CN106589253B - Preparation method of anti-mud polycarboxylate superplasticizer - Google Patents
Preparation method of anti-mud polycarboxylate superplasticizer Download PDFInfo
- Publication number
- CN106589253B CN106589253B CN201611095721.0A CN201611095721A CN106589253B CN 106589253 B CN106589253 B CN 106589253B CN 201611095721 A CN201611095721 A CN 201611095721A CN 106589253 B CN106589253 B CN 106589253B
- Authority
- CN
- China
- Prior art keywords
- polyoxyethylene ether
- mixed solution
- allyl polyoxyethylene
- reducing agent
- mud
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A preparation method of a mud-resistant polycarboxylate superplasticizer comprises the following three steps: evenly dividing the mixed solution of the allyl polyoxyethylene ether into three parts; adding methacrylamide and an initiator into the first part of the mixed solution of allyl polyoxyethylene ether, then simultaneously dropwise adding end-capped amide phosphate, a reducing agent and a chain transfer agent to obtain a mixed solution I, adding the initiator into the second part of the mixed solution of allyl polyoxyethylene ether, and then dropwise adding sodium methallyl sulfonate to obtain a mixed solution II; and adding an initiator into the third part of the mixed solution of the allyl polyoxyethylene ether, then simultaneously dropwise adding the acrylic acid, the reducing agent and the chain transfer agent, then adding the mixed solution I and the mixed solution II, and then continuously dropwise adding the acrylic acid, the reducing agent and the chain transfer agent. The invention adopts normal pressure production, has low equipment requirement and convenient operation, and is beneficial to industrial production; when the mud content of the aggregate is higher, the sensitivity of the water reducing agent to the mud content of the aggregate can be reduced and the fluidity of concrete can be improved by adopting the water reducing agent synthesized by the invention on the premise of not increasing the mixing amount of the water reducing agent.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures in building materials, and particularly relates to a preparation method of a mud-resistant polycarboxylic acid water reducer.
Background
The polycarboxylate superplasticizer is a high-molecular polymer prepared by copolymerizing a polyether monomer with double bonds and other unsaturated micromolecules or effective groups with double bonds, and is widely applied to the concrete industry due to the advantages of low mixing amount, high water reducing rate, high slump retaining property, environmental protection, high durability and the like. However, a number of engineering examples and studies have shown that polycarboxylic acid water reducing agents are particularly sensitive to the mud content of aggregates compared to naphthalene, melamine and sulfamic acid based water reducing agents. Along with the explosive increase of the concrete construction quantity in recent years, the high-quality sandstone aggregate resource is sharply reduced, the mud content of the aggregate is continuously improved, along with the increase of the clay content, the initial fluidity and the slump retention performance of the concrete doped with the common polycarboxylate superplasticizer are continuously reduced, particularly, the fluidity is greatly reduced, the fluidity of the concrete is quickly disappeared for the sandstone with the mud content of more than 3 percent by the common polycarboxylate superplasticizer, and the concrete can not meet the concrete transportation construction requirements of a construction party far away. Although the problem that the ratio of the setting time of concrete to the compressive strength is reduced easily can be solved by increasing the mixing amount of the water reducing agent, the cost is greatly increased, and the problem is also an important reason for influencing the large-scale popularization of the polycarboxylic acid water reducing agent in the premixed concrete industry.
In patent CN 101798197A, a slow-release polycarboxylic acid water reducer for inhibiting the mud content of aggregate is disclosed, which is mainly prepared by compounding an anti-mud polycarboxylic acid water reducer, a retarder and natural zeolite powder. Because the clay mineral substance can be preferentially adsorbed on the surfaces of the natural zeolite powder particles, the clay-resistant polycarboxylate superplasticizer molecules are liberated and are easier to be adsorbed on the surfaces of the cement particles, so that the problem that the clay adsorbs the polycarboxylate molecules too much is solved. However, the zeolite porous structure also adsorbs excessive polycarboxylic acid molecules, so that the mixing amount of the water reducing agent is still increased and the cost is increased when the premixed concrete reaches the same fluidity.
In patent CN102617811A, a method for preparing an amphoteric vinyl polymer concrete anti-mud agent is disclosed, which adopts a method of esterification followed by polymerization, and introduces a cationic group into the molecular structure to obtain an anti-mud agent, but the method has higher esterification and polymerization temperature, which is not beneficial to industrial application, and moreover, because of introducing a vinyl monomer containing chloride ions, steel bars can be corroded.
