CN115058001A - Retarding monomer and preparation method thereof, retarding water reducer and preparation method thereof - Google Patents
Retarding monomer and preparation method thereof, retarding water reducer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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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
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- 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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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Abstract
The invention relates to the technical field of concrete admixtures, in particular to a retarding monomer and a preparation method thereof, and a retarding water reducer and a preparation method thereof, wherein the preparation method of the retarding monomer comprises the steps of adding an unsaturated polyether monomer, a polyhydroxy acid, a catalyst and a polymerization inhibitor into a first reactor provided with a condensing device, keeping the temperature of 100-120 ℃ for 4-12 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain the retarding monomer. The retarding monomer provided by the invention can introduce a polyhydroxy structure into a polyether side chain of the water reducing agent during copolymerization, hydroxyl can form a hydrogen bond with water, when water reducing agent molecules are adsorbed on the surface of cement particles, a more compact hydration layer is formed through the polyhydroxy structure, so that a better dispersion effect is achieved, in addition, the polyhydroxy structure is connected through ester groups, gluconate can be gradually released along with the progress of hydration, and the gluconate can delay the hydration of cement, so that the retarding effect is achieved.
Description
The application is a divisional application of 'a retarding water reducer and a preparation method thereof' with the application number of CN2020114751622 and the application date of 14.12.2020.
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a retarding monomer and a preparation method thereof, and a retarding water reducer and a preparation method thereof.
Background
With the large-scale construction of basic engineering in China, the requirements on the performances of the concrete such as workability, strength, durability and the like are continuously improved, and the rapid development of concrete admixtures, especially the rapid development of polycarboxylic acid high-performance water reducing agents, is promoted. The polycarboxylic acid high-performance water reducing agent is used as an important component of a concrete admixture, has a certain air entraining effect when added into concrete, has a poor slump retaining effect, and is generally required to be compounded with a slump retaining agent and a retarder in order to meet the requirements of concrete transportation and pumping.
The patent application with the publication number of CN106279559A discloses a saccharide ester modified polycarboxylate water reducer and a preparation method thereof, wherein the saccharide ester is prepared by carrying out esterification reaction on unsaturated carboxylic acid and dried polyhydroxy saccharide compounds under the catalysis of concentrated sulfuric acid, and the esterification product is subjected to copolymerization reaction with unsaturated carboxylic acid and unsaturated alcohol polyether. Also as in patent applications with publication numbers CN110643003A and CN108864374A, a slow setting type water reducing agent is obtained by modifying a polycarboxylic acid water reducing agent by introducing polyhydroxy sugar compounds and unsaturated acids for esterification.
However, the esterification of polyhydroxy carbohydrate and unsaturated acid is difficult to obtain an esterified product with single and definite components, and the stability of the prepared product is difficult to control. Therefore, the method has important significance for improving the structure of the polyhydroxy carbohydrate.
Disclosure of Invention
In order to solve the problem of insufficient retarding effect of the existing water reducing agent mentioned in the background technology, the invention provides a retarding monomer, and the structural formula of the retarding monomer is as follows:
wherein, R is 1 Is H or CH 3 ，R 2 Is C n H 2n ，n＝0～4，R 3 Is (CHOH) n CH 2 OH，n＝2～20，x 1 ＝20～120，y 1 ＝0～20。
On the basis of the scheme, the slow-setting monomer is further prepared from an unsaturated polyether monomer and polyhydroxy acid through an esterification reaction.
On the basis of the scheme, the unsaturated polyether monomer is selected from one or more of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, isopentenyl polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methyl allyl polyoxyethylene polyoxypropylene ether or isopentenyl polyoxyethylene polyoxypropylene ether.
On the basis of the scheme, the polyhydroxy acid is gluconic acid.
On the basis of the scheme, the molar ratio of the unsaturated polyether monomer to the polyhydroxy acid is (1.0-1.2): 1.
The invention also provides a preparation method of the retarding monomer, which comprises the following operations:
adding an unsaturated polyether monomer, a polyhydroxy acid, a catalyst and a polymerization inhibitor into a first reactor provided with a condensing device, keeping the temperature of 100-120 ℃ for 4-12 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain a delayed coagulation monomer.
