CN114163578A - Viscosity-controlled polycarboxylate superplasticizer and preparation method thereof - Google Patents
Viscosity-controlled polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN114163578A CN114163578A CN202111335189.6A CN202111335189A CN114163578A CN 114163578 A CN114163578 A CN 114163578A CN 202111335189 A CN202111335189 A CN 202111335189A CN 114163578 A CN114163578 A CN 114163578A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- 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
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention relates to the field of concrete admixtures, in particular to a viscosity-controlled polycarboxylic acid water reducing agent and a preparation method thereof. The viscosity-regulating polycarboxylate superplasticizer comprises an unsaturated polyether monomer, unsaturated carboxylic acid, unsaturated amide, a viscosity regulating agent and a functional compound. Wherein the functional compound comprises at least one of unsaturated carboxylic acid/anhydride and unsaturated sulfonate; the viscosity regulator is prepared from an alcohol amine compound, an unsaturated ester monomer and an unsaturated phosphoric acid monomer. The polycarboxylate superplasticizer prepared by the invention has the advantages of low mixing amount, high water reducing rate, good workability, capability of remarkably reducing the viscosity of concrete slurry, wide application range of sand and stone mud content and the like, and has strong practical value and popularization value.
Description
Technical Field
The invention relates to the field of concrete admixtures, in particular to a viscosity-controlled polycarboxylic acid water reducing agent and a preparation method thereof.
Background
In recent years, with the increasing demand for strength and durability of concrete structures in large buildings, high-strength concrete having high overall strength and light dead weight has been widely used. Because the high-strength concrete adopts low water-cement ratio and a large amount of cementing materials, the viscosity of fresh concrete is often high, the flow rate is low, a series of challenges are brought to subsequent transportation, pumping, construction and the like, the development of the building material industry is greatly restricted, and the viscosity reduction research of the high-strength concrete at home and abroad is promoted to be continuously progressed. Therefore, starting from the core problems of the two concrete technical researches of material composition and mix proportion design, the viscosity reduction thought can be summarized as follows: the problems of high mixing viscosity, low flow rate and the like of the high-strength concrete are solved by optimizing material composition and adjusting the design of the mixing proportion.
At present, the viscosity reduction performance in the industrial application of high-strength concrete is realized mainly by three ways of increasing the mixing amount of a water reducing agent, selecting high-quality superfine powder and optimizing the grain composition. The increase of the mixing amount of the water reducing agent can not only increase the production cost, but also cause the problems of excessive slow setting of concrete, bleeding, bottom raking and the like, increase the construction difficulty and easily cause engineering accidents; the selection of high-quality ultrafine powder is limited by the locality and quality stability of the rubber material, and the optimization of the particle size distribution can improve the viscosity and the fluidity of the initial-mixed high-strength concrete to a certain extent, but the problem cannot be solved fundamentally.
Chinese patent document with publication number CN111138589A and publication number 2020, 5-month and 12-day discloses a concrete viscosity regulating agent and a preparation method and application thereof. The raw materials of the concrete viscosity regulating agent comprise a monomer and an initiator; the monomers include unsaturated acid, unsaturated amide and unsaturated organosilicon monomers. The concrete viscosity regulating agent endows the regulating agent with good affinity with cement particles and water reducing agent components in concrete by introducing hydration functional groups and silicon hydroxyl groups, so that the regulating agent is better suitable for the alkaline environment of the concrete and is beneficial to improving the workability of the concrete. However, the unsaturated organosilicon monomer adopted in the patent has a short molecular chain and has limited effect on cement particles in concrete.
Therefore, the viscosity reduction type polycarboxylate superplasticizer which effectively adapts to the mud content in the sand can be developed through the angle of molecular design, and has important significance for the development of concrete admixtures and the concrete industry.
Disclosure of Invention
In order to solve the problems of high production cost, insufficient adaptability to mud content and the like of the existing viscosity-reducing polycarboxylic acid water reducing agent, the invention provides a viscosity-regulating polycarboxylic acid water reducing agent which comprises an unsaturated polyether monomer, unsaturated carboxylic acid, unsaturated amide, a viscosity regulating agent and a functional compound.
