CN115505076A - High-adaptability water-reducing strip slump-retaining type polycarboxylate superplasticizer and preparation method thereof - Google Patents
High-adaptability water-reducing strip slump-retaining type polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN115505076A CN115505076A CN202211286964.8A CN202211286964A CN115505076A CN 115505076 A CN115505076 A CN 115505076A CN 202211286964 A CN202211286964 A CN 202211286964A CN 115505076 A CN115505076 A CN 115505076A
- Authority
- CN
- China
- Prior art keywords
- water
- slump
- adaptability
- reducing
- polyether macromonomer
- 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.)
- Pending
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
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a high-adaptability water reducing belt slump retaining type polycarboxylic acid water reducing agent, which comprises an unsaturated polyether macromonomer, an unsaturated carboxylic acid monomer, a phosphorus-containing group functional monomer, an oxidizing agent, a chain transfer agent and a reducing agent; the molar ratio of the unsaturated polyether macromonomer to the unsaturated carboxylic acid monomer to the phosphorus-containing functional monomer is 1.5-4, the dosage of the oxidant is 0.3-0.8% of the total mass of the unsaturated polyether macromonomer, the dosage of the reducing agent is 0.1-0.5% of the total mass of the unsaturated polyether macromonomer, and the dosage of the chain transfer agent is 0.2-0.6% of the total mass of the unsaturated polyether macromonomer. The invention also discloses a preparation method of the high-adaptability water reducing strip slump retaining type polycarboxylate superplasticizer. The high-adaptability water-reducing strip slump-retaining type polycarboxylic acid water reducing agent disclosed by the invention contains phosphate groups, has a low acid-ether ratio, is strong in adaptability to cement and sand materials, has a high water reducing rate and a good slump-retaining effect, and has the effects of reducing viscosity and extracting slurry for a stone powder sand system and high-strength concrete.
Description
Technical Field
The invention relates to the technical field of water reducing agents, and particularly relates to a high-adaptability water reducing strip slump retaining type polycarboxylic acid water reducing agent and a preparation method thereof.
Background
In recent years, with the development of national infrastructure, concrete technology has been advanced, building structures have been complicated, enlarged, and functionalized, and polycarboxylic acid series products have been widely used. However, the high-quality sandstone aggregate is increasingly deficient, and the clay and the sulfate which are inevitable impurities in the concrete base material can seriously affect the working performance of the polycarboxylic acid water reducing agent, so that the flowing performance, the slump loss resistance and the workability of the concrete are poor, the risk of shrinkage cracks is increased, and the safety and durability of building construction and a concrete structure are affected.
With the rapid development of national economy, the continuous progress of the technology in the building industry and the continuous improvement of the demand of people, the high-strength concrete gradually enters the visual field of people and becomes an important subject of the concrete technology development at present and in the future. At present, high-strength concrete is applied to some building engineering, the preparation and application technology thereof is mature, but a plurality of problems still exist to be solved. In actual construction engineering, concrete with higher strength usually needs higher cementing material content and lower water-cement ratio, which brings the problems of high concrete viscosity, slow flowing, difficult construction, low construction efficiency, difficult guarantee of engineering quality and the like, and seriously restricts the development of high-strength concrete.
How to effectively solve the increasingly serious compatibility problem between the polycarboxylic acid water reducing agent and different types of cement and sand has been widely regarded. The compatibility problem is mainly shown as follows: the water reducing agent has no water reducing and plasticizing effect, serious bleeding and segregation phenomena of fresh concrete, extremely quick concrete slump loss and abnormal coagulation; the strength of the hardened concrete at each age is not obviously increased, the shrinkage of the concrete is increased, and the hardened concrete is easy to crack. The content of calcium sulfate and calcium aluminate in cement is changed, so that the polycarboxylic acid water reducing agent is frequently subjected to great fluctuation in mixing amount and performance, and even shows performance difference on different batches of cement. With the excessive development of river sand, the shortage of river sand is caused, more and more projects use artificial sand and machine-made sand, and meanwhile, each construction site is made of local materials, so that the sandstone aggregate of each project is often very different.
Phosphate groups are introduced into the molecular structure of the water reducer by the aid of an additive synthesis technical means, a novel adsorption group water reducer product with excellent working performance can be constructed, slump retaining performance of the product is enhanced while the water reducing rate is high, and the effects of viscosity reduction and slurry extraction are achieved; the method utilizes the strong adaptability of the low-acid-ether-ratio polycarboxylate superplasticizer to continuously maintain the excellent state, good construction performance and durability of concrete, and is one of the core technologies of the admixture which urgently need to be solved at present.