On the basis of the scheme, further, the using amount of the catalyst is 0.2-5% of the mass of the unsaturated polyether; the dosage of the polymerization inhibitor is 0.01-1 percent of the mass of the unsaturated polyether.
On the basis of the scheme, the catalyst is one of concentrated sulfuric acid, heteropoly acid, stannous oxide or dibutyl tin oxide;
the polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, p-tert-butyl catechol or phenothiazine.
The invention also provides a retarding water reducer which adopts the retarding monomer or the retarding monomer prepared by the preparation method.
The invention also provides a preparation method of the retarding water reducer, which comprises the specific operations of placing the ether macromonomer, the retarding monomer, the reducing agent and deionized water into a reactor, stirring and dissolving, dropwise adding a mixed solution of unsaturated acid, unsaturated ester and air-entraining monomer, an oxidant solution and a chain transfer agent solution into the reactor, adjusting the temperature to 25-50 ℃ for reaction, wherein the dropwise adding time is 1-3 h, keeping the temperature for 0.5-1.5 h after the dropwise adding is finished, cooling to room temperature after the reaction is finished, and adjusting the pH to 6-7 by using liquid alkali to obtain the retarding water reducer;
wherein the mass ratio of the ether macromonomer, the air-entraining monomer, the retarding monomer, the unsaturated acid and the unsaturated ester is as follows: (0-200): (1-30), (50-200), (10-30), (1-10);
the air entraining monomer is prepared from unsaturated acyl chloride and hydroxyalkyl quaternary ammonium salt through esterification reaction.
On the basis of the scheme, the structural formula of the ether macromonomer is as follows:
wherein, R is 4 Is H or CH 3 ，R 5 Is C n H 2n ，n＝0～4，x 1 ＝20～120，y 1 ＝0～20。
On the basis of the scheme, the structural formula of the hydroxyalkyl quaternary ammonium salt is as follows:
wherein, R is 6 、R 7 Is CH 3 、C n H 2n OH、C n H (2n-1) OHCl or C n H 2n ph，n＝1～4，R 8 Is C n H 2n OH or C n H (2n-1) OHCl，n＝1～4，R 9 Is C n H (2n+1) N is 5-30, and Z is F, Cl, Br or I.
On the basis of the scheme, the molar ratio of the unsaturated acyl chloride to the hydroxyalkyl quaternary ammonium salt is (1-1.2): 1.
on the basis of the scheme, further, the unsaturated acyl chloride is acryloyl chloride or methacryloyl chloride.
On the basis of the scheme, the structural formula of the unsaturated acid is as follows:
wherein said R 10 Is H or CH 3 。
On the basis of the scheme, the structural formula of the unsaturated ester is as follows:
wherein, R is 11 Is H or CH 3 ，R 12 Is C n H 2n OH、C n H 2(n+1) PO 4 Or C n H 2(n+1) PO 4 NCl，n＝1～5。
On the basis of the scheme, the feed additive further comprises the following components in parts by mass:
compared with the prior art, the invention has the following beneficial effects:
1. the retarding monomer provided by the invention can be applied to water reducing agents, a polyhydroxy structure is introduced into a polyether side chain of the water reducing agent during copolymerization, hydroxyl can form a hydrogen bond with water, when water reducing agent molecules are adsorbed on the surfaces of cement particles, a more compact hydration layer is formed through the polyhydroxy structure, so that a better dispersion effect is achieved, in addition, the polyhydroxy structure is connected through ester groups, along with the progress of hydration, gluconate can be gradually released, the hydration of cement can be delayed, and the retarding effect is achieved.
2. The water reducing agent prepared by the preparation method of the slow-setting water reducing agent provided by the invention is characterized in that besides the addition of the slow-setting monomers, air entraining monomers are introduced for copolymerization, a long-chain alkyl quaternary ammonium salt structure is introduced into the water reducing agent molecules, alkyl has a hydrophobic characteristic, quaternary ammonium salt has a hydrophilic characteristic, air bubbles and stable air bubbles can be introduced into concrete, and the long-chain alkyl quaternary ammonium salt is connected through ester groups and releases long-chain alkyl quaternary ammonium salt along with the hydration, so that the long-acting air entraining effect is achieved.
