CN112608424B - Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof - Google Patents
Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN112608424B CN112608424B CN201911383838.2A CN201911383838A CN112608424B CN 112608424 B CN112608424 B CN 112608424B CN 201911383838 A CN201911383838 A CN 201911383838A CN 112608424 B CN112608424 B CN 112608424B
- Authority
- CN
- China
- Prior art keywords
- mixed solution
- parts
- ester ether
- acid
- type polycarboxylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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
- C04B24/2623—Polyvinylalcohols; Polyvinylacetates
- C04B24/2629—Polyvinylalcohols; Polyvinylacetates containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention discloses an ester ether copolymerization low bleeding type polycarboxylate superplasticizer which is prepared by polymerizing the following raw materials: polyethylene glycol monomethyl ether, maleic anhydride, a catalyst, a polymerization inhibitor, vinyl polyoxyethylene ether, unsaturated acid, unsaturated cyclic alcohol, a composite reducing agent, a chain transfer agent and an initiator. The invention also discloses a preparation method of the water reducing agent. The invention effectively adjusts the functional group distribution and molecular weight of the product through molecular structure design, and the prepared product effectively reduces the phenomena of concrete segregation and bleeding when the sand material is cleaner, especially when the sand material is in discontinuous grade distribution, and has obvious effect.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to an ester ether copolymerization low bleeding type polycarboxylate superplasticizer and a preparation method thereof.
Background
The polycarboxylate superplasticizer is used as a novel high-performance water reducing agent, has high attention paid to personnel in the building industry in recent years due to the characteristics of excellent performance, environmental protection, no pollution and the like, is developed and popularized at a high speed, the market share is continuously increased year by year, and the polycarboxylate superplasticizer is also used as a specified product in national key construction projects and projects. However, with the continuous expansion of the national infrastructure and the continuous improvement of the environmental protection requirement, the amount of high-quality sand and stone materials is gradually reduced, and in recent years, the sea sand desalination is gradually applied to the concrete industry. The sea sand desalting step is unreasonable in grading, and the sand is basically free of powder after being washed, so that the traditional polycarboxylate superplasticizer product is easy to bleed and isolate, and the problem of over sensitivity is directly exposed, and the sea sand desalting step is greatly limited in practical application. Therefore, the production and development of the low-water-secretion type polycarboxylate water reducer ensure concrete construction and ensure the quality of concrete are imperative.
The patent CN201410405710 and the patent CN201410252102 mainly synthesize an ether water-retaining polycarboxylic acid water reducer through molecular structure design. The designed ether water-retaining polycarboxylate superplasticizer has small difference with the conventional ether polycarboxylate superplasticizer, low selectivity, relatively low water-reducing rate of the simple ester superplasticizer and low cost performance.
In patent CN201110448118, an ether water reducing agent and an ester water reducing agent are mainly compounded, and then a certain amount of polyhydroxy carboxylate with excellent water retention performance and a saccharide compound are added for compounding, so as to comprehensively improve the water retention performance of the concrete admixture. The method belongs to a method of compounding by an external mixing method to obtain the polycarboxylic acid water-retaining agent, reduces the bleeding rate of concrete, has relatively low selectivity and adaptability, and is difficult to meet different market demands.
CN201610021360 introduces ester macromonomer MPEG-AA and organosilicon monomer for polymerization, directly polymerizes siloxane functional group on polycarboxylic acid molecular chain, and adopts TPEG and MPEG-MA for copolymerization to synthesize water-retaining polycarboxylic acid water reducer. According to the method, the water retention performance of the product is hopefully changed by introducing the organic silicon monomer, and as the organic silicon monomer is generally poor in water solubility, the reaction conditions and the reaction process are complex, the reaction conversion rate is low, and the obtained high water retention polycarboxylate water reducer is low in cost performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an ester ether copolymerization low bleeding type polycarboxylate superplasticizer.