Wherein the functional compound is at least one of unsaturated carboxylic acid/anhydride and unsaturated sulfonate;
the viscosity regulator is prepared from an alcohol amine compound, an unsaturated ester monomer and an unsaturated phosphoric acid monomer.
In one embodiment, the viscosity modifier is prepared as follows: dissolving an alcohol amine compound in isopropanol, heating to 30-50 ℃ under the atmosphere of nitrogen, reacting for 3-6 hours, adding an unsaturated ester monomer and an unsaturated phosphoric acid monomer through Michael addition, heating to 80-120 ℃ under the action of a catalyst and a polymerization inhibitor, and reacting for 4-6 hours to obtain the viscosity regulator.
In one embodiment, the alkanolamine compound is one or a combination of ethanolamine, diethanolamine, triethanolamine, isopropanolamine and isopropanolamine; the unsaturated ester monomer is one or a combination of hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, vinyl acetate and monoethyl maleate; the unsaturated phosphoric acid monomer is one or a combination of hydroxyethyl methacrylate phosphate, vinyl dimethyl phosphate and allyl dimethyl phosphate.
In one embodiment, the catalyst is one or a combination of 4-dimethylaminopyridine, concentrated sulfuric acid, ethylsulfonic acid concentrated sulfuric acid, heteropolyacids, stannous oxide, dibutyltin oxide, benzene sulfonic acid or p-toluene sulfonic acid; the polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, p-tert-butyl catechol or phenothiazine.
In one embodiment, the amount of the polymerization inhibitor is 0.5-6% of the mass of the alcohol amine monomer; the dosage of the catalyst is 0.1-8% of the mass of the unsaturated polyether monomer.
In one embodiment, the unsaturated carboxylic acid/anhydride is one or a combination of acrylic acid, acrylamide, methacrylic acid, maleic anhydride, itaconic acid, hydroxyethyl acrylate.
In one embodiment, the unsaturated sulfonate monomer is one or a combination of styrene sulfonic acid, p-styrene sulfonic acid, sodium propylene sulfonate, 2-acrylamide-2-methyl propane sulfonic acid, sodium methyl propylene sulfonate and sodium allyl sulfonate.
In one embodiment, the unsaturated polyether monomer is one or a combination of methallyl alcohol polyoxyethylene ether, isoamylene alcohol polyoxyethylene ether, allyl polyethylene glycol, 3-methyl-3-butene-1-polyethylene glycol, 2-methallyl polyethylene glycol, vinyl glycol ether and 4-hydroxybutyl vinyl ether.
Preferably, the molecular weight of the unsaturated polyether monomer is 600-3000.
In one embodiment, the unsaturated amide monomer is one or a combination of polyamide, N-dimethyl methylene acrylamide, N-methylene bisacrylamide, cyanoacetamide, acrylamide, cyclopropylamide and caprolactam.
In one embodiment, the unsaturated acid monomer is acrylic acid.
In one embodiment, the composition further comprises a chain transfer agent, wherein the chain transfer agent is one or a combination of thioglycolic acid, sodium hypophosphite, trisodium phosphate, mercaptopropionic acid, mercaptoethanol and mercaptoacetic acid.
Preferably, sodium methallyl sulfonate of the unsaturated sulfonate salt can be used as a chain transfer agent.
In one embodiment, the composition further comprises a reducing agent, wherein the reducing agent is one or a combination of sodium sulfite, sodium formaldehyde sulfoxylate, sodium bisulfite and sodium hypophosphite.
Preferably, sodium hypophosphite can be used as both a reducing agent and a chain transfer agent.
In one embodiment, the composition further comprises a sulfate, and the sulfate is one or a combination of ferric sulfate, ferrous sulfate, cuprous sulfate, copper sulfate, sodium sulfate, potassium sulfate and calcium sulfate.
Preferably, the sulfate is prepared into a solution with the mass concentration of 1-2%.
In one embodiment, the composition further comprises an oxidizing agent, and the oxidizing agent is one or a combination of hydrogen peroxide, sodium peroxide, potassium peroxide, magnesium peroxide, sodium persulfate, ammonium persulfate, sodium dichromate, potassium dichromate and potassium permanganate.
