kg/m3。
Preparation example 1
A preparation method of the composite air entraining agent comprises the following steps:
uniformly mixing a sulfonate air entraining agent and a polyether type cell structure regulator by using a high-speed mixer to obtain a composite air entraining agent, wherein the addition amount of the polyether type cell structure regulator in the composite air entraining agent is 2 wt%;
wherein the sulfonate air entraining agent is alpha-sodium alkenyl sulfonate;
the polyether type cell structure regulator is prepared by the following preparation method through block copolymerization:
mixing 9.2g of glycerol and a sodium hydroxide catalyst, stirring, heating to 80 ℃, vacuumizing, heating to 110 ℃, introducing 50.8g of propylene oxide, 15g of 1, 2-butylene oxide and 25g of ethylene oxide in sequence, reacting at 110 ℃ until 100g of polymer with the weight-average molecular weight of 1000 is obtained through polymerization, adding acid to neutralize the catalyst, and vacuumizing to remove low-boiling-point substances and water to obtain the low-boiling-point acrylic acid copolymer.
The amount of catalyst added was 0.3% of the sum of the masses of the monomers.
Preparation example 2
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 1, with the difference that,
uniformly mixing a sulfonate air entraining agent and a polyether type cell structure regulator by using a high-speed mixer to obtain a composite air entraining agent, wherein the addition amount of the polyether type cell structure regulator in the composite air entraining agent is 10 wt%;
the polyether type cell structure regulator is prepared by the following preparation method through block copolymerization:
mixing 3.1g of glycerol and a sodium hydroxide catalyst, stirring, heating to 100 ℃, vacuumizing, heating to 120 ℃, introducing 56.9g of propylene oxide, 15g of 1, 2-butylene oxide and 25g of ethylene oxide in sequence, reacting at 120 ℃ until 100g of polymer with weight-average molecular weight of 3000 is obtained by polymerization, adding acid to neutralize the catalyst, and vacuumizing to remove low-boiling-point substances and water to obtain the low-boiling-point acrylic acid copolymer.
The amount of catalyst added was 0.7% of the sum of the masses of the monomers.
Preparation example 3
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 1, with the difference that,
uniformly mixing a sulfonate air entraining agent and a polyether type cell structure regulator by using a high-speed mixer to obtain a composite air entraining agent, wherein the addition amount of the polyether type cell structure regulator in the composite air entraining agent is 5 wt%;
the polyether type cell structure regulator is prepared by the following preparation method through block copolymerization:
mixing 4.6g of glycerol and a sodium hydroxide catalyst, stirring, heating to 90 ℃, vacuumizing, heating to 110 ℃, introducing 55.4g of propylene oxide, 15g of 1, 2-butylene oxide and 25g of ethylene oxide in sequence, reacting at 110 ℃ until 100g of polymer with the weight-average molecular weight of 2000 is obtained through polymerization, adding acid to neutralize the catalyst, and vacuumizing to remove low-boiling-point substances and water to obtain the low-boiling-point acrylic acid copolymer.
The amount of catalyst added was 0.5% of the sum of the masses of the monomers.
Preparation example 4
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 3, and is characterized in that,
the polyether type cell structure regulator is prepared by the following preparation method through block copolymerization:
mixing 4.8g of glycerol and a sodium hydroxide catalyst, stirring, heating to 90 ℃, vacuumizing, heating to 110 ℃, introducing 50g of propylene oxide, 25g of 1, 2-butylene oxide and 25g of ethylene oxide in sequence, reacting at 110 ℃ until 104.8g of a polymer with the weight-average molecular weight of 2000 is obtained through polymerization, adding acid to neutralize the catalyst, and vacuumizing to remove low-boiling-point substances and water to obtain the low-boiling-point acrylic acid copolymer.
The amount of catalyst added was 0.5% of the sum of the masses of the monomers.
