CN110015858B - High-performance retarding high-efficiency pumping aid and preparation method thereof - Google Patents
High-performance retarding high-efficiency pumping aid and preparation method thereof Download PDFInfo
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- CN110015858B CN110015858B CN201910429569.2A CN201910429569A CN110015858B CN 110015858 B CN110015858 B CN 110015858B CN 201910429569 A CN201910429569 A CN 201910429569A CN 110015858 B CN110015858 B CN 110015858B
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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
- C04B2103/34—Flow improvers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the field of building materials, and particularly relates to a high-performance retarding high-efficiency pumping aid and a preparation method thereof. The water reducing agent is prepared by performing epoxy propanol hyperbranched modification on a carbon nano tube, hydrolyzing and grafting the carbon nano tube with a vinyl-containing silane coupling agent, performing graft copolymerization with an unsaturated monomer of a polycarboxylic acid water reducing agent to form the water reducing agent with high-efficiency water reducing and slow-setting effects, and finally compounding the water reducing agent with other conventional pumping components. Compared with the existing pumping aid, the pumping aid disclosed by the invention does not need to additionally add a retarder, has excellent mud resistance, can obtain higher water reduction rate (35-40%) and mechanical strength (28d compressive strength can reach 80MPa) under the condition of smaller mixing amount, is simple in preparation method and high in production efficiency, and is convenient for industrial production.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to a high-performance retarding high-efficiency pumping aid and a preparation method thereof.
Background
The most essential performance characteristics of concrete are strength, and special building facilities such as high-rise buildings, large-span bridges and the like put better requirements on the strength of concrete. In recent years, carbon nanotubes have attracted much attention as a novel nanomaterial. The carbon nanotube can be regarded as a hollow carbon cage tube formed by a single layer or a plurality of extremely small cylindrical graphite sheets, and each carbon atom in the carbon nanotube is connected with three adjacent carbon atoms to form a hexagonal netThe bonding relationship between atoms of the complex structure is represented by SP2C = C and C-C covalent bonds formed by hybridization. The excellent combination mode enables the carbon nano tube to have strong axial strength, toughness and elastic modulus. Therefore, many studies have been made on the incorporation of carbon nanotubes into concrete in order to improve the flexural and compressive strength of the concrete. However, in the prior art, the carbon nanotubes are added into the concrete in the form of a single additive, and due to the huge specific surface area of the carbon nanotubes, the carbon nanotubes are easy to agglomerate and are difficult to be uniformly dispersed in the concrete, thereby seriously restricting the development of the field.
The pumping aid can improve the pumping performance of concrete mixtures and is usually prepared by compounding a water reducing component, a retarding component, an air entraining component, a pumping aid, a plastic retaining agent and the like. The water reducing agent is an additive capable of reducing water consumption and improving the strength of concrete or mortar under the condition of not influencing the workability of concrete or mortar mixture, and comprises a lignin water reducing agent, a naphthalene water reducing agent, a water-soluble resin water reducing agent, a molasses water reducing agent, a humate water reducing agent and a polycarboxylic acid water reducing agent. Compared with other water reducing agents, the polycarboxylic acid water reducing agent has strong dispersing effect on cement particles under the condition of lower using amount, and has obvious water reducing effect. The water reducing agent is adsorbed on the surface of cement particles in a comb shape, and the side chain extends into a liquid phase, so that the cement particles have obvious steric hindrance repulsion effect; meanwhile, a plurality of hydrophilic active groups (such as-OH, -O-, -COO-and the like) are arranged on the side chain, so that the affinity of the cement particles and water is increased, the solvation effect on the surfaces of the cement particles is enhanced, and a hydration film is thickened. Therefore, the water reducing agent has stronger hydration film lubrication and water reduction effects. As the polycarboxylic acid water reducing agent contains a large amount of hydroxyl (-OH), ether (-O-) and carboxyl (-COO-) in molecules, and the polar groups have stronger liquid-gas interface activity, the water reducing agent also has a certain effect of causing the water reduction of isolated balls. The water reducing rate of the polycarboxylic acid water reducing agent is more linear to the characteristic curve of the mixing amount, and the water reducing rate is generally 25-35 percent and can reach 40 percent at most. The polycarboxylic acid water reducing agent also has certain air-entraining property and retarding property. However, the polycarboxylic acid water reducing agent is sensitive to the sand and gravel mud content, and when the mud content in a concrete system is high, the polycarboxylic acid water reducing agent shows the phenomena of insufficient water reducing rate, large slump loss and the like, so how to effectively solve the problem that the polycarboxylic acid water reducing agent is sensitive to the sand and gravel mud content is an urgent need to be solved.