Disclosure of Invention
The invention aims to provide a preparation method of an anti-mud polycarboxylate superplasticizer, which adopts normal pressure production, has low equipment requirement and convenient operation and is beneficial to industrial production; when the mud content of the aggregate is higher, the sensitivity of the polycarboxylate water reducer to the mud content of the aggregate can be reduced on the premise of not increasing the mixing amount of the water reducer by adopting the water reducer synthesized by the invention, and the fluidity of concrete is improved; the product does not contain chloride ions, and does not generate corrosion damage to reinforcing steel bars in concrete.
In order to realize the aim, the invention provides a preparation method of an anti-mud polycarboxylic acid water reducing agent, which comprises the following steps:
(1) adding a certain amount of allyl polyoxyethylene ether into a container filled with deionized water for dilution, stirring and heating to 45-65 ℃, uniformly stirring, and uniformly dividing the allyl polyoxyethylene ether mixed solution into three parts, namely an allyl polyoxyethylene ether mixed solution I, an allyl polyoxyethylene ether mixed solution II and an allyl polyoxyethylene ether mixed solution III;
(2-1) sequentially adding the allyl polyoxyethylene ether mixed solution I, a certain amount of methacrylamide and a certain amount of initiator at one time into a five-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel, keeping the temperature at 45-65 ℃ under the stirring condition, then simultaneously dropwise adding a certain amount of end-capped amide phosphate, a reducing agent and a chain transfer agent at a constant speed within 1-2 h, and keeping the stirring state after dropwise adding to obtain the mixed solution I;
(2-2) adding the mixed solution II of allyl polyoxyethylene ether and a certain amount of initiator into a three-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time, keeping the temperature at 45-65 ℃ under the stirring condition, then dropwise adding a certain amount of sodium methallyl sulfonate at a constant speed within 1-2 h, and keeping the stirring state after dropwise adding to obtain a mixed solution II;
(2-3) sequentially adding the allyl polyoxyethylene ether mixed solution III and a certain amount of initiator into a five-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time, keeping the temperature at 45-65 ℃ under the stirring condition, then simultaneously dropwise adding a certain amount of acrylic acid, a reducing agent and a chain transfer agent at a constant speed within 1-3 h, and keeping the stirring state to obtain a mixed solution III;
the step (2-1), the step (2-2) and the step (2-3) are carried out simultaneously;
(3) and (3) after the mixed solution I and the mixed solution II are added into the mixed solution III at one time, continuously and uniformly dripping acrylic acid, a reducing agent and a chain transfer agent within 1h, continuously stirring for 1h after dripping is finished, and cooling to normal temperature to obtain the anti-mud polycarboxylic acid water reducing agent.
Preferably, in the step (1), the temperature of the allyl polyoxyethylene ether mixed solution is raised to 55 ℃, and in the steps (2-1) to (2-3), the temperature is kept at 55 ℃ under the condition of stirring; in the step (2-1), the end-capped amide phosphate, the reducing agent and the chain transfer agent are dropwise added within 2h at a constant speed, in the step (2-2), sodium methallyl sulfonate is dropwise added within 2h at a constant speed, and in the step (2-3), acrylic acid, the reducing agent and the chain transfer agent are dropwise added within 2h at a constant speed.
Preferably, the mass ratio of the allyl polyoxyethylene ether to the deionized water in the step (1) is 1: 0.5-1: 1.2.
Preferably, the molar ratio of the allyl polyoxyethylene ether mixed liquor I to the methacrylamide in the step (2-1) is 1: 0.5-1: 1, and the molar ratio of the allyl polyoxyethylene ether mixed liquor I to the end-capped amide phosphate in the step (2-1) is 1: 0.6-1: 0.9.
Preferably, the molar ratio of the allyl polyoxyethylene ether mixed solution II to the sodium methallyl sulfonate in the step (2-2) is 1: 0.06-1: 0.08.
Preferably, the ratio of the molar amount of the allyl polyoxyethylene ether mixed liquid III in the step (2-3) to the total molar amount of the required acrylic acid in the steps (2-3) and (3) is 1: 2.5-1: 2.7.
Preferably, the initiator is hydrogen peroxide or sodium persulfate, and the molar ratio of the initiator to the allyl polyoxyethylene ether mixed liquor I, the allyl polyoxyethylene ether mixed liquor II and the allyl polyoxyethylene ether mixed liquor III is 1: 0.35-1: 0.55.