Disclosure of Invention
The invention aims to provide a high-adaptability water reducing zone slump retaining type polycarboxylate water reducing agent and a preparation method thereof, which are used for solving the technical problems of poor compatibility between the water reducing agent and different varieties of cement and gravels, high concrete viscosity, less slurry and high loss in the prior art.
In order to achieve the above purpose, one embodiment of the present invention provides a highly adaptive water reducing strip slump retaining type polycarboxylate water reducing agent, which comprises an unsaturated polyether macromonomer, an unsaturated carboxylic acid monomer, a phosphorus group functional monomer, an oxidizing agent, a chain transfer agent and a reducing agent;
the molar ratio of the unsaturated polyether macromonomer to the unsaturated carboxylic acid monomer to the phosphorus-containing functional monomer is 1.5-4, the dosage of the oxidant is 0.3-0.8% of the total mass of the unsaturated polyether macromonomer, the dosage of the reducing agent is 0.1-0.5% of the total mass of the unsaturated polyether macromonomer, and the dosage of the chain transfer agent is 0.2-0.6% of the total mass of the unsaturated polyether macromonomer.
In a preferred embodiment of the present invention, the phosphorus group-containing functional monomer is at least one of 2-hydroxyethyl methacrylate phosphate, polyethylene glycol methacrylate phosphate and end-capped amide phosphate.
In one preferable embodiment of the present invention, the unsaturated polyether macromonomer is at least one of ethylene glycol monovinyl polyglycol ether and 4-hydroxybutyl vinyl polyoxyethylene ether.
In a preferred embodiment of the present invention, the unsaturated carboxylic acid monomer is at least one of acrylic acid, methacrylic acid and maleic anhydride.
In a preferred embodiment of the present invention, the oxidizing agent is at least one of ammonium persulfate, sodium persulfate, potassium persulfate, and hydrogen peroxide.
In a preferred embodiment of the present invention, the reducing agent is at least one of vitamin C, ferrous sulfate, sodium sulfite, sodium bisulfite, sodium hypophosphite, and sodium hydrosulfite.
In a preferred embodiment of the present invention, the chain transfer agent is at least one of thioglycolic acid, mercaptoethanol and mercaptopropionic acid.
Based on the high-adaptability water reducing zone slump retaining type polycarboxylate superplasticizer disclosed by the invention, the invention also discloses a preparation method of the high-adaptability water reducing zone slump retaining type polycarboxylate superplasticizer, which comprises the following steps:
step (1): dissolving unsaturated polyether macromonomer in water, and then adding an oxidant to obtain a reactant solution;
step (2): and (2) respectively dropwise adding a mixed solution of an unsaturated carboxylic acid monomer, a phosphorus-containing functional monomer and a chain transfer agent and a mixed solution of a reducing agent into the reactant solution obtained in the step (1), carrying out heat preservation reaction after dropwise adding, and then adding alkali to adjust the pH value to obtain the high-adaptability slump-retaining polycarboxylic acid water reducer for the water reducing belt.
In one preferable embodiment of the present invention, in the step (2), the dropping time of the mixed solution of the unsaturated carboxylic acid monomer, the phosphorus-containing functional monomer and the chain transfer agent is 30min to 90min, and the dropping time of the mixed solution of the reducing agent is 50min to 120min under the stirring condition of 10 ℃ to 30 ℃.
In the preferable scheme of the invention, in the step (2), the temperature of the heat preservation reaction is 20-40 ℃, the reaction time is 0.5-1h, and the pH value is adjusted to 5-7.
In conclusion, the beneficial effects of the invention are as follows:
1. according to the invention, the unsaturated polyether macromonomer is introduced into a hydrophobic long side chain, so that steric hindrance equal resistance repulsion is provided, and the dispersion and dispersion retention performance of the water reducing agent are determined; the strong polar anion group on the main chain is introduced through the unsaturated carboxylic acid monomer, so that the effects of electrostatic repulsion and the like are provided; through the introduction of the functional monomer containing the phosphorus group, on one hand, the complexing ability of calcium ions is improved, the competitive adsorption capacity of the calcium ions and sulfate radicals is improved, the influence of clay on water reducing agent molecules is weakened, on the other hand, the viscosity of concrete is reduced, and the richness of concrete slurry is improved. By utilizing the carboxyl strong polar anion group, the molecular structure of the phosphorus-containing functional monomer and the high adaptability of the low-acid-ether-ratio water reducing agent, the slump-retaining polycarboxylate water reducing agent with the water reducing belt shows high water reducing performance and simultaneously enhances slump-retaining performance, and has the characteristics of viscosity reduction and slurry extraction. In a stone powder sand system, the sensitivity is low, the workability is good, the normal pumping construction is facilitated, and the quality of concrete is ensured.