Preparation example 5
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 4, except that in the preparation step of the polyether type cell structure regulator, propylene oxide and 1, 2-butylene oxide monomers are sequentially introduced, the using amount of the propylene oxide is 55.4g, the using amount of the 1, 2-butylene oxide monomer is 40g, and the using amount of glycerin is 4.6g, and 100g of polymer with the weight-average molecular weight of 2000 is obtained through polymerization.
Preparation example 6
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 4, except that in the preparation step of the polyether type cell structure regulator, the using amount of ethylene oxide is 30g, the using amount of propylene oxide is 30g, the using amount of 1, 2-butylene oxide is 40g, and the using amount of glycerin is 4.8g, and 104.8g of polymer with the weight-average molecular weight of 2000 is obtained through polymerization.
Preparation example 7
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 4, except that in the preparation step of the polyether type cell structure regulator, the using amount of ethylene oxide is 30g, the using amount of propylene oxide is 60.4g, the using amount of 1, 2-butylene oxide is 5g, and the using amount of glycerin is 4.6g, and 100g of polymer with the weight-average molecular weight of 2000 is obtained through polymerization.
Preparation examples 8 to 11
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 4, and is characterized in that in the preparation step of the polyether type cell structure regulator, the dosage of 1, 2-butylene oxide is respectively 5g, 15g, 33g and 40g, the dosage of propylene oxide is respectively 63.3g, 56.7g, 44.7g and 40g, and the dosage of ethylene oxide is respectively 31.7g, 28.3g, 22.3g and 20 g; the amounts of glycerol used were all 4.8g, and polymerization gave 104.8g of a polymer having a weight-average molecular weight of 2000.
Preparation examples 12 to 14
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 4, except that in the preparation step of the polyether type cell structure regulator, the using amounts of glycerin are respectively 9.2g, 4.6g and 3.1g, polymers with weight average molecular weights of 1000, 2000 and 3000 are obtained through polymerization, and the mass of the obtained polymer is 100 g.
Preparation example 15
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 4, and is characterized in that in the preparation step of the polyether type cell structure regulator, the sulfonate air entraining agent is sodium dodecyl benzene sulfonate.
Preparation example 16
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 4, and is characterized in that in the step of preparing the polyether type cell structure regulator, the sulfonate air entraining agent is fatty alcohol-polyoxyethylene ether sodium sulfate.
Preparation example 17
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 4, and is characterized in that in the preparation step of the polyether type cell structure regulator, the sulfonate air entraining agent is prepared by selecting the components with the mass ratio of 1: sodium dodecylbenzenesulfonate and sodium α -alkenylsulfonate of 1.
Preparation examples 18 to 20
A preparation method of a composite air entraining agent is carried out according to the method in preparation example 4, and is characterized in that the addition amounts of a polyether type cell structure regulator in the composite air entraining agent are respectively 2 wt%, 8 wt% and 10 wt%.
The application also discloses a preparation method obtained in the preparation exampleThe cement-based material applied by the composite air entraining agent is mortar or concrete, and the addition amount of the composite air entraining agent in the cement-based material is 0.05-0.08kg/m3. The following examples are given by way of example of mortar, considering the consistency of the properties of mortar and concrete.
Examples
Examples 1 to 20
A preparation method of mortar comprises the steps of mixing cement, sand, fly ash, water and a composite air entraining agent to obtain the mortar, wherein the cement is P.O42.5-grade ordinary portland cement, the sand is medium sand in a II area, the fly ash is FII-grade fly ash, and the addition amount of the cement is 240kg/m3The addition amount of the sand was 1450kg/m3The addition amount of the fly ash is 60kg/m3The amount of water added was 270kg/m3The addition amount of the composite air entraining agent is 0.06kg/m3And the composite air entraining agents obtained in the preparation examples 1-20 are respectively selected as the composite air entraining agents.
Example 21
A mortar preparation method was carried out in accordance with the method of example 4, except that the amount of the composite air entraining agent added was 0.05kg/m3。
Example 22
A mortar preparation method was carried out in accordance with the method of example 4, except that the amount of the composite air-entraining agent added was 0.08kg/m3。
Comparative example
The following comparative examples are comparative examples of mortars.
