CN112608422B - Preparation method of polycarboxylic acid workability regulator - Google Patents
Preparation method of polycarboxylic acid workability regulator Download PDFInfo
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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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
- 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
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention relates to a preparation method of a polycarboxylic acid type workability regulator, which is obtained by aqueous solution free radical polymerization of a monomer mixture, wherein the monomer mixture comprises a polymerizable reducing agent, an unsaturated acid and an unsaturated ester, and the polymerizable reducing agent has a tertiary amino group and a cellulose ether structure. The polycarboxylic acid workability regulator prepared by the invention can obviously improve the wrapping property and the fluidity of concrete, reduce the phenomenon of bleeding and segregation, and improve the dispersibility and the dispersion retentivity of the concrete.
Description
Technical Field
The invention belongs to the technical field of building material additives, and particularly relates to a preparation method of a polycarboxylic workability regulator.
Background
Under the situation that natural sandstone resources are deficient and the state continuously strengthens the ore resources and the environmental protection, machine-made sandstone, sea sand, recycled aggregate and the like become main products of sandstone aggregate for basic facilities such as buildings, roads, bridges and the like in China. The use of machine-made sandstone, sea sand, recycled aggregate and other poor-quality sandstone generally leads to the deterioration of the workability of concrete, and is mainly reflected in that: the medium and low strength concrete has poor cohesiveness and has the phenomena of segregation and bleeding; the high-strength concrete has too high viscosity, which is not beneficial to pumping construction and the like. In engineering, the workability of concrete is improved by adding a viscosity modifier to achieve good construction performance.
At present, the most widely used viscosity modifiers in China are cellulose modifiers and propylene modifiers, wherein the cellulose modifiers are powder and are generally introduced into concrete in a compounding way with a water reducing agent, and a good concrete viscosity modification effect can be achieved when the mixing amount is 0.02-0.04% of that of a single ton of water reducing agent finished product. However, the cellulose-based viscosity modifier has a problem of solubility, a problem of long dissolution time in a water-reducing agent solution and a problem of compatibility with the water-reducing agent, and is likely to cause delamination after standing, thereby affecting the use effect of the water-reducing agent. Although the propylene viscosity modifier has good compatibility with the water reducing agent, the propylene viscosity modifier also has the problem of compatibility with the water reducing agent after reaching a certain mixing amount.
Therefore, it is necessary to prepare a water reducing agent capable of adjusting the workability of concrete.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a method for preparing a polycarboxylic acid-based workability modifier, comprising the steps of:
1) And (3) copolymerization reaction: adding a polymerizable reducing agent, a polyether macromonomer and water into a reaction container, mixing, then respectively dropwise adding a mixed solution of unsaturated acid and unsaturated ester, an oxidant aqueous solution and a chain transfer agent aqueous solution, and reacting at the temperature of 10-50 ℃ for 0.5-6 h;
2) And (3) neutralization reaction: after the reaction is finished, adding alkali liquor, adjusting the pH value to 6-7 to obtain the polycarboxylic acid workability regulator,
wherein the polymerizable reducing agent has a tertiary amino group and a cellulose ether structure.
In the copolymerization reaction in step 1), the dropping time is preferably 0.5 to 3 hours, and the reaction is continued for 0.5 to 3 hours after the dropping is completed, and further preferably, the reaction temperature is room temperature.
In the neutralization reaction of step 2), the alkali solution used is any alkali solution commonly used in the art, such as liquid alkali, aqueous NaOH solution, aqueous KOH solution, etc., and the concentration thereof is preferably 10% to 40%, more preferably 20% to 40%.