The invention is realized by adopting the following scheme:
an ester ether copolymerization low bleeding type polycarboxylate superplasticizer is prepared by polymerizing the following raw materials in parts by mass:
the invention also aims to provide a preparation method of the ester ether copolymerized low-bleeding polycarboxylate superplasticizer, which adopts the following scheme:
a preparation method of an ester ether copolymerization low-bleeding type polycarboxylate superplasticizer applies any one of the raw materials, and comprises the following steps:
(1) mixing polyethylene glycol monomethyl ether, maleic anhydride, a catalyst and a polymerization inhibitor, heating to 160-180 ℃, stirring and simultaneously vacuumizing to enable the mixture to react for 5-7 hours under the vacuum degree of 0.3-0.5 MPa, adding 160 parts of deionized water after the reaction is finished, and cooling to below 60 ℃ to obtain an esterified monomer aqueous solution;
(2) adding vinyl polyoxyethylene ether into the esterified monomer aqueous solution, mixing, heating, stirring and dissolving;
(3) uniformly mixing unsaturated acid, unsaturated cyclic alcohol and a proper amount of deionized water to obtain a first mixed solution;
(4) uniformly mixing the composite reducing agent, the chain transfer agent and a proper amount of deionized water to obtain a second mixed solution;
(5) when the temperature of the material obtained in the step (2) is stable, controlling the temperature to be 60-70 ℃, adding an initiator into the material at one time, preserving the heat for 15-30 min, then simultaneously dripping a first mixed solution and a second mixed solution, finishing dripping the first mixed solution within 3h, finishing dripping the second mixed solution within 3.5h, and continuing preserving the heat for reaction for 1-1.5 h at 60-70 ℃ after finishing dripping;
(6) and (3) complementing deionized water to the material obtained in the step (5), cooling to 40 ℃, adding 15-20 parts of liquid alkali for neutralization, and thus obtaining the ester ether copolymerization low bleeding type polycarboxylate superplasticizer.
The invention has the beneficial effects that:
1. the ester ether copolymerization low bleeding type polycarboxylate superplasticizer introduces unsaturated cyclic alcohol with strong hydrophilicity, polyether and an esterification monomer to carry out ester ether copolymerization reaction through molecular structure design, and regulates the bleeding performance and the dispersing performance of target molecules by adjusting the grafting proportion of each functional monomer. A large number of cyclic alcohol structures are introduced into the structure, and due to the steric hindrance effect and the hydroxyl effect formed by the cyclic structure, the release of free water can be effectively reduced, and the dispersion effect is improved.
2. The ester ether copolymerization low-bleeding type polycarboxylate superplasticizer disclosed by the invention adopts an ester ether copolymerization method, so that the defects of low water reducing rate and poor flowing slump-retaining effect of a pure ester water-retaining polycarboxylate product are overcome, and the cost performance of the product is improved.
3. The ester ether copolymerization low bleeding type polycarboxylate superplasticizer disclosed by the invention has better cement adaptability and material adaptability. When sand materials are relatively clean, particularly in discontinuous grading, the phenomena of concrete segregation and bleeding are effectively reduced. Under the same test environment, the concrete water reducing agent has the same concrete water reducing rate as the conventional polycarboxylic acid water reducing agent while having the same mixing amount, and has better concrete slump retaining effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In an embodiment of the invention, one of the invention points is that the raw materials for preparing the ester ether copolymerized low-bleeding type polycarboxylate superplasticizer comprise:
in a preferred embodiment of the present invention, the polyethylene glycol monomethyl ether has a molecular weight of 600.
In a preferred embodiment of the invention, the polyoxyethylene vinyl ether has a molecular weight of 2400.
In a preferred embodiment of the present invention, the initiator is at least one of ammonium persulfate, sodium persulfate, and hydrogen peroxide.
In a preferred embodiment of the present invention, the chain transfer agent is at least one of thioglycolic acid, mercaptopropionic acid, and sodium methallylsulfonate.
In a preferred embodiment of the present invention, the complex reducing agent is at least one of L-ascorbic acid, sodium hypophosphite, and sodium bisulfite.
In a preferred embodiment of the present invention, the catalyst is one or a combination of concentrated sulfuric acid and p-toluenesulfonic acid.
In a preferred embodiment of the present invention, the polymerization inhibitor is one of phenothiazine, p-hydroxyanisole, and copper dibutyldithiocarbamate.
In a preferred embodiment of the present invention, the unsaturated acid is at least one of methacrylic acid and acrylic acid.
In a preferred embodiment of the present invention, the unsaturated cyclic alcohol is at least one of ethylene cyclohexanol, ethylene cyclopentanol; 1, 2-dimethyl-3- (1-methylvinyl) cyclopentanol, 2-methyl-5- (1-methylvinyl) cyclohexanol.