The inventor of the invention carries out a great deal of experimental research aiming at the technical problems and develops a high-performance retarding high-efficiency pumping agent for the first time. The water reducing agent is prepared by performing epoxy propanol hyperbranched modification on a carbon nano tube, hydrolyzing and grafting the carbon nano tube with a vinyl-containing silane coupling agent, performing graft copolymerization with an unsaturated monomer of a polycarboxylic acid water reducing agent to form the water reducing agent with high-efficiency water reducing and slow-setting effects, and finally compounding the water reducing agent with other conventional pumping components. After the carbon nano tube is subjected to epoxy propanol hyperbranched modification, the carbon nano tube can obviously open the agglomeration of adjacent molecules due to the existence of a large number of branched chains on the surface, and meanwhile, the carbon nano tube can be uniformly dispersed in concrete due to the fact that the epoxy propanol contains a large number of hydroxyl groups after ring opening, and has extremely strong hydrophilicity, and the existence of the hydroxyl groups can synergistically improve the water reducing and retarding effects of polycarboxylic acid and dilute the adsorption effect of clay on the polycarboxylic acid; in addition, due to the existence of a large number of branched chains, a certain steric hindrance is formed, and the adsorption of the clay on the polycarboxylic acid is hindered to a certain extent, so that the influence of the clay on the water reducing efficiency of the polycarboxylic acid is reduced. Compared with the existing pumping aid, the pumping aid disclosed by the invention does not need to additionally add a retarder, can obtain higher water reduction rate and mechanical strength under the condition of smaller mixing amount, and has higher economic and social meanings.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a high-performance retarding high-efficiency pumping agent and a preparation method thereof.
One of the purposes of the invention is to provide a high-performance retarding high-efficiency pumping aid, which is compounded by a polycarboxylate water reducing agent modified by epoxy propanol hyperbranched carbon nano tubes, a defoaming agent and an air entraining agent; wherein the addition amount of each component is as follows by weight:
10-25 parts of epoxy propanol hyperbranched carbon nanotube modified polycarboxylate superplasticizer
0.5-3 parts of defoaming agent
0.5-3 parts of air entraining agent
20-40 parts of water;
wherein the solid content of the epoxy propanol hyperbranched carbon nanotube modified polycarboxylate superplasticizer is 20-35 wt%.
Further, the defoaming agent is one of emulsified silicone oil, polyoxyethylene glyceryl ether and polydimethylsiloxane; the air entraining agent is sodium alkyl sulfonate.