In a preferred embodiment, the polymerizable reducing agent is prepared by:
in the presence of a catalyst and a polymerization inhibitor, carrying out ester exchange reaction on a compound A and a compound B in an organic solvent at the temperature of 80-120 ℃ for 5-24 h to obtain the polymerizable reducing agent,
wherein the compound A has a structural formula shown as the following formula (I):
wherein:
R 1 is straight chain or branched C 1 -C 5 Alkyl groups such as methyl or ethyl;
R 2 is- (CH) 2 ) n -, phenylene or ethoxyphenylene, where n is an integer from 1 to 10;
R 3 is a straight chain or branched chain C 1 -C 5 An alkyl group, such as a methyl or ethyl group,
compound B has the structural formula shown below in formula (II):
wherein R is H, CH 2 CH 2 OH、
Or straight or branched C 1 -C 5 Alkyl radicals such as CH 3 ，
n is an integer of 1 to 300.
In the preparation of the polymerizable reducing agent, it is preferred that compound B is dissolved in an organic solvent, then compound A is added, and after the end of the transesterification reaction, the reaction mixture is worked up, for example, by removing the solvent by distillation under reduced pressure, to give the polymerizable reducing agent.
In the method for preparing the polymerizable reducing agent, the organic solvent used is preferably a mixed solvent of a polar organic solvent and a nonpolar organic solvent, for example, a mixed solvent of toluene and isopropanol, and the mass ratio of the nonpolar organic solvent to the polar organic solvent is 1. The transesterification reaction time is preferably 5 to 15 hours.
Preferably, the compound A is ethyl 2-diethylaminoacetate, ethyl 2-dimethylaminoacetate, ethyl 3-dimethylaminopropionate, ethyl 4- (dimethylamino) butyrate, ethyl 4- (2- (dimethylamino) ethoxy) benzoate, 2-dimethylaminoethyl benzoate, ethyl p-N, N-dimethylaminobenzoate or methyl 4-diethylaminobenzoate, and more preferably the compound A is ethyl 2-diethylaminoacetate, ethyl 2-dimethylaminoacetate or ethyl 3-dimethylaminopropionate.
Preferably, the compound B is hydroxyethyl methylcellulose ether, hydroxypropyl methylcellulose, having a viscosity of usually at least 5000 mPa-s, preferably of from 5 to 50 ten thousand mPa-s, more preferably of from 10 to 30 ten thousand mPa-s.
The molar ratio of the anhydroglucose units of the compound A to the anhydroglucose units of the compound B is usually 0.02 to 3, the amount of the catalyst is 0.5 to 30% by mass of the compound B, and the amount of the polymerization inhibitor is 0.01 to 0.2% by mass of the compound B.
Preferably, the catalyst is concentrated sulfuric acid, p-toluenesulfonic acid or 4-dimethylaminopyridine, and the polymerization inhibitor is hydroquinone, phenothiazine or diphenylamine.
In another preferred embodiment, the unsaturated acid has a formula as shown in formula (III):
wherein:
R 4 is H, straight chain or branched C 1 -C 5 Alkyl or-COOH;
R 5 is H or straight or branched C 1 -C 5 An alkyl group.
Preferably, the unsaturated acid is acrylic acid or methacrylic acid.
In yet another preferred embodiment, the unsaturated ester has a formula as shown in formula (IV):
wherein:
R 6 is H or straight or branched C 1 -C 5 An alkyl group;
R 7 is H or straight or branched C 1 -C 5 An alkyl group;
R 8 is-C n H 2n OH or-C n H 2n PO 4 And n is an integer of 1 to 20.
Preferably, the unsaturated ester is selected from the group consisting of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, 2-methacryloxypropyl phosphate or 2-methacryloxyethyl phosphate and combinations thereof.
In yet another preferred embodiment, the polyether macromonomer is an unsaturated polyether and is selected from the group consisting of allyl polyoxyethylene ether, methallyl polyoxyethylene polyoxypropylene ether, isopentenyl polyoxyethylene ether, or isopentenyl polyoxyethylene polyoxypropylene ether, and combinations thereof.
In yet another preferred embodiment, the oxidizing agent is hydrogen peroxide or benzoyl peroxide.