2. The ratio of the unsaturated polyether macromonomer, the unsaturated carboxylic acid monomer and the phosphorus-containing functional monomer in the high-adaptability slump-retaining polycarboxylic acid water reducer has a large influence on the performance of the water reducer. The molar ratio of the unsaturated carboxylic acid monomer to the polyether macromonomer (acid ether ratio for short) is too low, and the water reduction rate is low; the acid-ether ratio is too high, the water reducing rate is possibly high, and the problems of bleeding, quick loss and the like easily occur in practical application. The molar ratio (ester ether ratio for short) of the phosphorus-containing functional monomer to the unsaturated polyether macromonomer is too low, so that on one hand, the quantity of carboxyl generated by hydrolysis of an ester group is less, and the slump-retaining performance is poor, and on the other hand, the viscosity reduction effect is not obvious, so that the construction of high-strength concrete is not facilitated; therefore, the acid-ether ratio, the ester-ether ratio, the dosage of the initiating system, the dosage of the bond transfer agent and the like influence the water reducing rate, slump loss resistance and viscosity reduction performance of the water reducing agent and influence the characteristic of the water reducing agent on the improvement workability.
3. The invention introduces phosphorus-containing functional groups into a molecular structure through free radical polymerization, reduces the acid-ether ratio, and synthesizes the high-adaptability water-reducing strip slump-retaining type polycarboxylate superplasticizer.
4. The high-adaptability water-reducing strip slump-retaining type polycarboxylic acid water reducing agent disclosed by the invention contains phosphate groups, has a low acid-ether ratio, is strong in adaptability to cement and sand materials, has a high water reducing rate and a good slump-retaining effect, and has the effects of reducing viscosity and extracting slurry for a stone powder sand system and high-strength concrete.
Detailed Description
The invention discloses a high-adaptability slump-retaining polycarboxylic acid water reducer for a water reducing belt, which comprises an unsaturated polyether macromonomer, an unsaturated carboxylic acid monomer, a phosphorus-containing group functional monomer, an oxidant, a chain transfer agent and a reducing agent;
wherein, the molar ratio of the unsaturated polyether macromonomer, the unsaturated carboxylic acid monomer and the phosphorus-containing functional monomer is 1.5-4, the dosage of the oxidant is 0.3-0.8% of the total mass of the unsaturated polyether macromonomer, the dosage of the reducing agent is 0.1-0.5% of the total mass of the unsaturated polyether macromonomer, and the dosage of the chain transfer agent is 0.2-0.6% of the total mass of the unsaturated polyether macromonomer;
the unsaturated polyether macromonomer is at least one of ethylene glycol monovinyl polyethylene glycol ether (EPEG) and 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG); the unsaturated carboxylic acid monomer is at least one of acrylic acid, methacrylic acid and maleic anhydride; the phosphorus-containing functional monomer is at least one of 2-hydroxyethyl methacrylate phosphate (HEMAP), polyethylene glycol methacrylate phosphate (PAP) and end-Capped Amide Phosphate (CAP); the oxidant is at least one of ammonium persulfate, sodium persulfate, potassium persulfate and hydrogen peroxide; the reducing agent is at least one of vitamin C, ferrous sulfate, sodium sulfite, sodium bisulfite, sodium hypophosphite and sodium hydrosulfite; the chain transfer agent is at least one of thioglycolic acid, mercaptoethanol and mercaptopropionic acid.
A preparation method of a high-adaptability water-reducing strip slump-retaining type polycarboxylate superplasticizer comprises the following steps:
step (1): sequentially adding unsaturated polyether macromonomer and water into a glass reactor provided with a thermometer and a mechanical stirrer, stirring at low temperature, and then adding an oxidant to obtain a reactant solution;
step (2): dissolving an unsaturated carboxylic acid monomer, a phosphorus-containing functional monomer and a chain transfer agent in water, and uniformly stirring and dispersing to obtain a solution A; dissolving a reducing agent in water, and stirring and dissolving to obtain a solution B;
and (3): respectively dripping the solution A and the solution B into the obtained reactant solution under the stirring state at 10-30 ℃, dripping the solution A for 30-90min, dripping the solution B for 50-120 min, keeping the temperature at 20-40 ℃ for reaction for 0.5-1 h after dripping is finished, and then adding alkali to adjust the pH value to 5-7, so as to obtain the water reducing belt slump retaining type polycarboxylic acid water reducer.