In the embodiment of the invention, the second invention is a method for preparing an ester ether copolymerized low bleeding type polycarboxylate water reducer, which comprises the following steps:
(1) mixing polyethylene glycol monomethyl ether, maleic anhydride, a catalyst inhibitor and a polymerization agent, heating to 160-180 ℃, stirring and simultaneously vacuumizing to enable the mixture to react for 5-7 hours under the vacuum degree of 0.3-0.5 MPa, adding 160 parts of deionized water after the reaction is finished, and cooling to below 60 ℃ to obtain an esterified monomer aqueous solution;
(2) adding vinyl polyoxyethylene ether into the esterified monomer aqueous solution, mixing, heating, stirring and dissolving;
(3) uniformly mixing unsaturated acid, unsaturated cyclic alcohol and a proper amount of deionized water to obtain a first mixed solution;
(4) uniformly mixing the composite reducing agent, the chain transfer agent and a proper amount of deionized water to obtain a second mixed solution;
(5) when the temperature of the material obtained in the step (2) is stable, controlling the temperature to be 60-70 ℃, adding an initiator into the material at one time, preserving the heat for 15-30 min, then simultaneously dripping a first mixed solution and a second mixed solution, finishing dripping the first mixed solution within 3h, finishing dripping the second mixed solution within 3.5h, and continuing preserving the heat for reaction for 1-1.5 h at 60-70 ℃ after finishing dripping;
(6) and (3) complementing deionized water to the material obtained in the step (5), cooling to 40 ℃, adding 15-20 parts of liquid alkali for neutralization, and thus obtaining the ester ether copolymerization low bleeding type polycarboxylate superplasticizer.
The following description is further provided in connection with specific examples.
Example 1
Respectively preparing a first mixed solution and a second mixed solution according to the following ratio:
first mixed solution: methacrylic acid (15 parts) + vinylcyclohexanol (3 parts) +1, 2-dimethyl-3- (1-methylethenyl) cyclopentanol (6 parts) + water (30 parts)
The second mixed solution: thioglycolic acid (1.2 parts) + L-ascorbic acid (0.2 parts) + sodium hypophosphite (0.5 parts) + water (40 parts)
(1) Mixing 30 parts of polyethylene glycol monomethyl ether, 8 parts of maleic anhydride, 0.5 part of concentrated sulfuric acid and 0.1 part of p-hydroxyanisole, heating to 160-180 ℃, stirring and simultaneously vacuumizing to enable the mixture to react for 5-7 hours under the vacuum degree of 0.3-0.5 MPa, adding 160 parts of deionized water after the reaction is finished, and cooling to below 60 ℃ to obtain an esterified monomer aqueous solution;
(2) adding 145 parts of vinyl polyoxyethylene ether into the esterified monomer aqueous solution, mixing, heating, stirring and dissolving;
(3) when the temperature of the material obtained in the step (2) is stable, controlling the temperature to be 60-70 ℃, adding 1.3 parts of 27.5% hydrogen peroxide into the material at one time, preserving the heat for 15-30 min, then beginning to simultaneously dropwise add a first mixed solution and a second mixed solution, finishing dropwise adding the first mixed solution within 3h, finishing dropwise adding the second mixed solution within 3.5h, and continuing to carry out heat preservation reaction at 60-70 ℃ for 1h after finishing dropwise adding;
(4) and (4) adding 70 parts of deionized water into the material obtained in the step (3), cooling to 40 ℃, adding 18 parts of 32% liquid alkali for neutralization, and thus obtaining the ester ether copolymerization low bleeding type polycarboxylate superplasticizer.