In yet another preferred embodiment, the chain transfer agent is a mercapto-containing chain transfer agent, preferably thioglycolic acid, mercaptopropionic acid or mercaptoethanol.
In yet another preferred embodiment, the mass ratio of the polyether macromonomer, unsaturated acid, unsaturated ester, polymerizable reducing agent, oxidizing agent, chain transfer agent is 30-150.
Correspondingly, the invention also provides the polycarboxylic acid workability regulator prepared by the preparation method of the polycarboxylic acid workability regulator, which is characterized in that the normal-pressure bleeding rate of concrete doped with the workability regulator is less than 1%.
The preparation method of the invention and the polycarboxylic acid workability regulator prepared by the preparation method of the invention have the following technical principles and beneficial effects:
1. the invention introduces tertiary amino on the cellulose ether structure through the ester exchange reaction of the compound A and the compound B, the tertiary amino can react with an oxidizing agent to form an active free base point, thereby continuously initiating the polymerization of unsaturated polyether, unsaturated acid and unsaturated ester, and introducing a hydrophilic polymer molecular chain on the cellulose ether structure to improve the water solubility of the cellulose ether. The prepared polycarboxylic acid workability regulator contains a cellulose ether structure, can improve the wrapping property and the fluidity of concrete and reduce the phenomenon of bleeding and segregation, thereby improving the working performance of the concrete.
2. The prepared polycarboxylic acid workability regulator has a hyperbranched structure, has a larger steric hindrance effect, and provides better dispersibility for concrete. And the copolymer molecular chain of the unsaturated polyether, the unsaturated acid and the unsaturated ester is connected with the cellulose ether structure through an ester group, and the ester group is continuously hydrolyzed to release the copolymer molecular chain along with the hydration, so that the consumed water reducing agent is continuously supplemented, and the dispersibility and the retentivity of the concrete are improved.
Detailed Description
To make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments are described clearly and completely in conjunction with the embodiments, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the 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 present invention provides the following examples:
1. preparation of polymerizable reducing agent
Example 1:
adding 3g of hydroxypropyl methyl cellulose ether with the viscosity of 10 ten thousand mPa.s, 120g of toluene and 40g of isopropanol into a four-neck flask provided with a stirrer, a water separator, a thermometer and a nitrogen guide pipe, stirring to dissolve the hydroxypropyl methyl cellulose ether, then adding 3g of 2-diethylaminoethyl acetate, 0.3g of concentrated sulfuric acid and 0.001g of hydroquinone, raising the reaction temperature to 90 ℃ under the stirring condition, reacting for 10 hours, and after the reaction is finished, removing the solvent by reduced pressure distillation to obtain the polymerizable reducing agent C1.
Example 2:
4g of hydroxypropyl methyl cellulose ether having a viscosity of 10 ten thousand mPas, 120g of toluene and 40g of isopropyl alcohol were put into a four-necked flask equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, and stirred to dissolve the hydroxypropyl methyl cellulose ether. Then, adding 3g of 2-dimethylamino ethyl acetate, 0.8g of 4-dimethylaminopyridine and 0.001g of hydroquinone, heating the reaction temperature to 90 ℃ under the condition of stirring, reacting for 10 hours, removing the solvent by reduced pressure distillation, and obtaining the polymerizable reducing agent C2 after the reaction is finished.
Example 3:
4g of hydroxypropyl methyl cellulose ether having a viscosity of 20 ten thousand mPa · s, 120g of toluene and 40g of isopropyl alcohol were put into a four-necked flask equipped with a stirrer, a water separator, a thermometer and a nitrogen introduction tube, and stirred to dissolve the hydroxypropyl methyl cellulose ether. Then 2.5g of 3-dimethyl amino ethyl propionate, 0.25g of concentrated sulfuric acid and 0.001g of phenothiazine are added, the reaction temperature is increased to 90 ℃ under the stirring condition, the reaction is carried out for 10 hours, and after the reaction is finished, the solvent is removed through reduced pressure distillation, thus obtaining the polymerizable reducing agent C3.