Example 1
A highly-adaptive water reducing strip slump retaining type polycarboxylic acid water reducing agent comprises 400g of unsaturated polyether macromonomer 4-hydroxybutyl vinyl polyoxyethylene ether, 25g of unsaturated carboxylic acid monomer acrylic acid, 12g of phosphorus group functional monomer 2-hydroxyethyl methacrylate phosphate, 1.5g of oxidant hydrogen peroxide, 1.2g of chain transfer agent mercaptopropionic acid and 0.7g of reducing agent vitamin C;
wherein the molar ratio of the unsaturated polyether macromonomer to the unsaturated carboxylic acid monomer to the phosphorus-containing functional monomer is 1.
A preparation method of a high-adaptability slump-retaining type polycarboxylic acid water reducer for water reducing belts comprises the following steps:
step (1): adding 400g of 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG) and 460g of deionized water into a glass reactor provided with a thermometer and a mechanical stirrer in sequence, stirring at a low speed for dissolving for 20min, and then adding 1.5g of hydrogen peroxide to obtain a reactant solution;
step (2): dissolving 25g of acrylic acid, 12g of 2-hydroxyethyl methacrylate phosphate and 1.2g of mercaptopropionic acid in 30g of deionized water, and uniformly stirring and dispersing to obtain a solution A; dissolving 0.7g of vitamin C in 80g of water, and stirring and dissolving to obtain a B solution;
and (3): and respectively dripping the solution A and the solution B into the obtained reactant solution under the stirring state at the temperature of 20 ℃, dripping the solution A for 40min, dripping the solution B for 60min, keeping the temperature at the temperature of 30-40 ℃ for reaction for 1h after dripping is finished, and then adding alkali to adjust the pH value to 6 to obtain the water reducing belt slump retaining type polycarboxylate water reducer.
Example 2
A high-adaptability slump-retaining polycarboxylic acid water reducer for a water reducing belt comprises 400g of unsaturated polyether macromonomer 4-hydroxybutyl vinyl polyoxyethylene ether, 34g of unsaturated carboxylic acid monomer acrylic acid, 15g of phosphorus group functional monomer polyethylene glycol methacrylate phosphate (PAP), 1.5g of oxidant hydrogen peroxide, 1.5g of chain transfer agent mercaptoethanol and 0.5g of reducing agent vitamin C;
wherein, the molar ratio of the unsaturated polyether macromonomer, the unsaturated carboxylic acid monomer and the phosphorus-containing functional monomer is 1.
A preparation method of a high-adaptability slump-retaining type polycarboxylic acid water reducer for water reducing belts comprises the following steps:
step (1): adding 400g of 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG) and 460g of deionized water into a glass reactor provided with a thermometer and a mechanical stirrer in sequence, stirring at a low speed for dissolving for 20min, and then adding 1.5g of hydrogen peroxide to obtain a reactant solution;
step (2): dissolving 34g of acrylic acid, 15g of polyethylene glycol methacrylate phosphate (PAP) and 1.5g of mercaptoethanol in 30g of deionized water, and uniformly stirring and dispersing to obtain a solution A; dissolving 0.5g of vitamin C in 80g of water, and stirring and dissolving to obtain a solution B;
and (3): respectively dripping the solution A and the solution B into the obtained reactant solution under the stirring state at 20 ℃, dripping the solution A for 55min, dripping the solution B for 80min, keeping the temperature at 30-40 ℃ for reaction for 1h after finishing dripping, and then adding alkali to adjust the pH value to 6 to obtain the water reducing strip slump retaining type polycarboxylate superplasticizer.
Example 3
A highly-adaptive water reducing strip slump retaining type polycarboxylate superplasticizer comprises 400g of unsaturated polyether macromonomer 4-hydroxybutyl vinyl polyoxyethylene ether, 29g of unsaturated carboxylic monomer acrylic acid, 35g of phosphorus-containing group functional monomer, 2g of oxidant hydrogen peroxide, 1.2g of chain transfer agent mercaptoethanol and 0.6g of reducing agent vitamin C;
wherein the molar ratio of the unsaturated polyether macromonomer to the unsaturated carboxylic acid monomer to the phosphorus-containing functional monomer is 1; the phosphorus group-containing functional monomer was a mixture of 15g of Capped Amide Phosphate (CAP) and 20g of 2-hydroxyethyl methacrylate phosphate (HEMAP).