Comparative example 1
A mortar preparation method is carried out according to the method in the embodiment 4, and the difference is that in the preparation step of the polyether type cell structure regulator in the composite air entraining agent, the sulfonate air entraining agent is replaced by a rosin air entraining agent, and specifically sodium abietate is selected.
Comparative example 2
A mortar preparation method is carried out according to the method of example 4, except that in the preparation step of the polyether type cell structure regulator in the composite air entraining agent, 1, 2-butylene oxide is not added into the monomer, and only ethylene oxide and propylene oxide are added.
Comparative example 3
A mortar preparation method was carried out in the same manner as in example 4 except that in the polyether cell structure regulator preparation step in the composite air entraining agent, 1, 2-butylene oxide was used in an amount of 3g, propylene oxide was used in an amount of 64.7g, ethylene oxide was used in an amount of 32.3g, and glycerin was used in an amount of 4.8g, and 104.8g of a polymer having a weight average molecular weight of 2000 was obtained by polymerization.
Comparative example 4
A mortar preparation method was carried out in the same manner as in example 4 except that in the polyether cell structure regulator preparation step in the composite air entraining agent, 45g of 1, 2-epoxybutane, 36.7g of propylene oxide, 18.3g of ethylene oxide and 4.8g of glycerin were polymerized to obtain 104.8g of a polymer having a weight average molecular weight of 2000.
Comparative example 5
A mortar preparation method was carried out in the same manner as in example 4, except that in the polyether cell structure adjusting agent preparation step in the composite air entraining agent, the amount of glycerin was 11.5g, and 100g of a polymer having a weight average molecular weight of 800 was polymerized.
Comparative example 6
A mortar preparation method was carried out in the same manner as in example 4, except that in the polyether cell structure adjusting agent preparation step in the composite air entraining agent, the amount of glycerin was 2.6g, and 100g of a polymer having a weight average molecular weight of 3500 was obtained by polymerization.
Comparative example 7
A mortar preparation method was carried out in the same manner as in example 4 except that the polyether cell structure regulator was added in an amount of 1 wt% in the composite air-entraining agent.
Comparative example 8
A mortar preparation method was carried out in the same manner as in example 4, except that the polyether cell structure regulator was added in an amount of 12% by weight in the composite air-entraining agent.
Comparative example 9
A mortar preparation method was carried out in accordance with the method of example 4, except that the amount of the composite air entraining agent added was 0.04kg/m3。
Comparative example 10
A mortar preparation method was carried out in accordance with the method of example 4, except that the amount of the composite air entraining agent added was 0.09kg/m3。
Comparative example 11
A preparation method of mortar is carried out according to the method of the embodiment 4, and is characterized in that a composite air entraining agent is not added into raw materials.
Comparative example 12
A preparation method of mortar is carried out according to the method of the embodiment 4, and is characterized in that the composite air entraining agent is replaced by alpha-sodium alkenyl sulfonate in the raw materials.
Comparative example 13
A preparation method of mortar is carried out according to the method of the embodiment 4, and is characterized in that the composite air entraining agent is replaced by the raw materials with the mass ratio of 1: 1, the alpha-sodium alkenyl sulfonate and the sodium abietate are compounded.
Performance detection
The air content of the mortars prepared in the above examples and comparative examples is detected, the detection method is performed according to JGJ/T70-2009 Standard test method for basic performance of building mortar, the specific detection items and detection results are shown in tables 1 and 2, table 1 is the detection result of the example, and table 2 is the detection result of the comparative example.