Example 4:
4g of 20 ten thousand mPa.s hydroxypropyl methyl cellulose ether, 120g of toluene and 40g of isopropyl alcohol were put into a four-necked flask equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, and stirred to dissolve the hydroxypropyl methyl cellulose ether. Then 3.5g of 3-dimethyl amino ethyl propionate, 0.5g of 4-dimethyl aminopyridine and 0.001g of hydroquinone are added, the reaction temperature is increased to 90 ℃ under the condition of stirring, the mixture reacts for 10 hours, and after the reaction is finished, the solvent is removed by reduced pressure distillation, thus obtaining the polymerizable reducing agent C4.
2. Preparation of polycarboxylic acid-based workability modifier
Example 5
0.2g of polymerizable reducing agent C1, 200g of methallyl polyoxyethylene ether and 130g of deionized water are placed in a reactor, stirring is carried out to dissolve the polymerizable reducing agent C1, the mixed solution of 21g of acrylic acid and 4g of hydroxyethyl methacrylate, 2g of aqueous hydrogen peroxide solution and 1.1g of aqueous thioglycolic acid are dropwise added into the reactor, reaction is carried out at room temperature, the dropwise adding time is 1.5h, reaction is continued for 1h after the dropwise adding is finished, and after the reaction is finished, the pH is adjusted to 6-7 by 32wt% of liquid alkali, so that the polycarboxylic acid workability regulator D1 is obtained.
Example 6
Placing 0.25g of polymerizable reducing agent C2, 200g of isopentenyl polyoxyethylene ether and 135g of deionized water in a reactor, stirring to dissolve, dropwise adding a mixed solution of 20g of acrylic acid and 4g of hydroxyethyl acrylate, 2.5g of aqueous hydrogen peroxide and 0.7g of aqueous mercaptopropionic acid into the reactor, reacting at room temperature for 1.5h, continuing to react for 1h after dropwise adding, and after the reaction is finished, adjusting the pH to 6-7 by using 32wt% of liquid alkali to obtain the polycarboxylic acid workability regulator D2.
Example 7
0.3g of polymerizable reducing agent C3, 200g of methallyl polyoxyethylene ether and 135g of deionized water are placed in a reactor, stirring is carried out to dissolve the polymerizable reducing agent C, a mixed solution of 20g of acrylic acid and 4g of hydroxypropyl methacrylate, 2.1g of aqueous hydrogen peroxide solution and 0.6g of aqueous mercaptoethanol are dropwise added into the reactor, reaction is carried out at room temperature, the dropwise adding time is 1.5h, reaction is continued for 1h after the dropwise adding is finished, and after the reaction is finished, the pH value is adjusted to 6-7 by using 32wt% of liquid alkali, so that the polycarboxylic acid workability regulator D3 is obtained.
Example 8
Placing 0.35g of polymerizable reducing agent C4, 200g of isopentenyl polyoxyethylene ether and 135g of deionized water in a reactor, stirring to dissolve, dropwise adding a mixed solution of 20g of acrylic acid and 3.5g of hydroxypropyl acrylate, 2g of aqueous hydrogen peroxide and 0.7g of aqueous mercaptopropionic acid into the reactor, reacting at room temperature for 1.5h, continuing to react for 1h after dropwise adding, and after the reaction is finished, adjusting the pH to 6-7 by using 32wt% of liquid alkali to obtain the polycarboxylic acid workability regulator D4.
Example 9
0.2g of polymerizable reducing agent C1, 200g of isopentenyl polyoxyethylene ether and 135g of deionized water are placed in a reactor, stirring is carried out to dissolve the polymerizable reducing agent C1, the prenyl polyoxyethylene ether and the deionized water, a mixed solution of 20g of acrylic acid and 4g of 2-methacryloxypropyl phosphate, 2.2g of aqueous hydrogen peroxide and 0.8g of aqueous solution of mercaptopropionic acid are dropwise added into the reactor, the reaction is carried out at room temperature, the dropwise adding time is 1.5h, the reaction is continued for 1h after the dropwise adding is finished, and after the reaction is finished, 32wt% of liquid alkali is used for adjusting the pH to 6-7, so that the polycarboxylic acid workability regulator D5 is obtained.