A preparation method of a high-adaptability slump-retaining type polycarboxylic acid water reducer for water reducing belts comprises the following steps:
step (1): adding 400g of 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG) and 460g of deionized water into a glass reactor provided with a thermometer and a mechanical stirrer in sequence, stirring at a low speed for dissolving for 20min, and then adding 2g of hydrogen peroxide to obtain a reactant solution;
step (2): dissolving 29g of acrylic acid, 15g of end-Capped Amide Phosphate (CAP), 20g of 2-hydroxyethyl methacrylate phosphate (HEMAP) and 1.2g of mercaptoethanol in 30g of deionized water, and stirring and dispersing uniformly to obtain a solution A; dissolving 0.6g of vitamin C in 80g of water, and stirring and dissolving to obtain a B solution;
and (3): respectively dripping the solution A and the solution B into the obtained reactant solution under the stirring state at 20 ℃, dripping the solution A for 55min, dripping the solution B for 80min, keeping the temperature at 30-40 ℃ for reaction for 1h after finishing dripping, and then adding alkali to adjust the pH value to 6 to obtain the water reducing strip slump retaining type polycarboxylate superplasticizer.
Example 4
A high-adaptability water-reducing strip slump-retaining type polycarboxylic acid water reducer comprises 400g of unsaturated polyether macromonomer 4-hydroxybutyl vinyl polyoxyethylene ether, 38g of unsaturated carboxylic acid monomer acrylic acid, 15g of phosphorus-containing group functional monomer polyethylene glycol methacrylate phosphate (PAP), 1.5g of oxidant hydrogen peroxide, 1.5g of chain transfer agent mercaptoethanol and 0.5g of reducing agent vitamin C;
wherein the molar ratio of the unsaturated polyether macromonomer to the unsaturated carboxylic acid monomer to the phosphorus-containing functional monomer is 1.
A preparation method of a high-adaptability slump-retaining type polycarboxylic acid water reducer for water reducing belts comprises the following steps:
step (1): adding 400g of 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG) and 460g of deionized water into a glass reactor provided with a thermometer and a mechanical stirrer in sequence, stirring at a low speed for dissolving for 20min, and then adding 1.5g of hydrogen peroxide to obtain a reactant solution;
step (2): dissolving 38g of acrylic acid, 15g of polyethylene glycol methacrylate phosphate (PAP) and 1.5g of mercaptoethanol in 30g of deionized water, and uniformly stirring and dispersing to obtain a solution A; dissolving 0.5g of vitamin C in 80g of water, and stirring and dissolving to obtain a B solution;
and (3): respectively dripping the solution A and the solution B into the obtained reactant solution under the stirring state at 20 ℃, dripping the solution A for 55min, dripping the solution B for 80min, keeping the temperature at 30-40 ℃ for reaction for 1h after finishing dripping, and then adding alkali to adjust the pH value to 6 to obtain the water reducing strip slump retaining type polycarboxylate superplasticizer.
Comparative example 1
A high-adaptability water-reducing strip slump-retaining type polycarboxylic acid water reducer comprises 400g of unsaturated polyether macromonomer 4-hydroxybutyl vinyl polyoxyethylene ether, 44g of unsaturated carboxylic acid monomer acrylic acid, 15g of phosphorus-containing group functional monomer polyethylene glycol methacrylate phosphate (PAP), 1.5g of oxidant hydrogen peroxide, 1.5g of chain transfer agent mercaptoethanol and 0.5g of reducing agent vitamin C;
wherein the molar ratio of the unsaturated polyether macromonomer to the unsaturated carboxylic acid monomer to the phosphorus-containing functional monomer is 1.
A preparation method of a high-adaptability water-reducing strip slump-retaining type polycarboxylate superplasticizer comprises the following steps:
step (1): adding 400g of 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG) and 460g of deionized water into a glass reactor provided with a thermometer and a mechanical stirrer in sequence, stirring at a low speed for dissolving for 20min, and then adding 1.5g of hydrogen peroxide to obtain a reactant solution;
step (2): dissolving 44g of acrylic acid, 15g of polyethylene glycol methacrylate phosphate (PAP) and 1.5g of mercaptoethanol in 30g of deionized water, and uniformly stirring and dispersing to obtain a solution A; dissolving 0.5g of vitamin C in 80g of water, and stirring and dissolving to obtain a solution B;
and (3): respectively dripping the solution A and the solution B into the obtained reactant solution under the stirring state at 20 ℃, dripping the solution A for 55min, dripping the solution B for 80min, keeping the temperature at 30-40 ℃ for reaction for 1h after finishing dripping, and then adding alkali to adjust the pH value to 6 to obtain the water reducing strip slump retaining type polycarboxylate superplasticizer.