Example 2
Respectively preparing a first mixed solution and a second mixed solution according to the following ratio:
first mixed solution: methacrylic acid (12 parts) + vinylcyclohexanol (6 parts) +1, 2-dimethyl-3- (1-methylethenyl) cyclopentanol (7 parts) + water (30 parts)
The second mixed solution: thioglycolic acid (1.2 parts) + L-ascorbic acid (0.2 parts) + sodium hypophosphite (0.5 parts) + water (40 parts)
(1) Mixing 30 parts of polyethylene glycol monomethyl ether, 8 parts of maleic anhydride, 0.5 part of concentrated sulfuric acid and 0.1 part of p-hydroxyanisole, heating to 160-180 ℃, stirring and simultaneously vacuumizing to enable the mixture to react for 5-7 hours under the vacuum degree of 0.3-0.5 MPa, adding 160 parts of deionized water after the reaction is finished, and cooling to below 60 ℃ to obtain an esterified monomer aqueous solution;
(2) adding 145 parts of vinyl polyoxyethylene ether into the esterified monomer aqueous solution, mixing, heating, stirring and dissolving;
(3) when the temperature of the material obtained in the step (2) is stable, controlling the temperature to be 60-70 ℃, adding 1.3 parts of 27.5% hydrogen peroxide into the material at one time, preserving the heat for 15-30 min, then beginning to simultaneously dropwise add a first mixed solution and a second mixed solution, finishing dropwise adding the first mixed solution within 3h, finishing dropwise adding the second mixed solution within 3.5h, and continuing to carry out heat preservation reaction at 60-70 ℃ for 1h after finishing dropwise adding;
(4) and (4) adding 70 parts of deionized water into the material obtained in the step (3), cooling to 40 ℃, adding 18 parts of 32% liquid alkali for neutralization, and thus obtaining the ester ether copolymerization low bleeding type polycarboxylate superplasticizer.
Example 3
Respectively preparing a first mixed solution and a second mixed solution according to the following ratio:
first mixed solution: methacrylic acid (12 parts) + vinylcyclohexanol (6 parts) +1, 2-dimethyl-3- (1-methylethenyl) cyclopentanol (7 parts) + water (30 parts)
Second mixed solution: thioglycolic acid (1.2 parts) + L-ascorbic acid (0.2 parts) + sodium hypophosphite (0.5 parts) + water (40 parts)
(1) Mixing 40 parts of polyethylene glycol monomethyl ether, 10 parts of maleic anhydride, 0.6 part of concentrated sulfuric acid and 0.1 part of p-hydroxyanisole, heating to 160-180 ℃, stirring and simultaneously vacuumizing to enable the mixture to react for 5-7 hours under the vacuum degree of 0.3-0.5 MPa, adding 160 parts of deionized water after the reaction is finished, and cooling to below 60 ℃ to obtain an esterified monomer aqueous solution;
(2) adding 135 parts of vinyl polyoxyethylene ether into the esterified monomer aqueous solution, mixing, heating, stirring and dissolving;
(3) when the temperature of the material obtained in the step (2) is stable, controlling the temperature to be 60-70 ℃, adding 1.3 parts of 27.5% hydrogen peroxide into the material at one time, preserving the heat for 15-30 min, then beginning to simultaneously dropwise add a first mixed solution and a second mixed solution, finishing dropwise adding the first mixed solution within 3h, finishing dropwise adding the second mixed solution within 3.5h, and continuing to carry out heat preservation reaction at 60-70 ℃ for 1h after finishing dropwise adding;
(4) and (4) adding 70 parts of deionized water into the material obtained in the step (3), cooling to 40 ℃, adding 18 parts of 32% liquid alkali for neutralization, and thus obtaining the ester ether copolymerization low bleeding type polycarboxylate superplasticizer.
Example 4:
respectively preparing a first mixed solution and a second mixed solution according to the following mixture ratio:
first mixed solution: methacrylic acid (15 parts) + vinylcyclohexanol (3 parts) +1, 2-dimethyl-3- (1-methylethenyl) cyclopentanol (6 parts) + water (30 parts)
The second mixed solution: sodium methallyl sulfonate (1.8 parts) + L-ascorbic acid (0.3 parts) + water (40 parts)
(1) Mixing 30 parts of polyethylene glycol monomethyl ether, 8 parts of maleic anhydride, 0.5 part of concentrated sulfuric acid and 0.1 part of p-hydroxyanisole, heating to 160-180 ℃, stirring and simultaneously vacuumizing to enable the mixture to react for 5-7 hours under the vacuum degree of 0.3-0.5 MPa, adding 160 parts of deionized water after the reaction is finished, and cooling to below 60 ℃ to obtain an esterified monomer aqueous solution;
(2) adding 145 parts of vinyl polyoxyethylene ether into the esterified monomer aqueous solution, mixing, heating, stirring and dissolving;
(3) when the temperature of the material obtained in the step (2) is stable, controlling the temperature to be 60-70 ℃, adding 1.3 parts of 27.5% hydrogen peroxide into the material at one time, preserving the heat for 15-30 min, then beginning to simultaneously dropwise add a first mixed solution and a second mixed solution, finishing dropwise adding the first mixed solution within 3h, finishing dropwise adding the second mixed solution within 3.5h, and continuing to carry out heat preservation reaction at 60-70 ℃ for 1h after finishing dropwise adding;
(4) and (4) adding 70 parts of deionized water into the material obtained in the step (3), cooling to 40 ℃, adding 18 parts of 32% liquid alkali for neutralization, and thus obtaining the ester ether copolymerization low bleeding type polycarboxylate superplasticizer.