Preferably, the reducing agent is one of ascorbic acid, sodium ascorbate and azodiisoheptanonitrile; the molar ratio of the reducing agent to the mixed solution I of allyl polyoxyethylene ether and the mixed solution III of allyl polyoxyethylene ether is 1: 0.009-1: 0.015.
Preferably, the chain transfer agent is thioglycolic acid or mercaptopropionic acid; the molar ratio of the chain transfer agent to the mixed solution I of allyl polyoxyethylene ether and the mixed solution III of allyl polyoxyethylene ether is 1: 0.05-1: 0.09.
Preferably, the molecular weight of the allyl polyoxyethylene ether is 2000-2400.
Compared with the prior art, the method has the advantages that the effective groups are firstly aggregated and synthesized into effective micromolecules, and then the effective micromolecules are copolymerized into high molecular polymers, so that the effective groups can be better aggregated together; the preparation method adopts normal pressure production, has low equipment requirement, low production cost and convenient operation, and is beneficial to industrial production; when the mud content of the aggregate is higher, the mud-resistant polycarboxylate water reducer synthesized by the method realizes the resistance effect on the clay on the premise of not increasing the mixing amount of the polycarboxylate water reducer, reduces the sensitivity of the polycarboxylate water reducer on the mud content of the aggregate, and improves the water reducing effect of the polycarboxylate water reducer, so that the fluidity of concrete is improved, and the product does not contain chloride ions and has no corrosion hazard on reinforcing steel bars in the concrete.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A preparation method of a mud-resistant polycarboxylate superplasticizer comprises the following steps:
(1) adding a certain amount of allyl polyoxyethylene ether into a container filled with deionized water for dilution, wherein the molecular weight of the allyl polyoxyethylene ether is 2000, and the mass ratio of the allyl polyoxyethylene ether to the deionized water is 1:1.2, stirring and heating to 45 ℃, uniformly stirring, and uniformly dividing the allyl polyoxyethylene ether mixed solution into three parts, namely an allyl polyoxyethylene ether mixed solution I, an allyl polyoxyethylene ether mixed solution II and an allyl polyoxyethylene ether mixed solution III;
(2-1) sequentially adding the allyl polyoxyethylene ether mixed solution I, a certain amount of methacrylamide and a certain amount of hydrogen peroxide at one time into a five-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel; keeping the temperature at 45 ℃ under the stirring condition, then simultaneously dropwise adding a certain amount of end-capped amide phosphate, ascorbic acid and thioglycolic acid at a constant speed within 1h, and keeping the stirring state after dropwise adding to obtain a mixed solution I; the molar ratio of the allyl polyoxyethylene ether mixed liquor I to the methacrylamide and the end-capped amide phosphate ester is 1:0.5:0.6, the molar ratio of the hydrogen peroxide to the allyl polyoxyethylene ether mixed liquor I is 1:0.35, the molar ratio of the ascorbic acid to the allyl polyoxyethylene ether mixed liquor I is 1:0.009, and the molar ratio of the thioglycolic acid to the allyl polyoxyethylene ether mixed liquor I is 1: 0.05;
(2-2) adding the mixed solution II of allyl polyoxyethylene ether and a certain amount of hydrogen peroxide into a three-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time, keeping the temperature at 45 ℃ under the stirring condition, then dropwise adding a certain amount of sodium methallyl sulfonate at a constant speed within 1h, and keeping the stirring state after dropwise adding to obtain a mixed solution II; the molar ratio of the allyl polyoxyethylene ether mixed liquor II to the sodium methallyl sulfonate is 1:0.06, and the molar ratio of the hydrogen peroxide to the allyl polyoxyethylene ether mixed liquor II is 1: 0.35;
(2-3) sequentially adding an allyl polyoxyethylene ether mixed solution III and a certain amount of hydrogen peroxide into a five-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time, wherein the molar ratio of the hydrogen peroxide to the allyl polyoxyethylene ether mixed solution III is 1:0.35, keeping the temperature at 45 ℃ under the stirring condition, then simultaneously dropwise adding a certain amount of acrylic acid, ascorbic acid and thioglycolic acid at a constant speed within 1h, and keeping the stirring state to obtain a mixed solution III; the molar ratio of the ascorbic acid to the mixed solution III of the allyl polyoxyethylene ether is 1:0.009, and the molar ratio of the thioglycolic acid to the mixed solution III of the allyl polyoxyethylene ether is 1: 0.05;
the step (2-1), the step (2-2) and the step (2-3) are carried out simultaneously;
(3) and (3) adding the mixed solution I and the mixed solution II into the mixed solution III at one time, continuously and uniformly dripping acrylic acid, ascorbic acid and thioglycollic acid within 1h, wherein the ratio of the molar quantity of the allyl polyoxyethylene ether mixed solution III in the step (2-3) to the total molar quantity of the acrylic acid required in the step (2-3) and the step (3) is 1:2.5, continuously stirring for 1h after dripping is finished, and cooling to normal temperature to obtain the anti-mud polycarboxylic acid water reducer.