In one embodiment, the components are as follows in parts by mass:
the overall acid-ether ratio is 1.0 to 3.0.
In one embodiment, the unsaturated carboxylic acid/anhydride to viscosity modifier mass ratio is 1: 1.6 to 5.
A preparation method for preparing the viscosity-controlled polycarboxylate superplasticizer as described in any one of the above comprises the following steps:
b1: mixing unsaturated polyether monomer with water, fully dissolving and putting into a reaction container;
b2: adding a reducing agent, sulfate, unsaturated carboxylic acid and unsaturated amide into a B1 reaction container as a bottom material, and stirring until the reducing agent, the sulfate, the unsaturated carboxylic acid and the unsaturated amide are uniformly and fully dissolved;
b3: and (3) controlling the speed of the functional compound, the viscosity regulating agent aqueous solution, the oxidant aqueous solution and the chain transfer agent aqueous solution to be respectively dropwise added into the base material at a controlled speed, preserving the temperature after dropwise adding, adjusting the concentration, and adding liquid alkali for neutralization to obtain the viscosity regulating polycarboxylate superplasticizer.
Specifically, the detailed parameters and steps are as follows:
s1: mixing unsaturated polyether monomer with water, fully dissolving and putting into a reaction container;
s2: adding a reducing agent, sulfate, unsaturated carboxylic acid and unsaturated amide into an S1 reaction container as a bottom material, and stirring for 5-10 min to ensure uniform and sufficient dissolution;
s3: respectively dripping the A liquid functional compound, the viscosity regulator aqueous solution, the B liquid oxidant aqueous solution and the C liquid chain transfer agent aqueous solution into the backing material for 100-150 min; the reaction temperature is controlled to be 20-40 ℃; after the dripping is finished, keeping the temperature for 60-90 min; and then adding water for concentration regulation, and controlling the pH value to be 6.0-7.0 by using liquid caustic soda to obtain the viscosity regulation polycarboxylate superplasticizer.
The viscosity-controlled polycarboxylate superplasticizer provided by the invention has the following beneficial effects:
1. the method has the advantages of common and easily-obtained raw materials, low cost, simple and convenient preparation process, low temperature required by the copolymerization process, energy conservation and environmental protection.
2. The modified polyether is prepared by copolymerizing an unsaturated polyether monomer, an unsaturated acid monomer, unsaturated carboxylic acid/anhydride, unsaturated sulfonate, an unsaturated amide monomer and a viscosity regulator, and phosphate radical, carboxylate radical, ester radical, amide radical and sulfonic radical are introduced into the molecular structure of the polymer. Phosphate radical has strong adsorption capacity on cement and has a synergistic effect with carboxylate radical, so that the phosphate radical is favorable for wetting and adsorbing the cement and improving the dispersibility of concrete; meanwhile, ester group is continuously hydrolyzed in the cement hydration process and continuously reacts with cement hydration products to inhibit Ca (OH)2And AFt crystal nucleus growth, hydration speed reduction and cement hydration induction period extension, thereby playing a role in improving dispersion retentivity. The amido protects the carboxyl to a certain extent, reduces the initial adsorption rate of the carboxyl in the water reducing agent to cement particles, gradually hydrolyzes under an alkaline environment, releases the carboxyl, and continuously and slowly adsorbs the cement particles by the carboxyl, thereby showing good dispersibility. The sulfonic group forms a hydrogen bond with water of the slurry, and can also interfere the adsorption of the cement, thereby improving the dispersibility.
3. The formula system designed by the invention can enable the polymer to be slightly branched, and further improve the branching degree.
4. The polycarboxylic acid water reducing agent prepared by the invention has the advantages of low mixing amount, high water reducing rate, good workability, capability of obviously reducing the viscosity of slurry and the like.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and other advantages of the present invention can be realized and attained by means of the instrumentalities and combinations particularly pointed out in the specification and claims.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; the technical features designed in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any inventive step, are within the scope of the present invention.