Example 10
Placing 0.23g of polymerizable reducing agent C1, 200g of methallyl polyoxyethylene ether and 135g of deionized water in a reactor, stirring to dissolve, dropwise adding a mixed solution of 20g of acrylic acid and 3g of 2-methacryloyloxyethyl phosphate, 2g of aqueous hydrogen peroxide and 0.8g of aqueous mercaptopropionic acid into the reactor, reacting at room temperature for 1.5h, continuing to react for 1h after dropwise adding, and after the reaction is finished, adjusting the pH to 6-7 by using 32wt% of liquid alkali to obtain the polycarboxylic acid workability regulator D6.
3. Comparative example
Comparative example 1
0.7g of sodium formaldehyde sulfoxylate, 200g of isopentenyl polyoxyethylene ether and 135g of deionized water are placed in a reactor, stirred to be dissolved, a mixed solution of 20g of acrylic acid and 4g of 2-methacryloxypropyl phosphate, 2.2g of aqueous hydrogen peroxide and 0.8g of aqueous mercaptopropionic acid are dropwise added into the reactor, the reaction is carried out at room temperature, the dropwise adding time is 1.5h, the reaction is continued for 1h after the dropwise adding is finished, and after the reaction is finished, the pH value is adjusted to 6-7 by using 32wt% of liquid alkali, so that the polycarboxylic acid water reducer E1 is obtained.
Comparative example 2
Placing 1.0g of ascorbic acid, 200g of methallyl polyoxyethylene ether and 130g of deionized water into a reactor, stirring to dissolve, dropwise adding a mixed solution of 21g of acrylic acid and 4g of hydroxyethyl methacrylate, 2g of aqueous hydrogen peroxide and 0.8g of aqueous mercaptopropionic acid into the reactor, reacting at room temperature for 1.5h, continuing to react for 1h after dropwise adding is finished, and adjusting the pH to 6-7 by using 32wt% of liquid alkali after the reaction is finished to obtain the polycarboxylic acid water reducer E2.
The polycarboxylic acid type workability obtained in examples 5 to 10Concrete tests were carried out on the regulator and the polycarboxylic acid water reducing agents prepared in comparative examples 1 and 2, and the concrete slump, the concrete slump with time, the concrete slump expansion, the concrete slump with time, the concrete bleeding distance and the normal pressure bleeding rate were measured according to GB 8076-2008 "concrete admixture". The mixing amount is adjusted to make the concrete expansion degree 550 +/-10 mm, and comparison is carried out. The concrete mixing proportion is as follows: cement 360kg/m 3 790kg/m of sand 3 1050kg/m stone 3 170kg/m of water 3 The results obtained are shown in table 1.
TABLE 1 concrete test results
The test results in table 1 show that the polycarboxylic acid workability regulator prepared in the invention in examples 5 to 10 can not only effectively improve the workability of concrete, but also improve the slump retaining performance of concrete, compared with comparative examples.
Finally, it should be noted that: the above examples are intended to illustrate the invention, but not to limit it; while the invention has been described in detail with reference to the foregoing embodiments and examples, those of ordinary skill in the art will understand that: the technical solutions can still be modified, or some or all of the technical features can be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present invention.
Claims (12)
1. A method for preparing a polycarboxylic acid-based workability modifier, characterized by comprising the steps of:
1) And (3) copolymerization reaction: adding a polymerizable reducing agent, a polyether macromonomer and water into a reaction container, mixing, then respectively dropwise adding a mixed solution of unsaturated acid and unsaturated ester, an oxidant aqueous solution and a chain transfer agent aqueous solution, and reacting at the temperature of 10-50 ℃ for 0.5-6 h;
2) And (3) neutralization reaction: after the reaction is finished, adding alkali liquor, adjusting the pH value to 6-7 to obtain the polycarboxylic acid workability regulator,
wherein the polymerizable reducing agent has a tertiary amino group and a cellulose ether structure.