The invention also aims to provide a preparation method of the high-performance retarding high-efficiency pumping aid, which comprises the following preparation steps:
(1) dispersing the carbon nano tube in water, adding mixed acid solution, heating and stirring at the temperature of 100 ℃ and 160 ℃ for reaction for 5-10h to obtain the oxidized carbon nano tube; in the process, the surface of the carbon nano tube is provided with a large number of oxygen-containing groups such as hydroxyl, carboxyl and the like;
(2) placing the carbon oxide nanotube obtained in the step (1) in a methanol solution of saturated potassium formate, performing ultrasonic treatment at room temperature for 1-4h to obtain a homogeneous dispersion liquid, performing reflux reaction at 50-100 ℃ for 2-4h, filtering after the reaction is finished, washing with methanol for several times, and performing vacuum drying; adding a proper amount of epoxy propanol into the carbon nano tube, reacting for 5-10h at 80-120 ℃, filtering and washing after the reaction is finished to obtain the hyperbranched carbon nano tube, wherein the reaction process is as follows:
(3) hydrolyzing a vinyl-containing silane coupling agent with the mass being 2 times that of the carbon nano tube in an acetic acid solution for 1-4 h; dispersing the hyperbranched carbon nano tube obtained in the step (2) in a mixed solvent of ethanol and water with the volume of 10-20 times, uniformly stirring, adding the hydrolyzed silane coupling agent solution, heating to 40-70 ℃, and reacting for 5-15h to graft vinyl on the hyperbranched carbon nano tube;
(4) copolymerizing the vinyl-containing hyperbranched carbon nano tube obtained in the step (3), polyether, methacrylic acid and sodium methallyl sulfonate in the presence of an initiator to obtain an epoxy propanol hyperbranched carbon nano tube modified polycarboxylic acid water reducing agent;
(5) and compounding 10-25 parts of epoxy propanol hyperbranched carbon nanotube modified polycarboxylic acid water reducing agent, 0.5-3 parts of defoaming agent, 0.5-3 parts of air entraining agent and 20-40 parts of water to obtain the high-performance retarding high-efficiency pumping aid.
Further, the carbon nanotube is a single-walled carbon nanotube or a multi-walled carbon nanotube.
Further, the mixed acid solution in the step (1) is a mixed solution of sulfuric acid and nitric acid, the molar ratio of the sulfuric acid to the nitric acid is 1:4-4:1, and the total acid concentration is 5-10 wt%.
Further, the addition amount of the epoxy propanol in the step (2) is 10-50wt% of the mass of the carbon nano tube.
Further, the silane coupling agent containing vinyl in the step (3) is one or more of vinyltriethoxysilane and vinyltrimethoxysilane.
Further, the polyether in the step (4) is one or more of isopentenyl polyoxyethylene ether (TPEG) and methallyl polyoxyethylene ether (HPEG); the initiator is ammonium persulfate or ferrous sulfate; the polymerization reaction temperature is 70-100 ℃ and the time is 1-5 h.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the carbon nano tube can form a large amount of hyperbranched branched chains on the surface of the carbon nano tube after ring-opening modification by the epoxypropanol, the agglomeration of adjacent molecules can be obviously opened by the large amount of branched chains, and meanwhile, the carbon nano tube can be uniformly dispersed in concrete due to the fact that the epoxypropanol contains a large amount of hydroxyl groups after ring-opening, and the carbon nano tube has extremely strong hydrophilicity; in addition, the existence of the hydroxyl can synergistically improve the water reducing and retarding effects of the polycarboxylic acid, dilute the adsorption effect of the clay on the polycarboxylic acid, and provide possibility for the hydrolytic condensation of a silane coupling agent so as to introduce an ethylene group; in addition, due to the existence of a large number of branched chains, a certain steric hindrance is formed, and the adsorption of the clay on the polycarboxylic acid is hindered to a certain extent, so that the influence of the clay on the water reducing efficiency of the polycarboxylic acid is reduced. Compared with the existing pumping aid, the pumping aid disclosed by the invention does not need to additionally add a retarder, can obtain higher water reduction rate (35-40%) and mechanical strength (28d compressive strength can reach 80MPa) under the condition of smaller mixing amount (1-1.8 wt%), and has higher economic and social meanings.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Dispersing carbon nanotubes in water, adding mixed acid solution, heating at 120 ℃, stirring and reacting for 5 hours to obtain oxidized carbon nanotubes;