3. The water reducing agent prepared by the invention has antibacterial and anticorrosive effects due to the introduced long-chain alkyl quaternary ammonium salt structure, so that the mildew of the water reducing agent can be prevented, and the standing time is prolonged; and a quaternary ammonium salt structure is introduced into the polycarboxylic acid structure, so that the curling of water reducing agent molecules in an alkaline environment can be reduced, the sensitivity of the water reducing agent to inorganic salt ions is reduced, and the retention time of the water reducing agent molecule in a stretching conformation is prolonged, so that the dispersibility and slump retention of the water reducing agent are improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. 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.
The preparation steps of the retarding monomer provided by the invention are as follows:
adding an unsaturated polyether monomer, a polyhydroxy acid, a catalyst and a polymerization inhibitor into a first reactor provided with a condensing device, keeping the temperature of 100-120 ℃ for 4-12 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain a delayed coagulation monomer C; wherein the molar ratio of the unsaturated polyether monomer to the polyhydroxy acid is (1.0-1.2): 1, and the dosage of the catalyst is 0.2-5% of the mass of the unsaturated polyether; the dosage of the polymerization inhibitor is 0.01-1 percent of the mass of the unsaturated polyether.
The unsaturated polyether monomer can adopt at least one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, isopentenyl polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methyl allyl polyoxyethylene polyoxypropylene ether or isopentenyl polyoxyethylene polyoxypropylene ether.
Gluconic acid can be used as the polyhydroxy acid.
The catalyst can adopt concentrated sulfuric acid, heteropoly acid, stannous oxide or dibutyl tin oxide;
the polymerization inhibitor can adopt p-hydroxyanisole, hydroquinone, p-tert-butyl catechol or phenothiazine.
The invention provides a preparation method of a retarding water reducer, which comprises the following steps:
placing an ether macromonomer, a retarding monomer, a reducing agent and a proper amount of deionized water into a reactor, stirring and dissolving, dropwise adding a mixed solution of an unsaturated acid, an unsaturated ester and an air entraining monomer, an oxidant solution and a chain transfer agent solution into the reactor, adjusting the temperature to 25-50 ℃, reacting, wherein the dropwise adding time is 1-3 h, keeping the temperature for 0.5-1.5 h after the dropwise adding is finished, cooling to room temperature after the reaction is finished, and adjusting the pH to 6-7 by using liquid caustic soda to obtain a retarding water reducer;
wherein the mass ratio of the ether macromonomer, the air-entraining monomer, the retarding monomer, the unsaturated acid and the unsaturated ester is as follows: (0-200): (1-30), (50-200), (10-30) and (1-10).
The oxidant can adopt at least one of hydrogen peroxide, benzoyl peroxide or sodium persulfate;
the reducing agent can adopt ascorbic acid, sodium formaldehyde sulfoxylate and Bruggolit TM At least one of FF6 or sodium hypophosphite;
the chain transfer agent is at least one of thioglycolic acid, mercaptopropionic acid or mercaptoethanol;
the ether macromonomer can adopt at least one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, isopentenyl polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methyl allyl polyoxyethylene polyoxypropylene ether or isopentenyl polyoxyethylene polyoxypropylene ether;
the unsaturated acid can adopt acrylic acid or methacrylic acid;
the unsaturated ester can adopt at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, 2-methacryloyloxyethyl phosphate or 2-methacryloyloxypropyl phosphate, and 2-methacryloyloxyethyl phosphorylcholine;
the preparation method of the air-entraining monomer B comprises the following steps:
placing unsaturated acyl chloride, hydroxyalkyl quaternary ammonium salt, a solvent and an acid binding agent in a reactor, reacting for 4-16 h at 5-50 ℃, and carrying out reduced pressure distillation and recrystallization purification on the product to obtain an air entraining type monomer B. The molar ratio of the unsaturated acyl chloride to the hydroxyalkyl quaternary ammonium salt to the acid-binding agent is (1-1.2) 1: (0.8-1.2), and the mass amount of the solvent is 1.2-2.5 times of that of the hydroxyalkyl quaternary ammonium salt.
The unsaturated acyl chloride can adopt acryloyl chloride or methacryloyl chloride.