2. The method of claim 1, wherein the polymerizable reducing agent is prepared by:
in the presence of a catalyst and a polymerization inhibitor, carrying out ester exchange reaction on a compound A and a compound B in an organic solvent at the temperature of 80-120 ℃ for 5-24 h to obtain the polymerizable reducing agent,
wherein the compound A has a structural formula shown as the following formula (I):
wherein:
R 1 is straight chain or branched C 1 -C 5 An alkyl group;
R 2 is- (CH) 2 ) n -, phenylene or ethoxyphenylene, where n is an integer from 1 to 10;
R 3 is a straight chain or branched chain C 1 -C 5 An alkyl group, a carboxyl group,
compound B has the structural formula shown below in formula (II):
wherein: r is H, straight chain or branched chain C 1 -C 5 Alkyl, -CH 2 CH 2 OH or
n is an integer of 1 to 300.
3. The method according to claim 2, wherein the organic solvent is a mixed solvent of a polar organic solvent and a non-polar organic solvent, and the mass ratio of the non-polar organic solvent to the polar organic solvent is 1.
4. The method according to claim 2, wherein the molar ratio of the anhydroglucose units of compound a to compound B is 0.02 to 3; the dosage of the polymerization inhibitor is 0.01 to 0.2 percent of the mass of the compound B.
5. The method of claim 2, wherein the catalyst is concentrated sulfuric acid, p-toluenesulfonic acid, or 4-dimethylaminopyridine, and the polymerization inhibitor is hydroquinone, phenothiazine, or diphenylamine.
6. The method of any one of claims 1-5, wherein the polyether macromonomer is selected from the group consisting of allyl polyoxyethylene ether, methallyl polyoxyethylene polyoxypropylene ether, isopentenyl polyoxyethylene polyoxypropylene ether, and combinations thereof.
7. The method of any one of claims 1-5, wherein the unsaturated acid has a formula as shown in formula (III):
wherein:
R 4 is H, straight chain or branched C 1 -C 5 Alkyl or-COOH;
R 5 is H or straight or branched C 1 -C 5 An alkyl group.
8. The method of any one of claims 1-5, wherein the unsaturated ester has a structural formula as shown in formula (IV):
wherein:
R 6 is H or straight or branched C 1 -C 5 An alkyl group;
R 7 is H or straight or branched C 1 -C 5 An alkyl group;
R 8 is-C n H 2n OH or-C n H 2n PO 4 And n is an integer of 1 to 20.
9. The method of any one of claims 1 to 5, wherein the oxidizing agent is hydrogen peroxide or benzoyl peroxide.
10. The method of any one of claims 1-5, wherein the chain transfer agent is a mercapto-containing chain transfer agent.
11. The method according to any one of claims 1 to 5, wherein the mass ratio of the polyether macromonomer, the unsaturated acid, the unsaturated ester, the polymerizable reducing agent, the oxidizing agent and the chain transfer agent is 30 to 150.
