CN111170671A - Preparation method of slump-retaining solid polycarboxylate superplasticizer - Google Patents
Preparation method of slump-retaining solid polycarboxylate superplasticizer Download PDFInfo
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- CN111170671A CN111170671A CN201811343789.5A CN201811343789A CN111170671A CN 111170671 A CN111170671 A CN 111170671A CN 201811343789 A CN201811343789 A CN 201811343789A CN 111170671 A CN111170671 A CN 111170671A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a preparation method of a slump-retaining solid polycarboxylic acid water reducing agent. The invention takes unsaturated polyoxyethylene ether, unsaturated carboxylic acid and unsaturated ester as monomer raw materials, and adopts a free radical body polymerization process under the action of an initiator and a chain transfer agent to prepare the slump-retaining solid polycarboxylic acid water reducing agent. The slump-retaining solid polycarboxylic acid water reducing agent prepared by the invention has the advantages of simple and efficient synthesis process, environmental protection, transportation cost saving and the like, has good workability and slump retention performance in concrete application, and can better meet the requirements of remote transportation and construction of fresh concrete.
Description
Technical Field
The invention relates to the field of building additives, in particular to a preparation method of a slump-retaining solid polycarboxylic acid water reducing agent.
Background
The polycarboxylate superplasticizer has the advantages of low mixing amount, high dispersibility, good slump retention, designable molecular structure, environmental friendliness and the like, and is widely applied to engineering. At present, the most common preparation method of the polycarboxylic acid water reducing agent adopts an aqueous solution free radical polymerization process, so that liquid products with mass concentration of 20-40% are common in the market. However, the liquid polycarboxylate superplasticizer is influenced by packaging and transportation cost, and particularly in projects far away from construction sites, the cost is obviously increased, so that the research and development of preparing the solid polycarboxylate superplasticizer are of great significance for reducing the transportation cost, and popularizing and developing the polycarboxylate superplasticizer.
Patent CN100366565C reports a preparation method of a powder polycarboxylate superplasticizer. The patent is that the polycarboxylate superplasticizer solution is atomized by an atomizer, and then dried and settled to obtain the powder polycarboxylate superplasticizer. The method solves the problems of wall hanging and possible combustion of the water reducing agent powder in the spray drying process, but the high energy consumption caused by high temperature required for drying, and the partial crosslinking of the polycarboxylate water reducing agent is easily caused in the high-temperature atomization process to damage the structure of the polycarboxylate water reducing agent.
Patent CN102936349A reports a method for producing a solid polycarboxylic acid water reducing agent. This patent is sent into microwave drying oven with liquid polycarboxylate water reducing agent and is carried out the conveying and dry, and drying temperature is 93 ~ 98 ℃. The invention avoids the problems of high energy consumption of spray drying and low performance of solid products, but the microwave drying increases the production cost of the solid products and is not suitable for large-scale industrial production.
Patent CN105061690A reports a preparation method of a high water-reducing type solid polycarboxylic acid high performance water reducing agent. According to the method, unsaturated polyoxyethylene ether is heated and melted, and then mixed liquid of unsaturated carboxylic acid, unsaturated amide and a chain transfer agent is dripped under the action of an initiator, so that the solid polycarboxylic acid high-performance water reducing agent is prepared through free radical bulk polymerization. The invention has the advantages of simple process, high conversion rate, environmental protection, no pollution and the like, but the product has poor dispersion retentivity and is difficult to meet the requirement of long-distance transportation of the ready-mixed concrete.
Patent CN106749967A reports a preparation method of a solid slump-retaining polycarboxylic acid water reducing agent. The patent reduces the concentration of the reaction system by adding an organic solvent into the polymerization system, avoids the occurrence of gel reaction, and removes the organic solvent by vacuum after the reaction is completed. The solid polycarboxylate superplasticizer prepared by the method has excellent water reducing and dispersing effects and dispersion and retention capacity, but the removal by using an organic solvent not only increases the production cost, but also easily causes environmental pollution.
Based on the existing problems, the invention improves the preparation method of the slump-retaining solid polycarboxylic acid water reducing agent so as to meet the use requirements of the slump-retaining solid polycarboxylic acid water reducing agent in different projects.