The hydroxyalkyl quaternary ammonium salt is preferably hydroxyalkyl ammonium chloride which can adopt bis (hydroxyethyl) methyl dodecyl ammonium chloride, bis (2-hydroxyethyl) -methyl-tridecyl ammonium chloride, octadecyl bis (2-hydroxyethyl) methyl ammonium chloride, (3-chloro-2-hydroxypropyl) dodecyl dimethyl ammonium chloride, (3-chloro-2-hydroxypropyl) dimethyl octadecyl ammonium chloride, N-dodecyl-N, N-bis (2-hydroxyethyl) benzyl ammonium chloride, bis (2-hydroxyethyl) methyl tetradecyl chloride quaternary ammonium salt, (3-chloro-2-hydroxypropyl) dodecyl dimethyl ammonium chloride, benzyl bis (2-hydroxypropyl) octadecyl ammonium chloride, benzyl bis (2-hydroxyethyl) octadecyl ammonium chloride, benzyl bis (2-hydroxypropyl) octadecyl ammonium chloride, and the like, Benzyldi (2-hydroxyethyl) octadecyl ammonium chloride, benzyldi (2-hydroxypropyl) tetradecyl ammonium chloride, benzyldi (2-hydroxyethyl) tetradecyl ammonium chloride, hexadecyl (2-hydroxyethyl) dimethyl ammonium chloride, benzyldi (2-hydroxypropyl) ammonium chloride, dodecyloxymethyl-tri (2-hydroxyethyl) ammonium chloride, tri (2-hydroxyethyl) [ (octadecyloxy) methyl ] ammonium chloride, di (2-hydroxyethyl) -methyl-undecyl ammonium chloride, hexadecylmethyldihydroxyethyl ammonium bromide, dodecyl (2-hydroxyethyl) dimethylammonium bromide, dodecylmethyldihydroxyethyl ammonium bromide, tetradecylmethyldihydroxyethyl ammonium bromide, hexadecylmethyldihydroxyethyl ammonium bromide, benzyldi (2-hydroxyethyl) tetradecyl ammonium chloride, benzyldi (2-hydroxypropyl) tetradecyl ammonium chloride, benzyldi (2-hydroxyethyl) ammonium chloride, dodecylmethyldihydroxyethyl ammonium bromide, tetradecylmethyldihydroxyethyl ammonium bromide, hexadecylmethyldihydroxyethyl ammonium bromide, dodecylmethyl, At least one of octadecyl methyl dihydroxy ethyl ammonium bromide;
the solvent can adopt at least one of dichloroethane, 1,4 dioxane, N, N-dimethylformamide or tetrahydrofuran;
the acid-binding agent can adopt at least one of sodium hydroxide, triethylamine or pyridine.
The invention also provides application examples of the retarding monomers shown in the following table:
example 1
(1) Preparation of air-entraining monomer B1: 0.1mol of bis (hydroxyethyl) methyl dodecyl ammonium chloride, 0.1mol of acryloyl chloride, 40mL of 1, 4-dioxane and 0.1mol of pyridine are placed in a reactor, the reaction is carried out for 10 hours at the temperature of 15 ℃, and the product is subjected to reduced pressure distillation and recrystallization purification to obtain the air entraining type monomer B1.
(2) Preparation of a setting-retarding monomer C1: 200 parts of isopentenyl polyoxyethylene ether-2400 with molecular weight, 15 parts of gluconic acid, 1.0 part of concentrated sulfuric acid and 0.1 part of p-hydroxyanisole are added into a first reactor provided with a condensing device, the temperature is kept constant at 120 ℃ for 6 hours under the protection of nitrogen, and the temperature is reduced to 40 ℃ after the reaction is finished, so that the delayed coagulation monomer C1 is obtained.
(3) And (3) copolymerization reaction: 50 parts of isopentenyl polyoxyethylene ether-2400, 150 parts of retarding monomer C1, 1.5 parts of sodium formaldehyde sulfoxylate and a proper amount of deionized water are placed in a reactor and stirred to be dissolved, a mixed solution of 20 parts of acrylic acid, 4 parts of 2-methacryloyloxyethyl phosphorylcholine, 4 parts of air-entraining monomer B1, 2 parts of hydrogen peroxide solution and 1 part of mercaptopropionic acid solution are dropwise added into the reactor at 30 ℃ for 3 hours, heat is preserved for 1 hour after the dropwise addition is finished, and the pH is adjusted to 6-7 by using liquid alkali after the reaction is finished, so that the retarding water reducer PC-1 is obtained. Wherein, the water consumption is the consumption which leads the solid content of the mother solution to be 50 percent.