In the description of the present invention, it is to be noted that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Preparation of viscosity control agent
Example 1
Dissolving 30g of ethanolamine in 60g of isopropanol, stirring for 10min under the nitrogen atmosphere, heating to 40 ℃ for reaction for 4h, adding 20g of hydroxyethyl acrylate and 20g of hydroxyethyl methacrylate phosphate in 1g of concentrated sulfuric acid and 0.2g of p-hydroxyanisole, heating to 100 ℃, reacting for 5h under the protection of nitrogen, and cooling to room temperature after the reaction is finished to prepare the viscosity regulator A.
Example 2
Dissolving 30g of diethanolamine amine in 60g of isopropanol, stirring for 10min under the nitrogen atmosphere, heating to 40 ℃ for reaction for 4h, adding 20g of hydroxyethyl acrylate, 20g of hydroxyethyl methacrylate phosphate in 1g of concentrated sulfuric acid and 0.2g of p-hydroxyanisole, heating to 100 ℃, reacting for 5h under the protection of nitrogen, and cooling to room temperature after the reaction is finished to prepare the viscosity regulator B.
Example 3
Dissolving 30g of diethanolamine amine in 60g of isopropanol, stirring for 10min under the nitrogen atmosphere, heating to 40 ℃ for reaction for 4h, adding 20g of methyl methacrylate, 20g of hydroxyethyl methacrylate phosphate in 1g of concentrated sulfuric acid and 0.2g of p-hydroxyanisole, heating to 100 ℃, reacting for 5h under the nitrogen protection, and cooling to room temperature after the reaction is finished to prepare the viscosity regulator C.
Example 4
Dissolving 30g of diethanolamine amine in 60g of isopropanol, stirring for 10min under the nitrogen atmosphere, heating to 40 ℃ for reaction for 4h, adding 20g of methyl methacrylate and 20g of allyl dimethyl phosphate in 1g of concentrated sulfuric acid and 0.2g of p-hydroxyanisole, heating to 100 ℃, reacting for 5h under the protection of nitrogen, and cooling to room temperature after the reaction is finished to prepare the viscosity regulator D.
Example 5
30g of diethanolamine amine is dissolved in 60g of isopropanol, stirred for 10min under the nitrogen atmosphere, heated to 40 ℃ for reaction for 4h, then 20g of methyl methacrylate, 20g of allyl dimethyl phosphate, 0.8g of 4-dimethylaminopyridine and 0.2g of p-hydroxyanisole are added, heated to 100 ℃, all the reactions are reacted for 5h under the protection of nitrogen, and the temperature is reduced to room temperature after the reaction is finished to prepare the viscosity regulator E.
Example 6
30g of diethanolamine amine is dissolved in 60g of isopropanol, stirred for 10min under the nitrogen atmosphere, heated to 40 ℃ for reaction for 4h, then 20g of methyl methacrylate, 20g of allyl dimethyl phosphate, 0.8g of 4-dimethylaminopyridine and 0.3g of hydroquinone are added, heated to 100 ℃, all the reactions are reacted for 5h under the protection of nitrogen, and the temperature is reduced to room temperature after the reaction is finished to prepare the viscosity regulator F.