Example 5
The embodiment is a performance test of the ester ether copolymerization low bleeding type polycarboxylate superplasticizer prepared in the embodiment 1-4.
A concrete performance comparison test is carried out on the ester ether copolymerization low bleeding type polycarboxylate water reducer prepared in the embodiment 1-4 and a conventional polycarboxylate water reducer according to GB 8076-.
The test materials were as follows:
cement: southern P.0.42.5 cement;
coal ash: II-grade ash;
grading the mineral powder: s95;
coarse sand: fineness modulus is 2.8, mud content is 0.3%, and grading is discontinuous;
the spun yarn has a fineness modulus of 0.8 and a mud content of 0.2 percent.
Stone: the nominal grain diameter is 5 mm-30 mm continuous gradation, and the mud content is 0.3 percent.
And (3) test environment: the room temperature was 20 ℃.
Concrete mix ratio table 1:
TABLE 1
The performance data of the concrete obtained by using the water reducing agent of examples 1-4 in the concrete are shown in Table 2.
TABLE 2
As can be seen from the concrete data in Table 2, under the condition that sand is relatively clean and is in discontinuous gradation, compared with the conventional polycarboxylic acid, the ester ether copolymerized low bleeding type polycarboxylic acid water reducer has the water reducing rate equivalent to that of the conventional carboxylic acid under the condition of the same mixing amount, has better slump retaining effect, higher strength and low bleeding rate, improves the workability of concrete to a limited extent, and fully embodies the characteristics of the water reducer.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The ester ether copolymerized low-bleeding polycarboxylate superplasticizer is characterized by being prepared by polymerizing the following raw materials in parts by mass:
the unsaturated cyclic alcohol is a mixture of ethylene cyclohexanol and 1, 2-dimethyl-3- (1-methylvinyl) cyclopentanol;
the molecular weight of the vinyl polyoxyethylene ether is 2400;
the preparation method of the ester ether copolymerization low bleeding type polycarboxylate superplasticizer comprises the following steps:
(1) mixing polyethylene glycol monomethyl ether, maleic anhydride, a catalyst and a polymerization inhibitor, heating to 160-180 ℃, stirring and simultaneously vacuumizing to enable the mixture to react for 5-7 hours under the vacuum degree of 0.3-0.5 MPa, adding 160 parts of deionized water after the reaction is finished, and cooling to below 60 ℃ to obtain an esterified monomer aqueous solution;
(2) adding vinyl polyoxyethylene ether into the esterified monomer aqueous solution, mixing, heating, stirring and dissolving;
(3) uniformly mixing unsaturated acid, unsaturated cyclic alcohol and a proper amount of deionized water to obtain a first mixed solution;
(4) uniformly mixing the composite reducing agent, the chain transfer agent and a proper amount of deionized water to obtain a second mixed solution;
(5) when the temperature of the material obtained in the step (2) is stable, controlling the temperature to be 60-70 ℃, adding an initiator into the material at one time, preserving the heat for 15-30 min, then simultaneously dripping a first mixed solution and a second mixed solution, finishing dripping the first mixed solution within 3h, finishing dripping the second mixed solution within 3.5h, and continuing preserving the heat for reaction for 1-1.5 h at 60-70 ℃ after finishing dripping;
(6) and (3) complementing deionized water to the material obtained in the step (5), cooling to 40 ℃, adding 15-20 parts of liquid alkali for neutralization, and thus obtaining the ester ether copolymerization low bleeding type polycarboxylate superplasticizer.