Example 2
200 parts of retarding type monomer C1, 1.5 parts of sodium formaldehyde sulfoxylate and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 20 parts of acrylic acid, 4 parts of 2-methacryloyloxyethyl phosphorylcholine, 4 parts of air-entraining type monomer B1, 2 parts of hydrogen peroxide solution and 1 part of mercaptopropionic acid solution are dripped into the reactor at 30 ℃ for 3 hours, heat preservation is carried out for 1 hour after the dripping is finished, and the pH is adjusted to 6-7 by liquid caustic soda after the reaction is finished, so that the retarding type water reducing agent PC-2 is obtained. Wherein, the water consumption is the consumption which leads the solid content of the mother solution to be 50 percent.
Example 3
(1) Preparation of air-entraining monomer B2: placing 0.1mol of octadecyl di (2-hydroxyethyl) methyl ammonium chloride, 0.1mol of acryloyl chloride, 45mL of 1, 4-dioxane and 0.1mol of pyridine in a reactor, reacting for 10h at 15 ℃, and carrying out reduced pressure distillation and recrystallization purification on the product to obtain the air entraining type monomer B2.
(2) Preparation of setting retarding monomer C2: 200 parts of methyl allyl polyoxyethylene ether-2400, 15 parts of gluconic acid, 0.9g of heteropoly acid and 0.1g of phenothiazine are added into a first reactor provided with a condensing device, the temperature is kept constant at 110 ℃ for 6 hours under the protection of nitrogen, and the temperature is reduced to 40 ℃ after the reaction is finished, so that the retarding monomer C2 is obtained.
(3) And (3) copolymerization reaction: 50 parts of methyl allyl polyoxyethylene ether-2400, 150 parts of retarding monomer C2, 1 part of BruggolitFF 6 and a proper amount of deionized water are placed in a reactor and stirred to be dissolved, a mixed solution of 20 parts of acrylic acid, 3 parts of 2-methacryloyloxyethyl phosphate, 3 parts of air-entraining monomer B2, 2 parts of hydrogen peroxide solution and 1 part of mercaptopropionic acid solution are dropwise added into the reactor for 3 hours at 30 ℃, the temperature is kept for 1 hour after the dropwise addition is finished, and the pH is adjusted to 6-7 by using liquid alkali after the reaction is finished, so that the retarding water reducer PC-3 is obtained. Wherein, the water consumption is the consumption which leads the solid content of the mother solution to be 50 percent.
Example 4
(1) Preparation of air-entraining monomer B3: 0.1mol of N-dodecyl-N, N-bis (2-hydroxyethyl) benzyl ammonium chloride, 0.1mol of acryloyl chloride, 50mL of 1, 4-dioxane and 0.1mol of pyridine are placed in a reactor and react for 10 hours at the temperature of 15 ℃, and the product is subjected to reduced pressure distillation and recrystallization purification to obtain the air entraining type monomer B3.
(2) And (3) copolymerization reaction: 200 parts of retarding type monomer C2, 1 part of Bruggolit FF6 and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 20 parts of acrylic acid, 3 parts of 2-methacryloyloxyethyl phosphate, 4 parts of air-entraining type monomer B3, 2 parts of hydrogen peroxide solution and 1 part of mercaptopropionic acid solution are dropwise added into the reactor at 30 ℃ for 3 hours, heat preservation is carried out for 1 hour after dropwise addition is finished, and after the reaction is finished, the pH is adjusted to 6-7 by using liquid caustic soda, so that the retarding type water reducing agent PC-4 is obtained. Wherein, the water consumption is the consumption which leads the solid content of the mother solution to be 50 percent.
The present invention also provides comparative examples shown below
Comparative example 1
200 parts of isopentenyl polyoxyethylene ether-2400, 1.5 parts of sodium formaldehyde sulfoxylate and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 20 parts of acrylic acid and 4 parts of 2-methacryloyloxyethyl phosphorylcholine, 2 parts of a hydrogen peroxide solution and 1 part of a mercaptopropionic acid solution are dropwise added into the reactor at 30 ℃ for 3 hours, heat is preserved for 1 hour after the dropwise addition is finished, and the pH is adjusted to 6-7 by using liquid alkali after the reaction is finished, so that the water reducer PC-5 is obtained. Wherein the water consumption is the consumption which leads the solid content of the mother solution to be 50 percent.