Table 1:
table 2:
as can be seen from the table 2, the mortar in the comparative example 11 is not added with the air entraining agent, although the compressive strength is good, the strength loss rate and the quality loss rate are both high after 50 times of freeze thawing, and the frost resistance is poor; the mortar in the comparative example 12 is added with the air entraining agent, and when the air entraining agent is selected from the commonly used alpha-sodium olefin sulfonate, the strength loss rate and the quality loss rate are greatly reduced after 50 times of freeze thawing, the frost resistance is obviously improved, and the compressive strength of the mortar can be detected to be reduced at the same time;
referring to the detection results in the examples, it can be seen that after the composite air entraining agent provided by the present application is added to the mortar, the frost resistance is further improved, the strength is also improved, the problem of strength reduction after the addition of the air entraining agent is significantly improved, although the air entraining rate is slightly reduced, the air entraining efficiency is basically not reduced, and the air entraining efficiency is high, and it can be seen that compared with the case of only adding the air entraining agent of alpha-alkenyl sodium sulfonate, although the initial air content is slightly reduced, the air content is relatively stable after 1 hour, the air entraining efficiency and the aging are better, and the comprehensive performance of the mortar is good.
Referring to the comparative example 1, when the sulfonate air-entraining agent is replaced by the rosin air-entraining agent in the composite air-entraining agent, the air-entraining efficiency is low, the frost resistance is low, and the compressive strength improvement effect of the mortar is small; in the comparative example 13, when the air entraining agent is prepared by compounding the common alpha-sodium alkenyl sulfonate and the sodium abietate, although the frost resistance is further improved, the problem that the compressive strength of the mortar is reduced is not solved;
the common types of sulfonate air entraining agents mainly include sodium dodecylbenzene sulfonate, sodium dodecylsulfate and sodium alpha-alkenyl sulfonate, the sodium dodecylbenzene sulfonate and sodium dodecylsulfate are sensitive to calcium and magnesium ions in water and are not hard water resistant, and the sodium alpha-alkenyl sulfonate is good in hard water resistance, and referring to the detection results of examples 15 to 17, it can be seen that when the sulfonate air entraining agent is sodium dodecylbenzene sulfonate or other sulfonate air entraining agents, the air entraining efficiency is lower and the strength reduction improvement effect is also reduced compared with the case of selecting sodium alpha-alkenyl sulfonate.
Referring to comparative example 2, 1, 2-butylene oxide is not used in the preparation of the monomer of the polyether type cell structure regulator in the composite air entraining agent, only ethylene oxide and propylene oxide are used, and the cell regulation effect cannot be achieved, so that the initial air content in the mortar is low, the air content is lower after 1 hour, the air entraining effect is poor, the freezing resistance is poor, and the strength is high.
Referring to the detection results of preparation examples 4, 8-11 and 3-4, the weight average molecular weights of the obtained polymers are all 2000, the amount of 1, 2-butylene oxide is changed, the total amount of the three monomers is kept the same as that of preparation example 4, and the ratio of propylene oxide to ethylene oxide is also the same as that of preparation example 4, the performance of the mortar is observed, and it can be seen that along with the increase of the amount of 1, 2-butylene oxide, namely the specific gravity of a butane unit in the final polymer is increased, the frost resistance of the mortar is slightly reduced after being increased, the improvement effect on strength reduction is increased firstly, and the change range is lower after being increased; when the using amount of the 1, 2-epoxybutane is too low or too high, the improvement effects of freezing resistance and strength reduction are poor;
referring to the test results of example 4, examples 12 to 14 and comparative examples 5 to 6, the amount of the three monomers is not changed, the weight average molecular weight of the polymer is changed by changing the amount of the glycerol, the frost resistance of the mortar is improved first and then reduced with the increase of the weight average molecular weight of the polymer, the strength reduction improvement effect is not obvious, and when the weight average molecular weight is too high or too low, the frost resistance of the mortar is not good and the strength reduction improvement effect is not obvious.
Referring again to the test results of example 4, examples 21 to 22 and comparative examples 9 to 10, it can be seen that the amount of the composite air entraining agent added to the mortar system is 0.05 to 0.08kg/m3When the addition amount is too small, the frost resistance is improved to a certain extent compared with the case of not adding an air entraining agent and adding a common air entraining agent, but the improvement range is low, the improvement effect on the problem of strength reduction is small, when the addition amount is too large, the compactness of the mortar is reduced, the strength is reduced, and the strength loss rate and the quality loss rate after 50 times of freeze thawing can be increasedAnd the frost resistance effect is poor.