12. The polycarboxylic acid-based workability modifier prepared according to any one of claims 1 to 11, characterized in that the normal pressure bleeding rate of concrete incorporating the workability modifier is 1% or less.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911274018.XA CN112608422B (en) | 2019-12-12 | 2019-12-12 | Preparation method of polycarboxylic acid workability regulator |
| RU2020123975A RU2751769C1 (en) | 2019-12-12 | 2020-06-04 | Method for preparing polycarboxylic acid-based workability regulator |
| PCT/CN2020/094399 WO2021114581A1 (en) | 2019-12-12 | 2020-06-04 | Polycarboxylic workable regulator preparation method |
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| CN201911274018.XA CN112608422B (en) | 2019-12-12 | 2019-12-12 | Preparation method of polycarboxylic acid workability regulator |
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| WO2008032800A1 (en) * | 2006-09-13 | 2008-03-20 | Toho Chemical Industry Co., Ltd. | Cement dispersing agent |
| JP2009161380A (en) * | 2007-12-28 | 2009-07-23 | Toho Chem Ind Co Ltd | New cement dispersant |
| CN104628972A (en) * | 2015-01-30 | 2015-05-20 | 江苏奥莱特新材料有限公司 | Preparation method of anti-crack shrinkage reducing polycarboxylate based superplasticizer |
| CN107778418A (en) * | 2017-11-16 | 2018-03-09 | 科之杰新材料集团有限公司 | A kind of efficiently defoaming type polycarboxylate water-reducer and preparation method thereof |
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| DE60136858D1 (en) * | 2000-12-27 | 2009-01-15 | Nippon Catalytic Chem Ind | COPOLYMER OF POLYCARBONIC ACID TYPE, PROCESS FOR ITS PREPARATION, CEMENT ADDITIVE AND CEMENT COMPOSITION |
| CN101293756B (en) * | 2002-04-25 | 2012-04-25 | 株式会社日本触媒 | Cement admixture and production method thereof |
| FR2911131B1 (en) * | 2007-01-09 | 2009-02-06 | Coatex S A S Soc Par Actions S | USE OF A RHEOLOGICAL ADDITIVE IN THE MANUFACTURE BY VIBROCOMPACTION OF A FORMULATION BASED ON WATER AND HYDRAULIC BINDER, FORMULATION OBTAINED. |
| JP2011084459A (en) * | 2009-09-18 | 2011-04-28 | Nippon Shokubai Co Ltd | Cement admixture, cement composition, and polycarboxylic acid copolymer for cement admixture |
| JP5848633B2 (en) * | 2011-03-15 | 2016-01-27 | 花王株式会社 | Dispersant for hydraulic composition |
| RU2624818C2 (en) * | 2013-05-29 | 2017-07-07 | Силкроуд К Энд Т | Macromonomer for obtaining additives for cement, method of its production, additive to cement, including polycarboxyl copolymer obtained from macromonomer and layered double hydroxide, and a method of obtaining additives to cement |
| CN103553413B (en) * | 2013-09-25 | 2016-05-04 | 中国建筑材料科学研究总院 | A kind of sticky type polycarboxylate water-reducer and preparation method thereof of adjusting |
| CN103980433B (en) * | 2014-05-16 | 2015-09-16 | 武汉汉星盛新型建材有限公司 | Generating vinyl carboxylate base co-polymer concrete thickening material and preparation method thereof |
| CA2990904C (en) * | 2015-07-22 | 2023-10-03 | Basf Se | Agroformulation comprising copolymers containing hydroxybutyl vinyl ether as associative thickener |
| CN106699984B (en) * | 2016-07-10 | 2019-05-17 | 济南大学 | A kind of lightweight aggregate floating inhibitor and preparation method thereof for lightweight aggregate concrete |
| 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 |
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|---|---|---|---|---|
| WO2008032800A1 (en) * | 2006-09-13 | 2008-03-20 | Toho Chemical Industry Co., Ltd. | Cement dispersing agent |
| JP2009161380A (en) * | 2007-12-28 | 2009-07-23 | Toho Chem Ind Co Ltd | New cement dispersant |
| CN104628972A (en) * | 2015-01-30 | 2015-05-20 | 江苏奥莱特新材料有限公司 | Preparation method of anti-crack shrinkage reducing polycarboxylate based superplasticizer |
| CN107778418A (en) * | 2017-11-16 | 2018-03-09 | 科之杰新材料集团有限公司 | A kind of efficiently defoaming type polycarboxylate water-reducer and preparation method thereof |
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| CN112608422A (en) | 2021-04-06 |
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