(2) placing the carbon oxide nanotube obtained in the step (1) in a methanol solution of saturated potassium formate, performing ultrasonic treatment at room temperature for 3 hours to obtain a homogeneous dispersion liquid, performing reflux reaction at 80 ℃ for 2 hours, filtering after the reaction is finished, washing with methanol for 3 times, and performing vacuum drying; adding epoxy propanol accounting for 20wt% of the mass of the carbon nano tube into the carbon nano tube, reacting for 5 hours at 100 ℃, filtering and washing after the reaction is finished to obtain the hyperbranched carbon nano tube;
(3) taking vinyltriethoxysilane with 2 times of mass of the carbon nano tube to hydrolyze in an acetic acid solution for 2 hours; dispersing the hyperbranched carbon nanotube obtained in the step (2) in a mixed solvent of ethanol and water with the volume of 20 times, uniformly stirring, adding the hydrolyzed vinyl triethoxysilane solution, heating to 70 ℃, and reacting for 5 hours to graft vinyl on the hyperbranched carbon nanotube;
(4) copolymerizing the vinyl-containing hyperbranched carbon nanotube obtained in the step (3), methyl allyl polyoxyethylene ether, methacrylic acid and sodium methallyl sulfonate at 70 ℃ for 5 hours in the presence of initiator ammonium persulfate to obtain the epoxy propanol hyperbranched carbon nanotube modified polycarboxylic acid water reducer;
(5) and (3) compounding 15 parts of epoxy propanol hyperbranched carbon nanotube modified polycarboxylic acid water reducer, 0.8 part of defoaming agent, 0.8 part of air entraining agent and 30 parts of water to obtain the pumping aid of the embodiment 1, which is marked as S1, wherein the solid content of the polycarboxylic acid water reducer is 28%. The pumping aid is added into concrete in an amount of 1.5wt% of the total admixture of the binder, and the performance of the concrete is measured.
Example 2
(1) Dispersing carbon nanotubes in water, adding mixed acid solution, heating at 100 ℃, stirring and reacting for 10 hours to obtain oxidized carbon nanotubes;
(2) placing the carbon oxide nanotube obtained in the step (1) in a methanol solution of saturated potassium formate, performing ultrasonic treatment at room temperature for 3 hours to obtain a homogeneous dispersion liquid, performing reflux reaction at 80 ℃ for 2 hours, filtering after the reaction is finished, washing with methanol for 3 times, and performing vacuum drying; adding epoxy propanol accounting for 30wt% of the mass of the carbon nano tube into the carbon nano tube, reacting for 5 hours at 100 ℃, filtering and washing after the reaction is finished to obtain the hyperbranched carbon nano tube;
(3) taking 2 times of vinyl trimethoxy silane by mass of the carbon nano tube, and hydrolyzing in an acetic acid solution for 2 hours; dispersing the hyperbranched carbon nano tube obtained in the step (2) in a mixed solvent of ethanol and water with the volume of 20 times, uniformly stirring, adding the hydrolyzed vinyltrimethoxysilane solution, heating to 70 ℃, and reacting for 5 hours to graft vinyl on the hyperbranched carbon nano tube;
(4) copolymerizing the vinyl-containing hyperbranched carbon nanotube, isopentenyl polyoxyethylene ether, methacrylic acid and sodium methallyl sulfonate obtained in the step (3) for 5 hours at 50 ℃ in the presence of initiator ammonium persulfate to obtain the epoxy propanol hyperbranched carbon nanotube modified polycarboxylic acid water reducer;
(5) and (3) compounding 20 parts of epoxy propanol hyperbranched carbon nanotube modified polycarboxylic acid water reducing agent, 1 part of defoaming agent, 1 part of air entraining agent and 40 parts of water to obtain the pumping aid of the embodiment 2, which is recorded as S2, wherein the solid content of the polycarboxylic acid water reducing agent is 30%. The pumping aid is added into concrete in an amount of 1.8wt% of the total admixture of the binder, and the performance of the concrete is measured.
Comparative example 1
The common polycarboxylate superplasticizer, the defoaming agent and the air entraining agent which are mixed in the same amount as in the example 1 are compounded into a pumping agent, recorded as D1, and the pumping agent is mixed into concrete to measure the performance of the concrete.
Comparative example 2
The carbon nanotubes, the polycarboxylic acid water reducing agent, the defoaming agent and the air entraining agent which are mixed in the same amount as in example 1 are compounded into a pumping agent, and the pumping agent is mixed into concrete to measure the performance of the concrete.