Referring to the test results of example 4, examples 18 to 20 and comparative examples 7 to 8, it can be seen that the addition amount of the polyether cell structure regulator in the composite air entraining agent has a great influence on the performance of the composite air entraining agent, and as the specific gravity of the polyether cell structure regulator in the composite air entraining agent increases, the improvement effect on strength reduction increases firstly and then decreases, and the frost resistance of the composite air entraining agent also increases firstly and then decreases, and when the addition amount is too large or too small, the strength and the frost resistance are poor.
The specific preparation examples are only for explaining the application and are not limiting to the application, and those skilled in the art can make modifications without inventive contribution to the preparation examples as required after reading the specification, but are protected by patent laws within the scope of the claims of the application.
Claims (8)
1. The composite air entraining agent is characterized by being prepared from a sulfonate air entraining agent and a polyether type cell structure regulator, wherein the addition amount of the polyether type cell structure regulator in the composite air entraining agent is 2-10%;
the polyether type cell structure regulator is obtained by using glycerol as an initiator and copolymerizing any several monomers of ethylene oxide, propylene oxide and 1, 2-butylene oxide, wherein the weight average molecular weight of the polyether type cell structure regulator is 1000-3000;
the weight portion of the epoxy resin is that the usage of the ethylene oxide is 0-30 parts, the usage of the propylene oxide is 30-65 parts, and the usage of the 1, 2-butylene oxide is 5-40 parts;
the sulfonate air entraining agent is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, alpha-alkenyl sodium sulfonate and fatty alcohol-polyoxyethylene ether sodium sulfate;
the molecular formula of the polyether type cell structure regulator obtained by polymerization is shown as the following formula I:
in the formula I, R is H, CH3 or CH2CH3, x, y and z are respectively and independently 1-15, and m, n and p are respectively and independently 0-5.
2. The composite air entraining agent according to claim 1, characterized in that: the polyether type cell structure regulator is obtained through block copolymerization.
3. The composite air entraining agent according to claim 1, characterized in that: the polyether type cell structure regulator is obtained by polymerizing the following method:
mixing glycerol and a catalyst, heating, stirring, heating to 90-120 ℃, sequentially adding propylene oxide, 1, 2-butylene oxide and ethylene oxide, maintaining the temperature at 90-120 ℃ for reaction until a polymer with the weight-average molecular weight of 1000-3000 is obtained by polymerization, and vacuumizing to remove low-boiling-point substances and moisture to obtain the polyether-type cell structure regulator.
4. The composite air entraining agent according to claim 3, characterized in that: the catalyst is one or two of sodium hydroxide and potassium hydroxide, and the addition amount of the catalyst is 0.3-0.7% of the sum of the mass of the monomers.
5. The composite air entraining agent according to claim 3, characterized in that: mixing glycerin and catalyst, heating to 80-100 deg.c, vacuumizing and heating to 90-120 deg.c.
6. The composite air entraining agent according to claim 3, characterized in that: after the polymer with the weight-average molecular weight of 1000-3000 is obtained by polymerization, acid is added to neutralize the catalyst, and then the low-boiling-point substance and the water are removed by vacuum pumping, so as to prepare the polyether type cell structure regulator.
7. A method for preparing the composite air entraining agent according to any one of the claims 1 to 6, characterized in that: and uniformly mixing the sulfonate air entraining agent and the polyether type cell structure regulator to obtain the composite air entraining agent.
8. A cement-based material characterized by: the cement-based material is concrete or mortar, the cement-based material comprises the composite air entraining agent as defined in any one of claims 1-6, and the addition amount of the composite air entraining agent in the cement-based material is 0.05-0.08kg/m3。
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