2. The ester ether copolymerized low bleeding type polycarboxylic acid water reducing agent according to claim 1, wherein the molecular weight of the polyethylene glycol monomethyl ether is 600.
3. The ester ether copolymerized low bleeding type polycarboxylate water reducer according to claim 1, wherein the initiator is at least one of ammonium persulfate, sodium persulfate and hydrogen peroxide.
4. The ester ether copolymerization low bleeding type polycarboxylate water reducer according to claim 1, wherein the chain transfer agent is at least one of thioglycolic acid, mercaptopropionic acid and sodium methallyl sulfonate.
5. The ester ether copolymerization low bleeding type polycarboxylate water reducer according to claim 1, wherein the composite reducing agent is at least one of L-ascorbic acid, sodium hypophosphite and sodium bisulfite.
6. The ester ether copolymerization low bleeding type polycarboxylate superplasticizer according to claim 1, wherein the catalyst is one or a combination of concentrated sulfuric acid and p-toluenesulfonic acid.
7. The ester ether copolymerized low-bleeding polycarboxylate water reducer of claim 1, wherein the polymerization inhibitor is one of phenothiazine, p-hydroxyanisole and copper dibutyldithiocarbamate.
8. The ester ether copolymerization low bleeding type polycarboxylate superplasticizer according to claim 1, wherein the unsaturated acid is at least one of methacrylic acid and acrylic acid.
9. A preparation method of an ester ether copolymerization low-bleeding type polycarboxylate superplasticizer is characterized by applying the raw materials as claimed in any one of claims 1 to 8, and comprises the following steps:
(1) mixing polyethylene glycol monomethyl ether, maleic anhydride, a catalyst and a polymerization inhibitor, heating to 160-180 ℃, stirring and simultaneously vacuumizing to enable the mixture to react for 5-7 hours under the vacuum degree of 0.3-0.5 MPa, adding 160 parts of deionized water after the reaction is finished, and cooling to below 60 ℃ to obtain an esterified monomer aqueous solution;
(2) adding vinyl polyoxyethylene ether into the esterified monomer aqueous solution, mixing, heating, stirring and dissolving;
(3) uniformly mixing unsaturated acid, unsaturated cyclic alcohol and a proper amount of deionized water to obtain a first mixed solution;
(4) uniformly mixing the composite reducing agent, the chain transfer agent and a proper amount of deionized water to obtain a second mixed solution;
(5) when the temperature of the material obtained in the step (2) is stable, controlling the temperature to be 60-70 ℃, adding an initiator into the material at one time, preserving the heat for 15-30 min, then beginning to simultaneously dropwise add a first mixed solution and a second mixed solution, finishing dropwise adding the first mixed solution within 3h, finishing dropwise adding the second mixed solution within 3.5h, and continuously preserving the heat at 60-70 ℃ for reaction for 1-1.5 h after finishing dropwise adding;
(6) and (3) complementing deionized water to the material obtained in the step (5), cooling to 40 ℃, adding 15-20 parts of liquid alkali for neutralization, and thus obtaining the ester ether copolymerization low bleeding type polycarboxylate superplasticizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911383838.2A CN112608424B (en) | 2019-12-28 | 2019-12-28 | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911383838.2A CN112608424B (en) | 2019-12-28 | 2019-12-28 | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112608424A CN112608424A (en) | 2021-04-06 |
| CN112608424B true CN112608424B (en) | 2022-08-16 |
Family
ID=75225673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911383838.2A Active CN112608424B (en) | 2019-12-28 | 2019-12-28 | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112608424B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563512B (en) * | 2021-08-01 | 2022-08-19 | 苏州依司特新材料科技有限公司 | Anti-rewetting dispersant for reactive dye and preparation method thereof |
| CN115340643A (en) * | 2022-09-20 | 2022-11-15 | 信丰华轩建材有限公司 | Concrete water-retaining agent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256054A (en) * | 1993-03-01 | 1994-09-13 | Denki Kagaku Kogyo Kk | Cement dispersant |
| CN102206060A (en) * | 2011-03-15 | 2011-10-05 | 赵争艳 | Synthetic method for maleic polycarboxylic water reducer |