Preparation of viscosity-controlled polycarboxylic acid water reducing agent
Example 7
200 parts of methallyl alcohol polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of acrylamide and 0.3 part of ferrous sulfate are added for standby. Preparing 20 parts of acrylic acid, 5 parts of viscosity regulator A and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; dripping A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is maintained at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 8
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of acrylamide and 0.3 part of ferrous sulfate are added for later use. Preparing 20 parts of acrylic acid, 4 parts of viscosity regulator A and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; dripping A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is maintained at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 9
Adding 200 parts of vinyl glycol ether and 130 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 20 ℃ to start reaction, and adding 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of acrylamide and 0.3 part of ferrous sulfate for later use. Preparing 20 parts of acrylic acid, 6 parts of viscosity regulator A and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; simultaneously dripping A, B, C solution into a four-neck flask for 120min, wherein the whole reaction temperature is kept at 10-40 ℃; and after the dripping is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 10
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of acrylamide and 0.3 part of ferrous sulfate are added for later use. Preparing 20 parts of acrylic acid, 5 parts of viscosity regulator B and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; dripping A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is maintained at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 11
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of acrylamide and 0.3 part of ferrous sulfate are added for later use. Preparing 20 parts of acrylic acid, 5 parts of viscosity regulator C and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; dripping A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is maintained at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 12
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of acrylamide and 0.3 part of ferrous sulfate are added for later use. Preparing 20 parts of acrylic acid, 5 parts of viscosity regulator D and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; dripping A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is maintained at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 13
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of acrylamide and 0.3 part of ferrous sulfate are added for later use. Preparing 20 parts of acrylic acid, 5 parts of viscosity regulator E and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; dripping A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is maintained at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 14
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of acrylamide and 0.3 part of ferrous sulfate are added for later use. Preparing 20 parts of acrylic acid, 5 parts of viscosity regulator F and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; dripping A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is maintained at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 15
Adding 300 parts of prenyl polyoxyethylene ether and 130 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 20 ℃ to start reaction, and adding 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of 2-acrylamide-2-methylpropanesulfonic acid and 0.3 part of ferrous sulfate for later use. Preparing 20 parts of methacrylic acid, 5 parts of viscosity regulator B and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; simultaneously dripping A, B, C solution into a four-neck flask for 120min, wherein the whole reaction temperature is kept at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 16
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of N, N-dimethyl methacrylamide and 0.3 part of ferrous sulfate are added for standby application. Preparing 20 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 5 parts of viscosity regulator B and 15 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; simultaneously dripping A, B, C solution into a four-neck flask for 120min, wherein the whole reaction temperature is kept at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 17
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of N, N-dimethyl methacrylamide and 0.3 part of ferrous sulfate are added for standby application. Preparing 20 parts of acrylic acid, 15 parts of p-styrene sulfonic acid, 5 parts of viscosity regulator B and 15 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; simultaneously dripping A, B, C solution into a four-neck flask for 120min, and keeping the whole reaction temperature at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Example 18
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of N, N-dimethyl methacrylamide and 0.3 part of ferrous sulfate are added for standby application. Preparing 20 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 5 parts of viscosity regulator B and 15 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of thioglycolic acid and 30 parts of water; simultaneously dripping A, B, C solution into a four-neck flask for 120min, wherein the whole reaction temperature is kept at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the viscosity-controlled polycarboxylate superplasticizer.
Comparative example 1
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of N, N-dimethyl methacrylamide and 0.3 part of ferrous sulfate are added for standby application. Preparing 20 parts of acrylic acid, 15 parts of sodium methallyl sulfonate and 15 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of thioglycolic acid and 30 parts of water; dripping the A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is kept at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the polycarboxylic acid water reducing agent.
Comparative example 2
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of N, N-dimethyl methacrylamide and 0.3 part of ferrous sulfate are added for standby application. Preparing a solution A from 35 parts of viscosity control agent A and 30 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of thioglycolic acid and 30 parts of water; dripping A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is maintained at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the polycarboxylic acid water reducer.
Comparative example 3
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of acrylamide and 0.3 part of ferrous sulfate are added for later use. Preparing 20 parts of acrylic acid, 3 parts of viscosity regulator A and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; dripping A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is maintained at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the polycarboxylic acid water reducer.
Comparative example 4
200 parts of prenyl polyoxyethylene ether and 130 parts of water are added into a four-neck flask, the temperature is raised to 30 ℃, pre-stirring is carried out for 10min to ensure uniform dissolution, then the temperature is reduced to 20 ℃ to start reaction, and 3.8 parts of sodium hypophosphite, 2 parts of acrylic acid, 1 part of acrylamide and 0.3 part of ferrous sulfate are added for later use. Preparing 20 parts of acrylic acid, 7 parts of viscosity regulator A and 30 parts of water into solution A; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.6 parts of sodium formaldehyde sulfoxylate and 30 parts of water; dripping A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 120min, and the whole reaction temperature is maintained at 10-40 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, supplementing 15 parts of water, and controlling the pH value to be 6.0-7.0 by using liquid alkali to obtain the polycarboxylic acid water reducer.
Comparative example 5
A commercially available polycarboxylic acid water reducing agent.