Example 2
A preparation method of a mud-resistant polycarboxylate superplasticizer comprises the following steps:
(1) adding a certain amount of allyl polyoxyethylene ether into a container filled with deionized water for dilution, wherein the molecular weight of the allyl polyoxyethylene ether is 2200, the mass ratio of the allyl polyoxyethylene ether to the deionized water is 1:0.85, stirring and heating to 55 ℃, uniformly stirring, and then uniformly dividing the allyl polyoxyethylene ether mixed solution into three parts, namely an allyl polyoxyethylene ether mixed solution I, an allyl polyoxyethylene ether mixed solution II and an allyl polyoxyethylene ether mixed solution III;
(2-1) sequentially adding the allyl polyoxyethylene ether mixed solution I, a certain amount of methacrylamide and a certain amount of sodium persulfate into a five-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time; keeping the temperature at 55 ℃ under the stirring condition, then simultaneously dropwise adding a certain amount of end-capped amide phosphate, sodium ascorbate and mercaptopropionic acid at a constant speed within 2h, and keeping the stirring state after dropwise adding to obtain a mixed solution I; the molar ratio of the allyl polyoxyethylene ether mixed liquor I to the methacrylamide and the end-capped amide phosphate ester is 1:0.75:0.75, the molar ratio of the sodium persulfate to the allyl polyoxyethylene ether mixed liquor III is 1:0.45, the molar ratio of the sodium ascorbate to the allyl polyoxyethylene ether mixed liquor I is 1:0.012, and the molar ratio of the mercaptopropionic acid to the allyl polyoxyethylene ether mixed liquor I is 1: 0.07;
(2-2) adding the mixed solution II of allyl polyoxyethylene ether and a certain amount of sodium persulfate into a three-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time, keeping the temperature at 55 ℃ under the stirring condition, then dropwise adding a certain amount of sodium methallyl sulfonate at a constant speed within 2h, and keeping the stirring state after dropwise adding to obtain a mixed solution II; the molar ratio of the allyl polyoxyethylene ether mixed liquor II to the sodium methallyl sulfonate is 1:0.07, and the molar ratio of the sodium persulfate to the allyl polyoxyethylene ether mixed liquor III is 1: 0.45;
(2-3) sequentially adding the allyl polyoxyethylene ether mixed solution III and a certain amount of sodium persulfate into a five-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time, wherein the molar ratio of the sodium persulfate to the allyl polyoxyethylene ether mixed solution III is 1:0.45, keeping the temperature at 55 ℃ under the stirring condition, then simultaneously dropwise adding a certain amount of acrylic acid, sodium ascorbate and mercaptopropionic acid at a constant speed within 2h, and keeping the stirring state to obtain a mixed solution III; the molar ratio of the sodium ascorbate to the allyl polyoxyethylene ether mixed solution III is 1:0.012, and the molar ratio of the mercaptopropionic acid to the allyl polyoxyethylene ether mixed solution III is 1: 0.07;
the step (2-1), the step (2-2) and the step (2-3) are carried out simultaneously;
(3) and (3) adding the mixed solution I and the mixed solution II into the mixed solution III at one time, continuously and uniformly dripping acrylic acid, sodium ascorbate and mercaptopropionic acid within 1h, wherein the ratio of the molar weight of the allyl polyoxyethylene ether mixed solution III in the step (2-3) to the total molar weight of the acrylic acid required in the step (2-3) and the step (3) is 1:2.6, continuously stirring for 1h after dripping is finished, and cooling to normal temperature to obtain the anti-mud polycarboxylic acid water reducer.