Disclosure of Invention
The invention aims to provide a preparation method of a slump-retaining solid polycarboxylic acid water reducing agent aiming at the defects of the prior art. The method adopts a bulk polymerization process to obtain the slump-retaining solid polycarboxylic acid water reducing agent, realizes the effect of slow release in the alkaline environment of cement, effectively prolongs the slump-retaining time and enhances the slump-retaining performance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: unsaturated polyoxyethylene ether, unsaturated carboxylic acid and unsaturated ester are used as monomer raw materials, a free radical body polymerization process is adopted under the action of an initiator and a chain transfer agent, a proper reaction monomer, an initiator, a chain transfer agent, reaction temperature and reaction time are selected through molecular design, and simultaneously, different initiator adding modes are adjusted to preferably prepare the slump-retaining solid polycarboxylic acid water reducer.
In addition, the invention also provides a preparation method of the slump-retaining solid polycarboxylic acid water reducing agent, which comprises the following specific steps:
step 1, adding unsaturated polyoxyethylene ether into a reaction kettle, heating to 40-50 ℃ under stirring, and enabling the unsaturated polyoxyethylene ether to be in a molten state;
step 2, preparing a mixed liquid containing unsaturated carboxylic acid, unsaturated ester and a chain transfer agent;
step 3, adjusting the unsaturated polyoxyethylene ether in a molten state in the step 1 to 60-70 ℃, adding an initiator into the unsaturated polyoxyethylene ether, and stirring and dissolving the initiator completely;
step 4, dropwise adding the mixed liquid in the step 2 into the material in the step 3 at a constant speed;
step 5, when half of the mixed liquid in the step 2 is dripped, adding an initiator into the material in the step 4;
step 6, after the mixed liquid in the step 2 is dripped, adding an initiator, and continuing to react for a certain time;
step 7, after the heat preservation is finished, cooling to 30-40 ℃, adding liquid caustic soda, and adjusting the pH to 5-7;
and 8, introducing the product into a condensation slicing machine to obtain a polycarboxylate superplasticizer sheet, and then pouring the polycarboxylate superplasticizer sheet into a crusher to be crushed to obtain the slump-retaining solid polycarboxylate superplasticizer.
The unsaturated polyoxyethylene ether in the step 1 is one or two of prenyl polyoxyethylene ether (TPEG) and isobutenol polyoxyethylene ether (HPEG), and the molecular weight is 3000.
The unsaturated carboxylic acid in the step 2 is one or more of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride and acrylamide, the unsaturated ester is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, and the chain transfer agent is one or more of sodium methallylsulfonate, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, sodium hypophosphite and sodium bisulfite. Wherein the unsaturated polyoxyethylene ether: unsaturated carboxylic acid: the molar ratio of unsaturated ester is 1: 2.0-3.5: 2.0-4.0 percent, and the dosage of the chain transfer agent is 0.5-1.2 percent of the mass of the unsaturated polyoxyethylene ether.
In the steps 3, 5 and 6, the initiator is one or more of dibenzoyl peroxide, azobisisobutyronitrile hydrochloride and dimethyl azobisisobutyrate. Wherein the total dosage of the initiator is 0.6-1.5% of the mass of the unsaturated polyoxyethylene ether, and the initiator is divided into three equal parts and added in batches according to the steps 3, 5 and 6.
More importantly, the mixed liquid of the small monomer and the chain transfer agent is dropwise added at a constant speed to participate in the reaction, the dropwise adding time is 2-4 hours, and the heat preservation time is 1-2 hours. In addition, the reaction kettle is connected with a temperature control system, and the reaction temperature is controlled to be stable at 60-70 ℃.
The liquid caustic soda is 60% by mass, and the reason for using the liquid caustic soda is that the neutralization reaction can be completed more uniformly, and the neutralization unevenness caused by the excessive viscosity of the system can be avoided.
The invention has the following beneficial effects:
1. the bulk polymerization process is adopted, the reaction is simple and efficient, green and environment-friendly, in addition, the raw materials for the reaction are simple and common, and the production cost is greatly reduced.