The polycarboxylic acid water reducer samples obtained by synthesis in examples 1-18 and comparative example 1 and a commercially available polycarboxylic acid water reducer are tested for initial slump and expansion, as well as time lapse slump and expansion, and the emptying time of a slump bucket for time lapse slump according to GB8076-2008 concrete admixture, GB 8077-2012 concrete admixture homogeneity test method and GJ281-2012 high-strength concrete application technical specification by adopting red lion cement (P.O 42.5), machine-made sand and crushed stone. Concrete and its production methodThe mixing ratio is as follows: 380kg/m cement380kg/m of fly ash (II level)350kg/m of mineral powder3750 kg/m of sand3980kg/m of stone3The initial spreading degree was controlled at 650. + -.30 mm, and the results are shown in Table 1.
TABLE 1 concrete application Properties
The experimental results of examples 1 to 18 and comparative examples 1 to 5 show that the initial extension degree of the viscosity-controlled polycarboxylate water reducer prepared by the invention is controlled in concrete experiments, and the mixing amount of the water reducer used in each example is far lower than that of the comparative examples. Meanwhile, under the condition that the mixing amount is lower than that of the comparative examples 1-5, the emptying time required by the examples 7-18 is still shorter than that of the comparative examples, which shows that the application performance of the concrete using the water reducing agent of the examples is far better than that of the comparative examples, and the superiority of the viscosity-controlled polycarboxylic acid water reducing agent is reflected. In addition, compared with the commercial polycarboxylate superplasticizers in the comparative example 5, the concrete strength performances of the concrete in the examples 7 to 18 are not inferior, and even have better performances, so that the viscosity-controlled polycarboxylate superplasticizer provided by the invention has very high practical value and popularization value.
As can be seen from the comparative example 1 and the example 7, in the formula system, the viscosity regulator is not added, the whole water reducer cannot form a slightly branched structure, and the prepared water reducer has poor effect and cannot meet the requirements. In contrast, as can be seen from comparison of comparative example 2 with example 7, the use of the viscosity modifier instead of the unsaturated carboxylic acid and the unsaturated sulfonate makes the carboxylic acid and the sulfonic acid groups in the whole formulation insufficient, and also affects the performance of the water reducer. Meanwhile, the comparative examples 3-4 show that the water reducing agent can not meet the requirements due to too much or too little viscosity regulating agent, the viscosity regulating agent needs to be in a control range, the whole water reducing agent can achieve the expected light branching effect, and the water reducing agent can achieve the expected performance by the combined action of all functional groups in the whole formula.
From the examples 7 to 9, it can be seen that the viscosity-controlled polycarboxylate water reducer synthesized by the invention can also adapt to various polyether macromonomers under the condition of using different polyether macromonomers, can be selectively prepared according to actual conditions, and has a wide application range.
Meanwhile, as can be seen from the examples 7 and 10 to 14, the viscosity regulating agent prepared from different raw materials is adopted in each example, and the viscosity regulating agent prepared from the viscosity regulating polycarboxylic acid water reducing agent can achieve the expected effect, and has a better water reducing and viscosity reducing effect. The viscosity-controlled polycarboxylate superplasticizer provided by the invention has the advantages of many raw material sources, good effect and strong practical value.
As can be seen from the examples 7 and 15 to 18, the unsaturated carboxylic acid/anhydride and the unsaturated sulfonate with different components and ratios are used in the formula system, so that the formula system can be adapted to, and the water reducing and viscosity reducing performance is further enhanced.
In conclusion, the viscosity-controlled polycarboxylate superplasticizer prepared by the invention has good viscosity-reducing performance, can effectively improve the workability of concrete, has no adverse effect on mechanical performance, is wide in suitability, quick to prepare and high in efficiency, and has strong practical value and popularization value.