| CN102503221A (en) * | 2011-08-12 | 2012-06-20 | 周绍春 | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof |
| CN103193410A (en) * | 2013-03-27 | 2013-07-10 | 华南理工大学 | Shrinkage-reducing poly carboxylic acid water reducing agent and preparation method |
| CN108102042A (en) * | 2017-12-21 | 2018-06-01 | 河海大学淮安研究院 | Collapse protection type copolymer and preparation method thereof is shunk in a kind of self compensation |
| CN109265627A (en) * | 2018-09-27 | 2019-01-25 | 武汉奥克化学有限公司 | A kind of ester ether copoly type polycarboxylate water-reducer and preparation method thereof |
-
2019
- 2019-12-28 CN CN201911383838.2A patent/CN112608424B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256054A (en) * | 1993-03-01 | 1994-09-13 | Denki Kagaku Kogyo Kk | Cement dispersant |
| CN102206060A (en) * | 2011-03-15 | 2011-10-05 | 赵争艳 | Synthetic method for maleic polycarboxylic water reducer |
| CN102503221A (en) * | 2011-08-12 | 2012-06-20 | 周绍春 | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof |
| CN103193410A (en) * | 2013-03-27 | 2013-07-10 | 华南理工大学 | Shrinkage-reducing poly carboxylic acid water reducing agent and preparation method |
| CN108102042A (en) * | 2017-12-21 | 2018-06-01 | 河海大学淮安研究院 | Collapse protection type copolymer and preparation method thereof is shunk in a kind of self compensation |
| CN109265627A (en) * | 2018-09-27 | 2019-01-25 | 武汉奥克化学有限公司 | A kind of ester ether copoly type polycarboxylate water-reducer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112608424A (en) | 2021-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111234095B (en) | Method for preparing polycarboxylate superplasticizer by using C6 monomer | |
| CN110642993B (en) | Preparation method of retarding ether polycarboxylate superplasticizer | |
| CN105837763B (en) | Silane polycarboxylic acid water reducing agent and preparation method thereof | |
| CN105110687A (en) | Mud resisting and slump retaining type polycarboxylic acids water reducer and preparation method thereof | |
| CN109627397B (en) | Polycarboxylate superplasticizer for improving rheological property of cement paste and preparation method thereof | |
| CN109337024B (en) | Preparation method of retarding polycarboxylate superplasticizer | |
| CN107337769B (en) | Slump-retaining type polycarboxylate superplasticizer and preparation method thereof | |
| CN114195421A (en) | Preparation method of polycarboxylic acid admixture for machine-made sand concrete | |
| CN111100253A (en) | Concrete anti-sensitive polycarboxylate superplasticizer and preparation method thereof | |
| CN109265052B (en) | Preparation method of crosslinking viscosity-reduction type polycarboxylate superplasticizer | |
| CN112608424B (en) | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof | |
| CN112876667B (en) | Ferrocene modified polyoxyethylene ether monomer, ferrocene modified mud-resistant polycarboxylic acid water reducer and preparation method | |
| CN111234131B (en) | Glucolactone-based polycarboxylate water reducer and preparation method thereof | |
| CN113754842A (en) | Amphoteric anti-mud polycarboxylate superplasticizer | |
| CN103613307A (en) | Slump type polycarboxylate superplasticizer and preparation method thereof | |
| CN109180876B (en) | Preparation method of viscosity-reducing polycarboxylate superplasticizer | |
| CN114230727A (en) | Shrinkage-reducing ether polycarboxylate superplasticizer and preparation method thereof | |
| CN114044856A (en) | Mud-blocking type polycarboxylate superplasticizer and preparation method thereof | |
| CN114349914A (en) | Ferrocene modified mud-resistant polycarboxylic acid water reducer and preparation method thereof | |
| CN114195953B (en) | Low-sensitivity high-water-retention polycarboxylate superplasticizer and preparation method thereof | |
| CN110003406B (en) | Rosin modified polycarboxylate superplasticizer and preparation method thereof | |
| CN109721271B (en) | Polycarboxylate water reducing agent composition for self-compacting high-workability concrete | |
| CN114736341A (en) | Cross-linked polycarboxylate superplasticizer and preparation method thereof | |
| CN110746549B (en) | Ultra-long slow-release polycarboxylic slump retaining agent and preparation method thereof | |
| CN108084358B (en) | Preparation method of collapse-proof polycarboxylate superplasticizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |