CN114031728A - High-water-reduction-type EPEG polycarboxylic acid water reducer and preparation method thereof - Google Patents
High-water-reduction-type EPEG polycarboxylic acid water reducer and preparation method thereof Download PDFInfo
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- 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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- 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
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
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Abstract
The invention relates to the field of concrete admixtures, in particular to a high water-reducing EPEG polycarboxylic acid water reducing agent and a preparation method thereof. Wherein, the high water-reducing EPEG polycarboxylic acid water reducing agent comprises ethylene glycol monovinyl polyethylene glycol ether (EPEG), unsaturated acid monomers, amide polymers, unsaturated carboxylic acid/anhydride, unsaturated sulfonate and a functional regulator; wherein the functional regulator is a polymer of an unsaturated alcohol amine compound, an unsaturated ester monomer and an unsaturated phosphoric acid monomer. The high water-reducing EPEG polycarboxylic acid water reducing agent provided by the invention has low temperature requirement, wide suitability, fast preparation and high efficiency, has high water reducing property and good dispersibility compared with similar products, and can solve the problems of poor workability and over-fast loss in concrete raw materials.
Description
Technical Field
The invention relates to the field of concrete admixtures, in particular to a high water-reducing EPEG polycarboxylic acid water reducing agent and a preparation method thereof.
Background
The concrete admixture is one of indispensable components for forming modern concrete, and the polycarboxylate water reducing agent is used as a third-generation water reducing agent, has the advantages of low mixing amount, high water reducing rate, designable diversity of molecular structures, environmental friendliness and the like, and is widely applied to projects such as buildings, highways, railways, bridges, dams, tunnels, super high-rise buildings and the like. Due to the widespread use of High Performance Concrete (HPC), the excellent workability of new cement-based materials is becoming more and more important, and workability is one of the research hotspots in the field of cement-based materials, which directly affects the construction efficiency, mechanical properties and durability of concrete.
The general method for improving the workability can be realized by reducing the water cement ratio, increasing the using amount of the cementing material, improving the proportion of the mineral admixture and the like, but the measures can also cause poor concrete state such as reduced fluidity and the like, more treatment methods achieve the requirements by compounding some functional additives at present, but the quality of the artificial sandstone material is poor along with the forbidden use of the natural sandstone material. Therefore, a more direct method is to research the polycarboxylic acid water reducing agent, which has important significance for the development of concrete admixtures and the concrete industry.
The ethylene glycol monovinyl polyglycol ether (EPEG) polyether macromonomer has higher reaction activity, good adaptability and easy regulation.
Chinese patent documents with publication number CN103467671A and publication date of 2013, 12 months and 25 days disclose a preparation method of a high water-reducing polycarboxylic acid water reducing agent, which comprises the steps of taking an unsaturated polyether macromonomer and an unsaturated sulfonic acid small monomer as dropwise-adding components 1, taking an azo initiator, a peroxidation initiator and an initiation accelerator as dropwise-adding components 2, taking acrylic acid as dropwise-adding components 3 and taking a molecular weight regulator as dropwise-adding components 4. The preparation method comprises the steps of putting unsaturated polyether macromonomer, unsaturated sulfonic acid small monomer and deionized water into a reactor, stirring and heating, when the temperature rises to the dripping temperature, dripping 1-4 components into the reactor in sequence for 3-4 hours, preserving heat for 0.5-1 hour after finishing dripping, and adding alkali for neutralization.
However, the synthesis of the polycarboxylic acid water reducing agent generally requires high-temperature heating to obtain the polycarboxylic acid water reducing agent, the process is complex, the requirements on reaction equipment are high, and how to reduce energy consumption in the synthesis of the polycarboxylic acid water reducing agent and improve synthesis efficiency and environmental suitability becomes an important problem facing the synthesis of polycarboxylic acid.
Therefore, the invention focuses on the preparation of the EPEG polycarboxylic acid water reducing agent with high water reducing capacity and has important significance.
Disclosure of Invention
In order to improve the synthesis efficiency and water reduction effect of the polycarboxylic acid water reducing agent and reduce the problem of energy consumption in the production process, the invention provides a high water reduction type EPEG polycarboxylic acid water reducing agent, which comprises ethylene glycol monovinyl polyglycol ether (EPEG), unsaturated acid monomers, amide polymers, unsaturated carboxylic acid/anhydride, unsaturated sulfonate and a function regulator;
wherein the functional regulator is a polymer of an unsaturated alcohol amine compound, an unsaturated ester monomer and an unsaturated phosphoric acid monomer.
In one embodiment, the functional regulator is prepared as follows: dissolving an unsaturated alcohol amine compound in isopropanol, heating to 30-50 ℃ under the atmosphere of nitrogen, reacting for 3-6 h, 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 h to obtain the functional regulator.
In one embodiment, the unsaturated 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.
In one embodiment, the catalyst is one or a combination of 4-dimethylaminopyridine, concentrated sulfuric acid ethylsulfonic acid, heteropolyacid, stannous oxide, dibutyltin oxide, benzenesulfonic acid or p-toluenesulfonic acid; the polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, p-tert-butyl catechol or phenothiazine.
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 amide polymer is prepared by performing Hofmann elimination reaction on an unsaturated amide comonomer with hypohalite and sodium hydroxide in a vacuum environment.
In one embodiment, the amide monomer is one or a combination of polyamide, N-dimethyl methylene acrylamide, N-methylene bisacrylamide, cyanoacetamide, acrylamide, cyclopropylamide and caprolactam; the hypohalite is at least one of sodium hypochlorite and sodium bromate.
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.
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 of the water reducing agent is 3.0-4.0.
In one embodiment, the mass ratio of the ethylene glycol monovinyl polyglycol ether to the functional regulator is 37.5-100: 1.
a preparation method for preparing the high water-reduction type EPEG polycarboxylic acid water reducer comprises the following steps:
b1: mixing ethylene glycol monovinyl polyglycol ether with water, fully dissolving and putting into a reaction container;
b2: adding a reducing agent, sulfate, unsaturated carboxylic acid and amide polymer into a B1 reaction container as a substrate, and stirring until the reducing agent, the sulfate, the unsaturated carboxylic acid and the amide polymer are uniformly and fully dissolved;
b3: and (3) controlling the speed of the unsaturated carboxylic acid/anhydride, the unsaturated sulfonate, the functional regulator aqueous solution, the oxidant aqueous solution and the chain transfer agent aqueous solution to be respectively dripped into the backing material at a controlled speed, and after dripping is finished, preserving heat and then supplementing water and adjusting the concentration to obtain the high water-reduction EPEG polycarboxylic acid water reducer.
Specifically, the detailed parameters and steps are as follows:
s1: mixing ethylene glycol monovinyl polyglycol ether (EPEG) and deionized water, fully dissolving and putting into a reaction container;
s2: adding a reducing agent, sulfate, unsaturated acid and amide polymer into an S1 reaction container as a base material, and stirring for 5-10 min to ensure uniform and sufficient dissolution;
s3: and (3) mixing the solution A: unsaturated carboxylic acid/anhydride, unsaturated sulfonate and functional regulator aqueous solution, liquid B: oxidant aqueous solution, solution C: respectively dripping the aqueous solution of the chain transfer agent into the bottom materials for 60-120 min; the reaction temperature is controlled to be 5-30 ℃; after the dripping is finished, preserving the heat for 80-120 min; and then water supplementing and thickening are carried out to obtain the high water-reducing EPEG polycarboxylic acid water reducer.
Preferably, the dropping time in S3 is 70 min.
Preferably, the reaction temperature in S3 is 10 ℃ and the holding time is 90 min.
The high water-reducing EPEG polycarboxylic acid water reducing agent provided by the invention has the following beneficial effects:
1. the raw materials required by the invention are common and easy to obtain, the cost is low, the preparation process is simple and convenient, the temperature required by the copolymerization process is low, and the method is energy-saving and environment-friendly.
2. The amide polymer can generate adsorption on the surface and among layers of cement under the action of electrostatic repulsion, and simultaneously protect carboxyl to a certain extent, so that the initial adsorption rate of the carboxyl in the water reducing agent to cement particles is reduced, and good dispersibility is shown.
3. The introduction of the amide polymer and the functional regulator increases the length of the side chain of the molecule, and the driving of the group on the side chain improves the related performances of water reduction and the like of the main body.
4. Phosphate radicals in the functional regulator have strong adsorption capacity on cement and have a synergistic effect with carboxylate radicals, so that the functional regulator 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.
5. The high water-reducing EPEG polycarboxylic acid water reducing agent provided by the invention has low requirement on preparation temperature, wide suitability, quick preparation and high efficiency, has high water reducing property and good dispersibility compared with similar products, and can solve the problems of poor workability and over-quick loss in concrete raw materials.
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 objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
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, but not all embodiments, of the present invention; 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 making any creative effort, shall fall within the protection 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 function regulator
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 into 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 functional 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 and 20g of hydroxyethyl methacrylate phosphate into 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 functional 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, 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 functional 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, heating 1g of concentrated sulfuric acid and 0.2g of p-hydroxyanisole to 100 ℃, reacting for 5h under the protection of nitrogen, and cooling to room temperature after the reaction is finished to prepare the functional 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, all the reactions are heated to 100 ℃ and all the reactions are reacted for 5h under the protection of nitrogen, and the reaction is cooled to room temperature after the reaction is finished to prepare the functional 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, all the reaction is carried out for 5h under the protection of nitrogen after the temperature is raised to 100 ℃, and the reaction is cooled to room temperature after the reaction is finished to prepare the functional regulator F.
Preparation of high water-reducing EPEG polycarboxylic acid water reducer
Example 7
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reaction of acrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 6 parts of a function regulator A and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; 1.5 parts of sodium formaldehyde sulfoxylate and 30 parts of water are prepared into solution C; dripping the A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Example 8
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 6 parts of a function regulator A and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 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 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Example 9
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 6 parts of a function regulator B and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 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 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Example 10
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 6 parts of a function regulator C and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 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 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Example 11
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 6 parts of a function regulator D and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 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 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Example 12
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 6 parts of a function regulator E and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 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 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Example 13
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 6 parts of a function regulator F and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 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 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Example 14
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of 2-acrylamide-2-methylpropanesulfonic acid, 4 parts of a function regulator A and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 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 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Example 15
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 8 parts of a function regulator A and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; 1.5 parts of thioglycolic acid and 30 parts of water to prepare a solution C; dripping the A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Example 16
Adding 400 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of ammonium persulfate, 3 parts of acrylic acid, 2 parts of amide polymer (obtained by reacting N, N-dimethyl methylene amide with sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of methacrylic acid, 15 parts of sodium methallyl sulfonate, 6 parts of a function regulator A and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 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 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Comparative example 1
Commercially available common polycarboxylic acid water reducing agent
Comparative example 2
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of 2-acrylamide-2-methylpropanesulfonic acid, 6 parts of a function regulator A and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 parts of thioglycolic acid and 30 parts of water; simultaneously dripping A, B, C solution into a four-neck flask for 70min, and keeping the whole reaction temperature at 50 ℃; and after the dropwise addition is finished, stirring for 90min under heat preservation, and supplementing 30 parts of water to obtain the polycarboxylic acid water reducer.
Comparative example 3
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of 2-acrylamide-2-methylpropanesulfonic acid, 6 parts of a function regulator A and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 parts of thioglycolic acid and 30 parts of water; dripping the A, B, C solution into a four-neck flask at the same time, wherein the dripping time is 50min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under heat preservation, and supplementing 30 parts of water to obtain the polycarboxylic acid water reducer.
Comparative example 4
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reacting N, N-dimethyl methacrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of 2-acrylamide-2-methylpropanesulfonic acid, 6 parts of a function regulator A and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; preparing solution C from 1.5 parts of thioglycolic acid and 30 parts of water; dripping the A, B, C solution into a four-neck flask at the same time, wherein the dripping time is 50min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, keeping the temperature and stirring for 60min, and supplementing 30 parts of water to obtain the polycarboxylic acid water reducer.
Comparative example 5
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reaction of acrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing solution A from 36 parts of acrylic acid, 15 parts of sodium methallyl sulfonate and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; 1.5 parts of sodium formaldehyde sulfoxylate and 30 parts of water are prepared into solution C; dripping the A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Comparative example 6
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of unsaturated amide monomer (acrylamide) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 30 parts of acrylic acid, 15 parts of sodium methallyl sulfonate, 6 parts of a function regulator A and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; 1.5 parts of sodium formaldehyde sulfoxylate and 30 parts of water are prepared into solution C; dripping the A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Comparative example 7
Adding 300 parts of ethylene glycol monovinyl polyglycol ether and 214 parts of water into a four-neck flask, heating to 30 ℃, pre-stirring for 10min to ensure uniform dissolution, then cooling to 10 ℃ to start reaction, and adding 7.8 parts of sodium hypophosphite, 3 parts of acrylic acid, 4 parts of amide polymer (obtained by reaction of acrylamide and sodium hypochlorite) and 4 parts of ferrous sulfate for later use. Preparing a solution A from 53 parts of a function regulator A and 15 parts of water; preparing solution B from 2 parts of hydrogen peroxide and 30 parts of water; 1.5 parts of sodium formaldehyde sulfoxylate and 30 parts of water are prepared into solution C; dripping the A, B, C solution into a four-neck flask simultaneously, wherein the dripping time is 70min, and the whole reaction temperature is kept at 10-20 ℃; and after the dropwise addition is finished, stirring for 90min under the condition of heat preservation, and supplementing 30 parts of water to obtain the high water reduction type EPEG polycarboxylic acid water reducer.
Mixing the polycarboxylic acid water reducing agent samples obtained by synthesis in examples 7-16 and comparative examples 1-7 with medium material cement (P.O 42.5), yellow sand, machine-made sand and crushed stone, and detecting the net slurry fluidity and the folded solid content of 0.1% according to GB8076-2008 concrete admixture, GB 8077-2012 concrete admixture homogeneity test method and GJ281-2012 high-strength concrete application technical specification; the initial slump and the expansion degree of the concrete and the slump and the expansion degree of the concrete with time are detected, the mixing proportion of the concrete is shown in Table 1, the expansion degree is controlled to be 550 +/-50 mm, and the obtained result is shown in Table 2.
Table 1 concrete mixing ratio/(Kg/m)3)
| Cement | Yellow sand | Machine-made sand | Gravel (5 mm to 20mm) | Gravel (16 mm to 31.5mm) | Water (W) |
| 380 | 250 | 692 | 200 | 902 | 165 |
TABLE 2 neat paste fluidity and concrete application Properties
The experimental results of examples 7-16 and comparative example 1 show that the initial extension degree of the high water-reducing EPEG polycarboxylic acid water reducing agent provided by the invention is controlled in concrete experiments, and the mixing amount of the water reducing agent used in the examples is far lower than that of the comparative example 1. Meanwhile, when the mixing amount is lower than that of the comparative example 1, the performances such as the fluidity of cement paste, the 60min expansion degree and the like of the cement paste in the examples 7 to 16 are still superior, and the superiority of the high water reduction type EPEG polycarboxylic acid water reducing agent is reflected. In addition, compared with the commercial polycarboxylate water reducer in the comparative example 1, the concrete strength performance of the concrete in the examples 7-16 is not inferior, and even has better performance, so that the high water reduction type EPEG polycarboxylate water reducer has strong practical value and popularization value.
As can be seen from the comparative example 2 and the examples 7 to 16, the high water-reducing EPEG polycarboxylic acid water reducing agent of the invention is carried out at a lower reaction temperature, and the excessively high reaction temperature can influence the water reducing effect of the finally prepared water reducing agent.
As can be seen from comparative examples 3-4 and examples 7-16, the dripping time and the heat preservation time in the reaction process need to be controlled, so that the phenomenon that the reaction is insufficient due to too short reaction time and the effect of the water reducing agent is influenced is avoided.
As can be seen from the comparative example 5 and the examples 7 to 16, under the condition that the functional regulator is not added, the required mixing amount is increased, and meanwhile, the performances of the water reducing agent in all aspects are partially reduced, so that the requirements cannot be met.
As can be seen from comparative example 6 and examples 7 to 16, after the amide-based polymer is replaced with the unsaturated amide monomer, the electrostatic repulsion effect of the amide-based polymer cannot be generated, and the carboxyl group is not sufficiently protected, resulting in performance degradation.
As can be seen from the comparative example 7 and the examples 7 to 16, the functional regulator is used for replacing unsaturated carboxylic acid and unsaturated sulfonate, so that the carboxylic acid and sulfonic acid groups in the whole formula are insufficient, and the performance of the water reducer is affected.
Meanwhile, as can be seen from examples 7 to 13, the functional regulator prepared from different raw materials and the amide polymer prepared from different raw materials are adopted in each example, and the high water-reducing EPEG polycarboxylic acid water reducer prepared from the amide polymer can achieve expected effects and has better water-reducing performance. The high water-reducing EPEG polycarboxylic acid water reducer has the advantages of multiple sources of raw materials, good effect and high practical value.
From the examples 14 to 16, it can be seen that the high water-reducing EPEG polycarboxylic acid water reducer still has good physical properties after the components and the proportion are regulated and controlled within the range of a formula system, has an obvious water-reducing effect, can be adjusted according to actual conditions, and has high practical value.
In conclusion, the high water-reducing EPEG polycarboxylic acid water reducing agent provided by the invention has better water reducing performance and less required mixing amount, can effectively improve the workability of concrete and the problem of excessive loss, has no adverse effect on mechanical performance, is wide in suitability and low in cost, 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. A high water-reducing EPEG polycarboxylic acid water reducing agent is characterized in that: comprises ethylene glycol monovinyl polyglycol ether (EPEG), unsaturated acid monomer, amide polymer, unsaturated carboxylic acid/anhydride, unsaturated sulfonate and function regulator;
wherein the functional regulator is a polymer of an unsaturated alcohol amine compound, an unsaturated ester monomer and an unsaturated phosphoric acid monomer.
2. The high water reduction type EPEG type polycarboxylic acid water reducing agent according to claim 1, characterized in that: the preparation process of the function regulator is as follows: dissolving unsaturated alcohol amine compounds 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 function regulator.
3. The high water reduction type EPEG type polycarboxylic acid water reducing agent according to claim 1, characterized in that: the unsaturated 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 high water reduction type EPEG type polycarboxylic acid water reducing agent 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 high water reduction type EPEG type polycarboxylic acid water reducing agent 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 high water reduction type EPEG type polycarboxylic acid water reducing agent according to claim 1, characterized in that: the amide polymer is prepared by carrying out Hofmann elimination reaction on unsaturated amide comonomer, hypohalite and sodium hydroxide in a vacuum environment.
7. The high water reduction type EPEG type polycarboxylic acid water reducing agent according to claim 6, characterized in that: the unsaturated amide comonomer is one or a combination of polyamide, N-dimethyl methacrylamide, N-methylene bisacrylamide, cyanoacetamide, acrylamide, cyclopropylamide and caprolactam; the hypohalite is at least one of sodium hypochlorite and sodium bromate.
8. The high water reduction type EPEG type polycarboxylic acid water reducing agent 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 high water reduction type EPEG type polycarboxylic acid water reducing agent according to claim 1, characterized in that: the weight portions of the components are as follows:
the overall acid-ether ratio is 3.0 to 4.0.
10. A method for preparing the high water reduction type EPEG-based polycarboxylic acid water reducing agent according to any one of claims 1 to 9, characterized by comprising the steps of:
a1: mixing ethylene glycol monovinyl polyglycol ether with water, fully dissolving and putting into a reaction container;
a2: adding a reducing agent, sulfate, unsaturated carboxylic acid and amide polymer into A1 as a base material, and stirring until the reducing agent, the sulfate, the unsaturated carboxylic acid and the amide polymer are uniformly and fully dissolved;
a3: and (3) controlling the speed of the unsaturated carboxylic acid/anhydride, the unsaturated sulfonate, the functional regulator aqueous solution, the oxidant aqueous solution and the chain transfer agent aqueous solution to be respectively dripped into the backing material at a controlled speed, and after dripping is finished, preserving heat and then supplementing water and adjusting the concentration to obtain the high water-reduction EPEG polycarboxylic acid water reducer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920509A (en) * | 2022-04-02 | 2022-08-19 | 北京马普新材料有限公司 | Method for resisting negative effects of flocculating agent in machine-made sand and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150291716A1 (en) * | 2012-12-05 | 2015-10-15 | Sobute New Materials Co., Ltd. | Slump retaining polycarboxylic acid superplasticizer |
| CN109824836A (en) * | 2019-01-29 | 2019-05-31 | 广东瑞安科技实业有限公司 | Workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof |
| CN109880019A (en) * | 2019-01-29 | 2019-06-14 | 广东瑞安科技实业有限公司 | A kind of workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof |
| CN109970926A (en) * | 2019-04-16 | 2019-07-05 | 山东卓星化工有限公司 | A method of polyocarboxy acid type high-thin arch dam water-reducing agent is prepared using ethylene glycol mono-vinyl polyoxyethylene ether ultralow temperature |
-
2021
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150291716A1 (en) * | 2012-12-05 | 2015-10-15 | Sobute New Materials Co., Ltd. | Slump retaining polycarboxylic acid superplasticizer |
| CN109824836A (en) * | 2019-01-29 | 2019-05-31 | 广东瑞安科技实业有限公司 | Workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof |
| CN109880019A (en) * | 2019-01-29 | 2019-06-14 | 广东瑞安科技实业有限公司 | A kind of workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof |
| CN109970926A (en) * | 2019-04-16 | 2019-07-05 | 山东卓星化工有限公司 | A method of polyocarboxy acid type high-thin arch dam water-reducing agent is prepared using ethylene glycol mono-vinyl polyoxyethylene ether ultralow temperature |
Non-Patent Citations (1)
| Title |
|---|
| 赵建庄等: "《有机化学》", 中国林业出版社, pages: 219 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920509A (en) * | 2022-04-02 | 2022-08-19 | 北京马普新材料有限公司 | Method for resisting negative effects of flocculating agent in machine-made sand and application |
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