Table 1 shows the performance parameters of the respective test samples
As can be seen from Table 1, the pumping aid obtained by the invention has higher water reduction rate, compressive strength and retarding efficiency compared with the common polycarboxylic acid pumping aid and the pumping aid doped with the carbon nano tubes.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the high-performance retarding high-efficiency pumping agent is characterized in that the pumping agent is prepared by compounding an epoxy propanol hyperbranched carbon nanotube modified polycarboxylic acid water reducing agent, a defoaming agent and an air entraining agent; wherein the addition amount of each component is as follows by weight:
10-25 parts of epoxy propanol hyperbranched carbon nanotube modified polycarboxylate superplasticizer
0.5-3 parts of defoaming agent
0.5-3 parts of air entraining agent
20-40 parts of water;
wherein the solid content of the epoxy propanol hyperbranched carbon nanotube modified polycarboxylate superplasticizer is 20-35 wt%;
the specific preparation method of the pumping agent comprises the following preparation steps:
(1) dispersing the carbon nano tube in water, adding mixed acid solution, heating and stirring at the temperature of 100 ℃ and 160 ℃ for reaction for 5-10h to obtain the oxidized carbon nano tube;
(2) placing the carbon oxide nanotube obtained in the step (1) in a methanol solution of saturated potassium formate, performing ultrasonic treatment at room temperature for 1-4h to obtain a homogeneous dispersion liquid, performing reflux reaction at 50-100 ℃ for 2-4h, filtering after the reaction is finished, washing with methanol for several times, and performing vacuum drying; adding a proper amount of epoxy propanol into the carbon nano tube, reacting for 5-10h at 80-120 ℃, filtering and washing after the reaction is finished to obtain the hyperbranched carbon nano tube;
(3) hydrolyzing a vinyl-containing silane coupling agent with the mass being 2 times that of the carbon nano tube in an acetic acid solution for 1-4 h; dispersing the hyperbranched carbon nano tube obtained in the step (2) in a mixed solvent of ethanol and water with the volume of 10-20 times, uniformly stirring, adding the hydrolyzed silane coupling agent solution, heating to 40-70 ℃, and reacting for 5-15h to graft vinyl on the hyperbranched carbon nano tube;
(4) copolymerizing the vinyl-containing hyperbranched carbon nano tube obtained in the step (3), polyether, methacrylic acid and sodium methallyl sulfonate in the presence of an initiator to obtain an epoxy propanol hyperbranched carbon nano tube modified polycarboxylic acid water reducing agent;
(5) and compounding 10-25 parts of epoxy propanol hyperbranched carbon nanotube modified polycarboxylic acid water reducing agent, 0.5-3 parts of defoaming agent, 0.5-3 parts of air entraining agent and 20-40 parts of water to obtain the high-performance retarding high-efficiency pumping aid.
2. The preparation method according to claim 1, wherein the defoaming agent is one of silicone emulsion, polyoxyethylene glyceryl ether, and polydimethylsiloxane; the air entraining agent is sodium alkyl sulfonate.
3. The method of claim 1, wherein the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes.
4. The preparation method according to claim 1, wherein the mixed acid solution in the step (1) is a mixed solution of sulfuric acid and nitric acid, the molar ratio of sulfuric acid to nitric acid is 1:4-4:1, and the total acid concentration is 5-10 wt%.
5. The method according to claim 1, wherein the amount of the epoxypropanol added in the step (2) is 10-50wt% of the mass of the carbon nanotubes.
6. The method according to claim 1, wherein the vinyl-containing silane coupling agent in step (3) is one or more of vinyltriethoxysilane and vinyltrimethoxysilane.
7. The preparation method according to claim 1, wherein the polyether in the step (4) is one or more of isopentenyl polyoxyethylene ether (TPEG) and methallyl polyoxyethylene ether (HPEG); the initiator is ammonium persulfate or ferrous sulfate; the polymerization reaction temperature is 70-100 ℃ and the time is 1-5 h.
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