Example 3
A preparation method of a mud-resistant polycarboxylate superplasticizer comprises the following steps:
(1) adding a certain amount of allyl polyoxyethylene ether into a container filled with deionized water for dilution, wherein the molecular weight of the allyl polyoxyethylene ether is 2400, the mass ratio of the allyl polyoxyethylene ether to the deionized water is 1:0.5, stirring and heating to 65 ℃, uniformly stirring, and uniformly dividing the allyl polyoxyethylene ether mixed solution into three parts, namely an allyl polyoxyethylene ether mixed solution I, an allyl polyoxyethylene ether mixed solution II and an allyl polyoxyethylene ether mixed solution III;
(2-1) sequentially adding the allyl polyoxyethylene ether mixed solution I, a certain amount of methacrylamide and a certain amount of hydrogen peroxide at one time into a five-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel; keeping the temperature at 65 ℃ under the stirring condition, then simultaneously dropwise adding a certain amount of end-capped amide phosphate, azodiisoheptanonitrile and thioglycolic acid at a constant speed within 2h, and keeping the stirring state after dropwise adding to obtain a mixed solution I; the molar ratio of the allyl polyoxyethylene ether mixed liquor I to the methacrylamide and the end-capped amide phosphate is 1:1:0.9, the molar ratio of the hydrogen peroxide to the allyl polyoxyethylene ether mixed liquor III is 1:0.55, the molar ratio of the azodiisoheptanonitrile to the allyl polyoxyethylene ether mixed liquor I is 1:0.015, and the molar ratio of the thioglycolic acid to the allyl polyoxyethylene ether mixed liquor I is 1: 0.09;
(2-2) adding the mixed solution II of allyl polyoxyethylene ether and a certain amount of hydrogen peroxide into a three-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time, keeping the temperature at 65 ℃ under the stirring condition, then dropwise adding a certain amount of sodium methallyl sulfonate at a constant speed within 2h, and keeping the stirring state after dropwise adding to obtain the mixed solution II; the molar ratio of the allyl polyoxyethylene ether mixed liquor II to the sodium methallyl sulfonate is 1:0.08, and the molar ratio of the hydrogen peroxide to the allyl polyoxyethylene ether mixed liquor III is 1: 0.55;
(2-3) sequentially adding an allyl polyoxyethylene ether mixed solution III and a certain amount of hydrogen peroxide into a five-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time, wherein the molar ratio of the hydrogen peroxide to the allyl polyoxyethylene ether mixed solution III is 1:0.55, keeping the temperature at 65 ℃ under the stirring condition, then simultaneously dropwise adding a certain amount of acrylic acid, azodiisoheptanonitrile and thioglycolic acid at a constant speed within 3h, and keeping the stirring state to obtain a mixed solution III; the molar ratio of the azodiisoheptanonitrile to the allyl polyoxyethylene ether mixed solution III is 1:0.015, and the molar ratio of the mercaptoacetic acid to the allyl polyoxyethylene ether mixed solution III is 1: 0.09;
the step (2-1), the step (2-2) and the step (2-3) are carried out simultaneously;
(3) and (3) adding the mixed solution I and the mixed solution II into the mixed solution III at one time, continuously and uniformly dripping acrylic acid, azodiisoheptanonitrile and thioglycollic acid within 1h, wherein the ratio of the molar weight of the allyl polyoxyethylene ether mixed solution III in the step (2-3) to the total molar weight of the acrylic acid required in the step (2-3) and the step (3) is 1:2.7, continuously stirring for 1h after dripping is finished, and cooling to normal temperature to obtain the anti-mud polycarboxylic acid water reducer.
Effects of the implementation
1. Mortar fluidity test
The experimental cement adopts conch P.O42.5 cement, the experimental sand is standard sand, the soil replaces the corresponding amount of standard sand (the mud is sieved by a 75 mu m sieve and is mixed into the standard sand according to different proportions), the mixing proportion of the mortar is shown in the table 1:
TABLE 1 mortar test mixing ratio
| Sand | Cement | Water (W) | Water reducing agent |
| 1424 | 824 | 292 | 4.532 |
The anti-mud polycarboxylate water reducer prepared in the embodiments 1-3 of the invention is compared with a comparative polycarboxylate water reducer sample (a commercially available and general polycarboxylate water reducer is selected), sand with different mud contents is used for a mortar fluidity comparison experiment, the mortar fluidity is determined according to the steps of national standard GB/T2419-:
TABLE 2 mortar flowability contrast
2. Concrete Performance test
The experimental cement adopts sea snail P.O42.5 cement, the experimental sand is water-washed clean sand (the mud content is 0 percent), the soil replaces the clean sand with corresponding amount (the mud is sieved by a 75-micron sieve to obtain the mud in the common yellow sand and is mixed into the clean sand according to different proportions), and the mixing proportion of the concrete is shown in a table 3:
TABLE 3 concrete test mix proportions
| Sand | Cement | Crushing stone | Water (W) | Water reducing agent |
| 795 | 375 | 1048 | 164 | 5.428 |
The anti-mud polycarboxylate water reducer prepared in the embodiments 1-3 of the invention is compared with a comparative polycarboxylate water reducer sample (a commercially available general polycarboxylate water reducer is selected), sand with different mud contents is used for a concrete performance comparison experiment, the concrete performance comparison experiment is carried out according to the steps of national standard GB/T50080 plus 2011 Standard of Performance test methods of common concrete mixtures, and the concrete test results are shown in Table 4:
TABLE 4 comparison of concrete Performance tests
Since the expansion degree of concrete is related to its fluidity, the larger the expansion degree. When the slump is more than 220mm, the slump cannot accurately reflect the fluidity of the concrete, and the average diameter of the expanded concrete, namely the slump expansion degree, is used as a fluidity index, so that the fluidity of the concrete is more accurately reflected.
As can be seen from tables 2 and 4, when the anti-mud polycarboxylic acid water reducing agent synthesized by the method is added into mortar and concrete, the initial fluidity of the mortar and the concrete is not disturbed basically along with the increase of the mud content in the sand, and the fluidity of the mortar and the concrete at the middle and later periods is also excellent in maintenance, which shows that the anti-mud polycarboxylic acid water reducing agent synthesized by the method can realize the resistance effect on clay on the premise of not increasing the mixing amount of the polycarboxylic acid water reducing agent, reduce the sensitivity of the polycarboxylic acid water reducing agent on the mud content of aggregate, thereby improving the water reducing effect of the polycarboxylic acid water reducing agent and the fluidity of the mortar and the concrete, and the water reducing performance is higher than that of a commercially available polycarboxylic acid water reducing agent sample under the condition of containing or not containing mud.
Claims (10)
1. The preparation method of the anti-mud polycarboxylate superplasticizer is characterized by comprising the following steps:
(1) adding a certain amount of allyl polyoxyethylene ether into a container filled with deionized water for dilution, stirring and heating to 45-65 ℃, uniformly stirring, and uniformly dividing the allyl polyoxyethylene ether mixed solution into three parts, namely an allyl polyoxyethylene ether mixed solution I, an allyl polyoxyethylene ether mixed solution II and an allyl polyoxyethylene ether mixed solution III;
(2-1) sequentially adding the allyl polyoxyethylene ether mixed solution I, a certain amount of methacrylamide and a certain amount of initiator at one time into a five-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel, keeping the temperature at 45-65 ℃ under the stirring condition, then simultaneously dropwise adding a certain amount of end-capped amide phosphate, a reducing agent and a chain transfer agent at a constant speed within 1-2 h, and keeping the stirring state after dropwise adding to obtain the mixed solution I;
(2-2) adding the mixed solution II of allyl polyoxyethylene ether and a certain amount of initiator into a three-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time, keeping the temperature at 45-65 ℃ under the stirring condition, then dropwise adding a certain amount of sodium methallyl sulfonate at a constant speed within 1-2 h, and keeping the stirring state after dropwise adding to obtain a mixed solution II;
(2-3) sequentially adding the allyl polyoxyethylene ether mixed solution III and a certain amount of initiator into a five-neck flask provided with a thermometer, a stirrer and a constant-pressure funnel at one time, keeping the temperature at 45-65 ℃ under the stirring condition, then simultaneously dropwise adding a certain amount of acrylic acid, a reducing agent and a chain transfer agent at a constant speed within 1-3 h, and keeping the stirring state to obtain a mixed solution III;
the step (2-1), the step (2-2) and the step (2-3) are carried out simultaneously;
(3) and (3) after the mixed solution I and the mixed solution II are added into the mixed solution III at one time, continuously and uniformly dripping acrylic acid, a reducing agent and a chain transfer agent within 1h, continuously stirring for 1h after dripping is finished, and cooling to normal temperature to obtain the anti-mud polycarboxylic acid water reducing agent.
2. The preparation method of the anti-mud type polycarboxylate superplasticizer according to claim 1, wherein the temperature of the allyl polyoxyethylene ether mixed solution in the step (1) is raised to 55 ℃, and the temperature of the allyl polyoxyethylene ether mixed solution in the steps (2-1) to (2-3) is kept at 55 ℃ under stirring conditions; in the step (2-1), the end-capped amide phosphate, the reducing agent and the chain transfer agent are dropwise added within 2h at a constant speed, in the step (2-2), sodium methallyl sulfonate is dropwise added within 2h at a constant speed, and in the step (2-3), acrylic acid, the reducing agent and the chain transfer agent are dropwise added within 2h at a constant speed.
3. The preparation method of the anti-mud polycarboxylic acid water reducer according to claim 1 or 2, characterized in that the mass ratio of allyl polyoxyethylene ether to deionized water in the step (1) is 1: 0.5-1: 1.2.
4. The preparation method of the anti-mud polycarboxylic acid water reducer according to claim 1 or 2, characterized in that the molar ratio of the allyl polyoxyethylene ether mixed liquor I to the methacrylamide in the step (2-1) is 1: 0.5-1: 1, and the molar ratio of the allyl polyoxyethylene ether mixed liquor I to the end-capped amide phosphate ester in the step (2-1) is 1: 0.6-1: 0.9.
5. The preparation method of the anti-mud polycarboxylic acid water reducer according to claim 1 or 2, characterized in that the molar ratio of the allyl polyoxyethylene ether mixed liquor II to the sodium methallyl sulfonate in the step (2-2) is 1: 0.06-1: 0.08.
6. The preparation method of the anti-mud type polycarboxylate superplasticizer according to claim 1 or 2, wherein the ratio of the molar amount of the allyl polyoxyethylene ether mixed liquor III in the step (2-3) to the total molar amount of acrylic acid required in the step (2-3) and the step (3) is 1: 2.5-1: 2.7.
7. The preparation method of the anti-mud polycarboxylic acid water reducer according to claim 1 or 2, characterized in that the initiator is hydrogen peroxide or sodium persulfate, and the molar ratio of the initiator to the allyl polyoxyethylene ether mixed liquor I, the allyl polyoxyethylene ether mixed liquor II and the allyl polyoxyethylene ether mixed liquor III is 1: 0.35-1: 0.55.
8. The preparation method of the anti-mud polycarboxylic acid water reducing agent according to claim 1 or 2, characterized in that the reducing agent is one of ascorbic acid, sodium ascorbate and azobisisoheptonitrile; the molar ratio of the reducing agent to the mixed solution I of allyl polyoxyethylene ether and the mixed solution III of allyl polyoxyethylene ether is 1: 0.009-1: 0.015.
9. The preparation method of the anti-mud type polycarboxylate superplasticizer according to claim 1 or 2, wherein the chain transfer agent is thioglycolic acid or mercaptopropionic acid; the molar ratio of the chain transfer agent to the mixed solution I of allyl polyoxyethylene ether and the mixed solution III of allyl polyoxyethylene ether is 1: 0.05-1: 0.09.
10. The preparation method of the anti-mud polycarboxylic acid water reducer according to claim 1 or 2, characterized in that the molecular weight of the allyl polyoxyethylene ether is 2000-2400.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611095721.0A CN106589253B (en) | 2016-12-02 | 2016-12-02 | Preparation method of anti-mud polycarboxylate superplasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611095721.0A CN106589253B (en) | 2016-12-02 | 2016-12-02 | Preparation method of anti-mud polycarboxylate superplasticizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106589253A CN106589253A (en) | 2017-04-26 |
| CN106589253B true CN106589253B (en) | 2021-02-23 |
Family
ID=58595422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611095721.0A Active CN106589253B (en) | 2016-12-02 | 2016-12-02 | Preparation method of anti-mud polycarboxylate superplasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589253B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107129180A (en) * | 2017-05-11 | 2017-09-05 | 长沙加美乐素化工有限公司 | A kind of synthesis of clay inhibitor and preparation method |
| CN108912278A (en) * | 2018-07-13 | 2018-11-30 | 贵州石博士科技有限公司 | A kind of constant temperature perseverance pH polycarboxylate water-reducer and preparation method thereof |
| CN109553729B (en) * | 2018-11-28 | 2021-06-04 | 中国建材检验认证集团厦门宏业有限公司 | Amphoteric anti-mud water reducer and preparation method thereof |
| CN109593166A (en) * | 2018-11-28 | 2019-04-09 | 河南科之杰新材料有限公司 | A kind of anti-mud polycarboxylate water-reducer and preparation method thereof |
| CN109650762B (en) * | 2018-12-24 | 2020-08-11 | 科之杰新材料集团有限公司 | Phosphate type polycarboxylate superplasticizer and preparation method thereof |
| CN111087516A (en) * | 2019-12-18 | 2020-05-01 | 深圳大学 | Mud-resistant polycarboxylic water reducer and preparation method and application thereof |
| CN111087552A (en) * | 2019-12-22 | 2020-05-01 | 同济大学 | Synthetic method of polycarboxylic acid water reducer with high water reducing rate and mud resistance |