Comparative example 2
A highly-adaptive slump-retaining polycarboxylic acid water reducer for a water reducing belt comprises 400g of unsaturated polyether macromonomer 4-hydroxybutyl vinyl polyoxyethylene ether, 34g of unsaturated carboxylic acid monomer acrylic acid, 1.5g of oxidant hydrogen peroxide, 1.5g of chain transfer agent mercaptoethanol and 0.5g of reducing agent vitamin C;
wherein the molar ratio of the unsaturated polyether macromonomer to the unsaturated carboxylic acid monomer is 1.
A preparation method of a high-adaptability water-reducing strip slump-retaining type polycarboxylate superplasticizer comprises the following steps:
step (1): adding 400g of 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG) and 460g of deionized water into a glass reactor provided with a thermometer and a mechanical stirrer in sequence, stirring at a low speed for dissolving for 20min, and then adding 1.5g of hydrogen peroxide to obtain a reactant solution;
step (2): dissolving 34g of acrylic acid and 1.5g of mercaptoethanol in 30g of deionized water, and uniformly stirring and dispersing to obtain a solution A; dissolving 0.5g of vitamin C in 80g of water, and stirring and dissolving to obtain a solution B;
and (3): and respectively dripping the solution A and the solution B into the obtained reactant solution under the stirring state at the temperature of 20 ℃, dripping the solution A for 55min, dripping the solution B for 80min, keeping the temperature at 30-40 ℃ for reaction for 1h after dripping is finished, and then adding alkali to adjust the pH value to 6 to obtain the water reducing belt slump retaining type polycarboxylate water reducer.
Comparative example 3
Commercially available Water reducing agent 1
Comparative example 4
Commercial water reducing agent 2
Test detection
The water reducing agents in the examples and the comparative examples were subjected to a net slurry fluidity test and a concrete test formulation test, and the net slurry fluidity of cement was measured in accordance with GB/T8077-2000, experimental method for homogeneity of concrete admixtures, and the test results are shown in Table 1. The cement is Emei cement, and the concrete tests are carried out by adopting C30 and C60, and the test results are shown in tables 2 and 3.
The concrete performance test is carried out according to GB 8076-2008 concrete admixture, the slump constant, the expansion degree and the like of the concrete are measured, the fineness modulus of machine-made sand in the concrete is 2.9, and the broken stone is continuous graded broken stone with the grain diameter of 5mm-30 mm.
The adaptability of the water reducing agent is considered, different machine-made sands and stone powders are selected to carry out C30 test, and the test results are shown in Table 4.
Table 1: net slurry fluidity data
Table 2: concrete Performance data C60
| Sample (I) | Amount of incorporation (%) | Viscosity of the oil | Collapse(s) | Collapse(s) |
| Example 1 | 1.8 | Is suitable for | 4.0 | 4.5 |
| Example 2 | 1.8 | Is suitable for | 3.8 | 4.2 |
| Example 3 | 1.8 | Is suitable for | 4.2 | 4.6 |
| Example 4 | 1.8 | Is suitable for | 4.3 | 4.8 |
| Comparative example 1 | 1.8 | High viscosity | 7 | 11 |
| Comparative example 2 | 1.9 | High viscosity | 9 | 12 |
| Comparative example 3 | 1.9 | High viscosity | 8 | 10 |
| Comparative example 4 | 1.8 | In general | 6 | 7.5 |
Table 3: concrete performance data C30
| Sample (I) | Doping amount (%) | Workability | Initial/mm | 1h/mm | 2h/mm |
| Example 1 | 2.0 | Is preferably used | 235/610 | 235/590 | 230/580 |
| Example 2 | 2.0 | Is preferably used | 235/630 | 235/610 | 230/595 |
| Example 3 | 2.0 | Is preferably used | 235/635 | 235/625 | 230/600 |
| Example 4 | 2.0 | Is better | 235/620 | 235/595 | 230/585 |
| Comparative example 1 | 2.0 | In general | 235/620 | 220/550 | 215/520 |
| Comparative example 2 | 2.2 | In general terms | 235/615 | 215/510 | 200/420 |
| Comparative example 3 | 2.1 | In general | 235/610 | 220/540 | 210/500 |
| Comparative example 4 | 2.0 | In general | 235/620 | 220/550 | 215/520 |
Table 4: data sheet for different sand contrast test
As can be seen from the results of the clear paste performance tests in Table 1, the concrete tests in tables 2 and 3 and the comparative tests in Table 4, the water reducing agents in examples 1 to 4 are superior to the water reducing agents in comparative examples 1 to 4 in performance, and the slump-retaining type polycarboxylic acid water reducing agent with the water reducing zone provided by the invention has strong adaptability, high water reducing rate, enhanced slump-retaining performance and effects of viscosity reduction and slurry extraction.