Comparative example 2
200 parts of isopentenyl polyoxyethylene ether-2400, 1 part of Bruggolit FF6 and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 20 parts of acrylic acid, 3 parts of 2-methacryloyloxyethyl phosphorylcholine, 3 parts of air-entraining monomer B2, 2 parts of hydrogen peroxide solution and 1 part of mercaptopropionic acid solution are dropwise added into the reactor at 30 ℃ for 3 hours, heat preservation is carried out for 1 hour after dropwise addition is finished, and after the reaction is finished, the pH is adjusted to 6-7 by liquid alkali, so that the water reducer PC-6 is obtained. Wherein the water consumption is the consumption which leads the solid content of the mother solution to be 50 percent.
Comparative example 3
200 parts of methyl allyl polyoxyethylene ether-2400, 1 part of Bruggolit FF6 and a proper amount of deionized water are placed in a reactor and stirred to dissolve, a mixed solution of 20 parts of acrylic acid and 3 parts of 2-methacryloyloxyethyl phosphate, 2 parts of a hydrogen peroxide solution and 1 part of a mercaptopropionic acid solution are dropwise added into the reactor for 3 hours at 30 ℃, heat preservation is carried out for 1 hour after the dropwise addition is finished, and after the reaction is finished, liquid alkali is used for adjusting the pH value to 6-7, so that the water reducer PC-7 is obtained. Wherein, the water consumption is the consumption which leads the solid content of the mother solution to be 50 percent.
Comparative example 4
50 parts of methyl allyl polyoxyethylene ether-2400, 150 parts of retarding monomer C2, 1 part of Bruggolit FF6 and a proper amount of deionized water are placed in a reactor and stirred to dissolve, a mixed solution of 20 parts of acrylic acid and 3 parts of 2-methacryloyloxyethyl phosphate, 2 parts of hydrogen peroxide solution and 1 part of mercaptopropionic acid solution are dropwise added into the reactor at 30 ℃ for 3 hours, heat preservation is carried out for 1 hour after dropwise addition is finished, and after the reaction is finished, liquid caustic soda is used for regulating the pH value to 6-7, so that the water reducing agent PC-8 is obtained. Wherein, the water consumption is the consumption which leads the solid content of the mother solution to be 50 percent.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
The retarding polycarboxylic acid water reducing agents of examples 1 to 4 were compared with the water reducing agents of comparative examples 1 to 4, and standard cement was usedThe air content, the air content in 1h, the slump constant, the expansion degree, the setting time and the strength of concrete at each age are measured according to GB8076-2008 "concrete admixture" with the mixing amount of 0.2 percent of the cement by weight (converted into solid parts). The concrete mixing proportion is as follows: cement 360kg/m 3 803kg/m of sand 3 Stone 1050kg/m 3 170kg/m of water 3 The concrete test results are shown in table 1.
TABLE 1 concrete Performance test results
The test result shows that compared with the comparative example 3 and the comparative example 4, the comparative example 3 does not introduce the retarding monomer, the prepared water reducing agent does not have the function of prolonging the setting time, and the comparative example 4 introduces the retarding monomer, so that the water reducing agent has the function of prolonging the setting time; the retarding monomer provided by the invention has a better retarding effect.
Compared with comparative example 2, comparative example 1 does not introduce a monomer with a gas-inducing function, and has poorer bubble-inducing and bubble-stabilizing functions; compared with the prior art, the air entraining functional monomer is introduced in the comparative example 2, so that the foam entraining and stabilizing functions are realized, and the flowability is improved; in the embodiments 1 to 4, the monomer with the functions of introducing air-entraining and coagulating, and the like have the advantages of better dispersibility and dispersion retentivity and no adverse effect on strength.