| CN111019064A (en) * | 2019-12-26 | 2020-04-17 | 河北铁园科技发展有限公司 | Polycarboxylate superplasticizer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229449A (en) * | 1988-06-30 | 1993-07-20 | Kawasaki Steel Corporation | Copolymer of polymerizable components in naphtha oil and maleic anhydride, process for producing said copolymer, and derivatives thereof |
| CN105085822A (en) * | 2015-08-07 | 2015-11-25 | 科之杰新材料集团有限公司 | Sludge-proof type polycarboxylate water-reducer and normal temperature preparing method thereof |
| CN105236806A (en) * | 2015-10-22 | 2016-01-13 | 石家庄市长安育才建材有限公司 | Phosphoric-acid-base modified polycarboxylic-acid water reducer with high adaptability and preparation method thereof |
-
2016
- 2016-12-02 CN CN201611095721.0A patent/CN106589253B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229449A (en) * | 1988-06-30 | 1993-07-20 | Kawasaki Steel Corporation | Copolymer of polymerizable components in naphtha oil and maleic anhydride, process for producing said copolymer, and derivatives thereof |
| CN105085822A (en) * | 2015-08-07 | 2015-11-25 | 科之杰新材料集团有限公司 | Sludge-proof type polycarboxylate water-reducer and normal temperature preparing method thereof |
| CN105236806A (en) * | 2015-10-22 | 2016-01-13 | 石家庄市长安育才建材有限公司 | Phosphoric-acid-base modified polycarboxylic-acid water reducer with high adaptability and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 抗泥型低坍损聚羧酸减水剂的制备与性能研究;骆志超等;《粉煤灰综合利用》;20161031;第37-40页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106589253A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106589253B (en) | Preparation method of anti-mud polycarboxylate superplasticizer | |
| CN105110687B (en) | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| CN105367720B (en) | A kind of diminishing collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| CN107140866B (en) | Universal anti-mud polycarboxylate superplasticizer and preparation method thereof | |
| CN103467670B (en) | Preparation method of anti-mud polycarboxylic water reducer | |
| CN112694574B (en) | Polycarboxylate superplasticizer with high mud resistance and high slump loss resistance and preparation method thereof | |
| CN104177562B (en) | Slow-release high-adaptability polyester polycarboxylic acid water-reducing agent and preparation method and application thereof | |
| CN112661914B (en) | Polycarboxylate superplasticizer special for machine-made sand and preparation method thereof | |
| CN105085822A (en) | Sludge-proof type polycarboxylate water-reducer and normal temperature preparing method thereof | |
| CN103897116A (en) | Mud-resistant polycarboxylic acid water reducer and preparation method thereof | |
| CN109651566A (en) | A kind of viscosity reduction type polycarboxylate water-reducer and preparation method thereof | |
| CN102515616A (en) | Composite slump-loss-resistant polycarboxylic acid water reducing agent and preparation method thereof | |
| CN108947301A (en) | A kind of anti-mud sacrifice agent of Compositional type and preparation method thereof | |
| CN105503012A (en) | Composition used for producing slow release anti-mud polycarboxylate-type water reducing agent | |
| CN104743957B (en) | Reduced and reinforced type polycarboxylate having high water-reducing rate and preparation method thereof | |
| CN105837738B (en) | A kind of anti-mud agent of polycarboxylic-acid cation and its preparation method and application | |
| CN112048035A (en) | Concrete segregation repairing agent and preparation method thereof | |
| CN107987235A (en) | A kind of preparation method of low hydration heat crack resistance type polycarboxylate water-reducer | |
| CN108047390B (en) | Preparation method of anti-mud-reduction type polycarboxylate superplasticizer | |
| CN106749962A (en) | A kind of anti-chamotte mould polycarboxylate water-reducer high and preparation method thereof | |
| CN114044856A (en) | Mud-blocking type polycarboxylate superplasticizer and preparation method thereof | |
| CN103641963B (en) | A kind of poly carboxylic acid series water reducer and preparation method thereof be applicable to containing mud aggregate | |
| CN105778010A (en) | Polycarboxylate superplasticizer with high slump retaining property and preparing method thereof | |
| CN104327221A (en) | Special anti-rusting type polycarboxylic acid water reducing agent for hydraulic engineering and preparation method of special anti-rust type polycarboxylic acid water reducing agent | |
| CN102206314A (en) | Polycarboxylic acid and application thereof, and cement water reducing agent containing polycarboxylic acid |
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 |