Comparing the water reducing agent in the comparative example 1 with the water reducing agent in the example 2, the concrete viscosity and the loss in the comparative example 1 are both larger than those in the example 2, and the acid ether ratio in the application is proved to have a larger influence on the performance of the water reducing agent.
Compared with the water reducing agent in the embodiment 2, the water reducing agent in the comparative example 2 has the characteristics that the fluidity of the cement paste and the working performance of the concrete are far inferior to those in the embodiment, and the introduction of the phosphorus-containing functional monomer is proved to have great influence on the water reducing rate and the viscosity reducing effect of the water reducing agent.
Comparing the water reducer of comparative example 3 with the water reducer of example 3, the flow property of the cement paste and the working property of the concrete are far inferior to those of example 3.
Compared with the water reducing agent in the embodiment 2, the water reducing agent in the comparative example 4 is compared, the mixing amount of the comparative example 4 in different sand tests fluctuates from 1.7% to 2.4%, the mixing amount of the embodiment 2 in the same sand test fluctuates from 1.9% to 2.2%, the mixing amount fluctuation of the embodiment 2 is small, the production construction control is more convenient, and the adaptability of different sands in the embodiment 2 is better than that of the comparative example 4.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. The high-adaptability water reducing belt slump retaining type polycarboxylic acid water reducing agent is characterized in that: comprises unsaturated polyether macromonomer, unsaturated carboxylic acid monomer, phosphorus-containing group functional monomer, oxidant, chain transfer agent and reducing agent;
the molar ratio of the unsaturated polyether macromonomer to the unsaturated carboxylic acid monomer to the phosphorus-containing functional monomer is 1.5-4, the dosage of the oxidant is 0.3-0.8% of the total mass of the unsaturated polyether macromonomer, the dosage of the reducing agent is 0.1-0.5% of the total mass of the unsaturated polyether macromonomer, and the dosage of the chain transfer agent is 0.2-0.6% of the total mass of the unsaturated polyether macromonomer.
2. The high-adaptability water-reducing strip slump-retaining type polycarboxylate water reducer as claimed in claim 1, wherein: the phosphorus-containing group functional monomer is at least one of 2-hydroxyethyl methacrylate phosphate, polyethylene glycol methacrylate phosphate and end-capped amide phosphate.
3. The high-adaptability water-reducing strip slump-retaining type polycarboxylate water reducer of claim 1, which is characterized in that: the unsaturated polyether macromonomer is at least one of ethylene glycol monoethyl ether and 4-hydroxybutyl ethylene polyoxyethylene ether.
4. The high-adaptability water-reducing strip slump-retaining type polycarboxylate water reducer of claim 1, which is characterized in that: the unsaturated carboxylic acid monomer is at least one of acrylic acid, methacrylic acid and maleic anhydride.
5. The high-adaptability water-reducing strip slump-retaining type polycarboxylate water reducer as claimed in claim 1, wherein: the oxidant is at least one of ammonium persulfate, sodium persulfate, potassium persulfate and hydrogen peroxide.
6. The high-adaptability water-reducing strip slump-retaining type polycarboxylate water reducer as claimed in claim 1, wherein: the reducing agent is at least one of vitamin C, ferrous sulfate, sodium sulfite, sodium bisulfite, sodium hypophosphite and sodium hydrosulfite.
7. The high-adaptability water-reducing strip slump-retaining type polycarboxylate water reducer of claim 1, which is characterized in that: the chain transfer agent is at least one of thioglycolic acid, mercaptoethanol and mercaptopropionic acid.