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 retarding monomer is characterized in that the structural formula of the retarding monomer is as follows:
wherein, R is 1 Is H or CH 3 ，R 2 Is C n H 2n ，n＝0～4，R 3 Is (CHOH) n CH 2 OH，n＝2～20，x 1 ＝20～120，y 1 ＝0～20。
2. The slow-setting monomer of claim 1, wherein the slow-setting monomer is prepared from an unsaturated polyether monomer and a polyhydroxy acid through an esterification reaction.
3. The setting retarding monomer of claim 2, wherein the unsaturated polyether monomer is selected from one or more of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, isopentenyl polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methyl allyl polyoxyethylene polyoxypropylene ether, and isopentenyl polyoxyethylene polyoxypropylene ether.
4. The setting retarding monomer of claim 2, wherein the polyhydroxy acid is gluconic acid.
5. The slow-setting monomer according to claim 2, wherein the molar ratio of the unsaturated polyether monomer to the polyhydroxy acid is (1.0-1.2): 1.
6. A method for preparing the retardation type monomer as claimed in any one of claims 1 to 5, which comprises the following operations:
adding an unsaturated polyether monomer, a polyhydroxy acid, a catalyst and a polymerization inhibitor into a first reactor provided with a condensing device, keeping the temperature of 100-120 ℃ for 4-12 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain a delayed coagulation monomer.
7. The method for preparing the set-retarding monomer according to claim 6, which is characterized in that: the dosage of the catalyst is 0.2-5% of the mass of the unsaturated polyether; the dosage of the polymerization inhibitor is 0.01 to 1 percent of the mass of the unsaturated polyether.
8. The method for preparing the set-retarding monomer according to claim 7, which is characterized in that: the catalyst is one of concentrated sulfuric acid, heteropoly acid, stannous oxide or dibutyl tin oxide;
the polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, p-tert-butyl catechol or phenothiazine.
9. A retarding water reducer, characterized in that the retarding monomer of any claim 1 to 5 or the retarding monomer prepared by the preparation method of any claim 6 to 8 is adopted.
10. A preparation method of the set-retarding water reducer of claim 9,
placing an ether macromonomer, a retarding monomer, a reducing agent and deionized water into a reactor, stirring and dissolving, dropwise adding a mixed solution of an unsaturated acid, an unsaturated ester and an air entraining monomer, an oxidant solution and a chain transfer agent solution into the reactor, adjusting the temperature to 25-50 ℃, reacting, wherein the dropwise adding time is 1-3 h, keeping the temperature for 0.5-1.5 h after the dropwise adding is finished, cooling to room temperature after the reaction is finished, and adjusting the pH to 6-7 by using liquid caustic soda to obtain a retarding water reducer;
wherein the mass ratio of the ether macromonomer, the air-entraining monomer, the retarding monomer, the unsaturated acid and the unsaturated ester is as follows: (0-200): (1-30), (50-200), (10-30), (1-10);
the air entraining monomer is prepared from unsaturated acyl chloride and hydroxyalkyl quaternary ammonium salt through esterification reaction.
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| US20150291716A1 (en) * | 2012-12-05 | 2015-10-15 | Sobute New Materials Co., Ltd. | Slump retaining polycarboxylic acid superplasticizer |
| CN109232828A (en) * | 2018-09-07 | 2019-01-18 | 科之杰新材料集团有限公司 | A kind of preparation method of ester ether copoly type viscosity reduction type polycarboxylate water-reducer |
| CN109293847A (en) * | 2018-09-07 | 2019-02-01 | 科之杰新材料集团有限公司 | A kind of preparation method of ethers viscosity reduction type polycarboxylate water-reducer |
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| CN108545978B (en) * | 2018-04-28 | 2021-06-22 | 中建商品混凝土广西有限公司 | Quaternary ammonium salt type concrete anti-mud agent and preparation method and application thereof |
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| US20150291716A1 (en) * | 2012-12-05 | 2015-10-15 | Sobute New Materials Co., Ltd. | Slump retaining polycarboxylic acid superplasticizer |
| CN109232828A (en) * | 2018-09-07 | 2019-01-18 | 科之杰新材料集团有限公司 | A kind of preparation method of ester ether copoly type viscosity reduction type polycarboxylate water-reducer |
| CN109293847A (en) * | 2018-09-07 | 2019-02-01 | 科之杰新材料集团有限公司 | A kind of preparation method of ethers viscosity reduction type polycarboxylate water-reducer |
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