In addition, it will be appreciated by those skilled in the art that, although there may be many problems with the prior art, each embodiment or aspect of the present invention may be improved only in one or several respects, without necessarily simultaneously solving all the technical problems listed in the prior art or in the background. It will be understood by those skilled in the art that nothing in a claim should be taken as a limitation on that claim.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The viscosity-controlled polycarboxylate superplasticizer is characterized in that: comprises unsaturated polyether monomer, unsaturated acid monomer, unsaturated amide, viscosity regulator and functional compound;
wherein the functional compound comprises at least one of unsaturated carboxylic acid/anhydride and unsaturated sulfonate;
the viscosity regulator is prepared from an alcohol amine compound, an unsaturated ester monomer and an unsaturated phosphoric acid monomer.
2. The viscosity-controlling polycarboxylate superplasticizer according to claim 1, characterized in that: the preparation process of the viscosity regulator is as follows: dissolving the alcamines compound in isopropanol, heating to react T under the atmosphere of nitrogen1h, adding unsaturated ester monomers and unsaturated phosphoric acid monomers through Michael addition, and heating to react T under the action of a catalyst and a polymerization inhibitor2h, obtaining the viscosity regulating agent.
3. The viscosity-controlling polycarboxylate superplasticizer according to claim 1, characterized in that: the alcohol amine compound is one or a combination of ethanolamine, diethanolamine, triethanolamine, isopropanolamine and isopropanolamine; the unsaturated ester monomer is one or a combination of hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, vinyl acetate and monoethyl maleate; the unsaturated phosphoric acid monomer is one or a combination of hydroxyethyl methacrylate phosphate, vinyl dimethyl phosphate and allyl dimethyl phosphate.
4. The viscosity-controlling polycarboxylate superplasticizer according to claim 1, characterized in that: the unsaturated carboxylic acid/anhydride is one or a combination of acrylic acid, acrylamide, methacrylic acid, maleic anhydride, itaconic acid and hydroxyethyl acrylate.
5. The viscosity-controlling polycarboxylate superplasticizer according to claim 1, characterized in that: the unsaturated sulfonate monomer is one or a combination of styrene sulfonic acid, p-styrene sulfonic acid, sodium propylene sulfonate, 2-acrylamide-2-methylpropanesulfonic acid, sodium methallyl sulfonate and sodium allyl sulfonate.
6. The viscosity-controlling polycarboxylate superplasticizer according to claim 1, characterized in that: the unsaturated polyether monomer is one or a combination of methyl allyl alcohol polyoxyethylene ether, isopentenol polyoxyethylene ether, allyl polyethylene glycol, 3-methyl-3-butylene-1-polyethylene glycol, 2-methyl allyl polyethylene glycol, vinyl glycol ether and 4-hydroxybutyl vinyl ether.
7. The viscosity-controlling polycarboxylate superplasticizer according to claim 1, characterized in that: the unsaturated amide monomer is one or a combination of polyamide, N-dimethyl methacrylamide, N-methylene bisacrylamide, cyanoacetamide, acrylamide, cyclopropylamide and caprolactam; the unsaturated acid monomer is acrylic acid.
8. The viscosity-controlling polycarboxylate superplasticizer according to claim 1, characterized in that: the component also comprises a chain transfer agent which is one or the combination of thioglycolic acid, sodium hypophosphite, trisodium phosphate, mercaptopropionic acid, mercaptoethanol and mercaptoacetic acid.
9. The viscosity-controlling polycarboxylate superplasticizer according to claim 1, characterized in that: the weight portions of the components are as follows:
the overall acid-ether ratio is 1.0 to 3.0.
10. The preparation method for preparing the viscosity-controlled polycarboxylate superplasticizer according to any one of claims 1 to 9 is characterized by comprising the following steps:
a1: mixing unsaturated polyether monomer with water, fully dissolving and putting into a reaction container;
a2: adding a reducing agent, sulfate, unsaturated carboxylic acid and unsaturated amide into A1 as a base material, and stirring until the reducing agent, the sulfate, the unsaturated carboxylic acid and the unsaturated amide are uniformly and fully dissolved;
a3: and (3) controlling the speed of the functional compound, the viscosity regulating agent aqueous solution, the oxidant aqueous solution and the chain transfer agent aqueous solution to be respectively dropwise added into the base material at a controlled speed, preserving the temperature after dropwise addition, regulating the concentration, and adding liquid alkali for neutralization to obtain the viscosity regulating polycarboxylate superplasticizer.
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