8. A preparation method of a high-adaptability slump-retaining type polycarboxylic acid water reducing agent for a water reducing zone is characterized by comprising the following steps:
step (1): dissolving unsaturated polyether macromonomer in water, and then adding an oxidant to obtain a reactant solution;
step (2): and (2) respectively dropwise adding a mixed solution of an unsaturated carboxylic acid monomer, a phosphorus-containing functional monomer and a chain transfer agent and a mixed solution of a reducing agent into the reactant solution obtained in the step (1), carrying out heat preservation reaction after dropwise adding, and then adding alkali to adjust the pH value to obtain the high-adaptability slump-retaining polycarboxylic acid water reducer for the water reducing belt.
9. The preparation method of the high-adaptability slump-retaining type polycarboxylate superplasticizer for water reducing belts as claimed in claim 8, wherein: in the step (2), the dropping time of the mixed solution of the unsaturated carboxylic acid monomer, the phosphorus-containing functional monomer and the chain transfer agent is 30-90 min and the dropping time of the mixed solution of the reducing agent is 50-120 min under the stirring condition of 10-30 ℃.
10. The preparation method of the high-adaptability slump-retaining type polycarboxylate superplasticizer for water reducing belts as claimed in claim 8, wherein: in the step (2), the temperature of the heat preservation reaction is 20-40 ℃, the time is 0.5-1h, and the pH is adjusted to 5-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211286964.8A CN115505076A (en) | 2022-10-20 | 2022-10-20 | High-adaptability water-reducing strip slump-retaining type polycarboxylate superplasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211286964.8A CN115505076A (en) | 2022-10-20 | 2022-10-20 | High-adaptability water-reducing strip slump-retaining type polycarboxylate superplasticizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115505076A true CN115505076A (en) | 2022-12-23 |
Family
ID=84509559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211286964.8A Pending CN115505076A (en) | 2022-10-20 | 2022-10-20 | High-adaptability water-reducing strip slump-retaining type polycarboxylate superplasticizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115505076A (en) |
-
2022
- 2022-10-20 CN CN202211286964.8A patent/CN115505076A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107325234B (en) | Anti-mud phosphate modified polycarboxylate superplasticizer and preparation method thereof | |
| CN109651566B (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN107286298B (en) | Slow-release polycarboxylate superplasticizer and preparation method thereof | |
| CN109776742A (en) | A kind of anti-chamotte mould polycarboxylate water-reducer of phosphate ester-containing and preparation method thereof | |
| CN105924592B (en) | Viscosity-reducing polycarboxylic acid water reducer and preparation method thereof | |
| CN109369859B (en) | Concrete tackifying type viscosity regulator and preparation method thereof | |
| CN111019060B (en) | Preparation method of tannic acid base star-shaped polycarboxylate superplasticizer | |
| CN101817657A (en) | Polycarboxylic acid slump retaining agent | |
| CN106467604A (en) | A kind of viscosity reduction type polycarboxylate water-reducer and preparation method thereof | |
| CN110642994A (en) | Preparation method of stone powder adaptive polycarboxylate superplasticizer | |
| CN111349199B (en) | Steady-state polycarboxylic acid superplasticizer with core-shell structure and preparation method thereof | |
| CN112126022A (en) | Formula and preparation method of polycarboxylate superplasticizer | |
| CN114044858A (en) | Comprehensive polycarboxylic acid water reducing agent and preparation method thereof | |
| CN110627972A (en) | Novel mud-resistant polyether polycarboxylic acid water reducer and normal-temperature synthesis process thereof | |
| CN111961148B (en) | Reaction air-entraining type polycarboxylate superplasticizer and preparation method thereof | |
| CN107759742A (en) | A kind of polycarboxylate water-reducer and preparation method thereof and application method | |
| CN111560105B (en) | Viscosity-reduction type tannic acid based star polycarboxylate superplasticizer and preparation method thereof | |
| CN109626860B (en) | Preparation method of block viscosity-reducing concrete admixture | |
| CN113773457B (en) | Low-creep high-efficiency polycarboxylate superplasticizer and preparation method thereof | |
| CN115505076A (en) | High-adaptability water-reducing strip slump-retaining type polycarboxylate superplasticizer and preparation method thereof | |
| CN115926066A (en) | Polycarboxylate superplasticizer and preparation method thereof | |
| CN113683736B (en) | Viscosity-reducing polycarboxylate superplasticizer for high-strength concrete and preparation method thereof | |
| CN114133492A (en) | Preparation method of polycarboxylic acid concrete water reducing agent | |
| CN113461870A (en) | Mud-resistant early-strength polycarboxylate superplasticizer and preparation method and application thereof | |
| CN109535347B (en) | Preparation method of block water-retaining concrete admixture |
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 |