2. The initiator is added into the reaction system in batches, so that the proper active center concentration can be maintained, and the polymerization reaction can be smoothly carried out. And a certain amount of initiator is added in the later stage of the reaction, so that the conversion rate of the monomer can be improved, and the product performance can be further improved.
3. The temperature is strictly controlled by the temperature control system in the polymerization process, so that the gel effect caused by reaction heat accumulation in the bulk polymerization process is avoided, and the method has the characteristics of controllable production process and stable product performance.
4. The slump-retaining solid polycarboxylic acid water reducing agent prepared by the invention has excellent water reducing dispersion effect and later-period slow-release slump-retaining capability in the alkaline environment of cement, has the characteristic of quick dissolution, and can be widely applied to the fields of concrete and mortar.
5. The slump-retaining solid polycarboxylic acid water reducing agent prepared by the invention has stable product performance, is convenient to store and transport, can greatly save the transport cost, and is particularly suitable for long-distance transport.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1
Adding 700g of prenyl polyoxyethylene ether with the molecular weight of 3000 into a reaction kettle, and heating to 50 ℃ under stirring to enable the prenyl polyoxyethylene ether to be in a molten state; preparing a mixed liquid consisting of 57.6g of acrylic acid, 98.6g of hydroxyethyl acrylate and 5.6g of 2-mercaptopropionic acid; adjusting the prenyl alcohol polyoxyethylene ether in a molten state to 70 ℃, adding 2.1g of dibenzoyl peroxide into the prenyl alcohol polyoxyethylene ether, uniformly stirring, then beginning to dropwise add the mixed liquid at a constant speed, wherein the dropwise adding time is 2 hours, when the mixed liquid is half dropwise added, continuously adding 2.1g of dibenzoyl peroxide, after the dropwise adding of the mixed liquid is finished, finally supplementing 2.1g of dibenzoyl peroxide, carrying out heat preservation reaction for 1 hour to complete the reaction, after the heat preservation is finished, cooling to 35 ℃, adding 23.6g of liquid caustic soda with the mass fraction of 60%, cooling after uniform stirring, slicing and crushing to obtain the slump-retaining solid polycarboxylic acid water reducer.
Example 2
Adding 700g of isobutylene alcohol polyoxyethylene ether with the molecular weight of 3000 into a reaction kettle, and heating to 40 ℃ under stirring to enable the isobutylene alcohol polyoxyethylene ether to be in a molten state; preparing a mixed liquid consisting of 68.8g of methacrylic acid, 98.6g of hydroxyethyl acrylate and 4.8g of thioglycolic acid; adjusting the isobutylene alcohol polyoxyethylene ether in a molten state to 65 ℃, adding 3.0g of azobisisobutylimidazoline hydrochloride into the isobutylene alcohol polyoxyethylene ether, uniformly stirring, then beginning to dropwise add the mixed liquid at a constant speed, wherein the dropwise adding time is 3 hours, when the mixed liquid is half dropwise added, continuously adding 3.0g of azobisisobutylimidazoline hydrochloride, after the dropwise adding of the mixed liquid is finished, finally supplementing 3.0g of azobisisobutylimidazoline hydrochloride, keeping the temperature for 2 hours to completely react, after the heat preservation is finished, cooling to 30 ℃, adding 22.2g of liquid alkali with the mass fraction of 60%, cooling after uniform stirring, slicing and crushing to obtain the slump-retaining solid polycarboxylic acid water reducer.
Example 3
Adding 700g of prenyl polyoxyethylene ether with the molecular weight of 3000 into a reaction kettle, and heating to 50 ℃ under stirring to enable the prenyl polyoxyethylene ether to be in a molten state; preparing a mixed liquid consisting of 43.2g of acrylic acid, 19.5g of itaconic acid, 104.4g of hydroxyethyl acrylate and 4.9g of thioglycolic acid; adjusting the prenyl alcohol polyoxyethylene ether in a molten state to 70 ℃, adding 1.8g of azobisisobutyronitrile into the prenyl alcohol polyoxyethylene ether, uniformly stirring, then beginning to dropwise add the mixed liquid at a constant speed, wherein the dropwise adding time is 2 hours, when the mixed liquid is half dropwise added, continuing to add 1.8g of azobisisobutyronitrile, after the dropwise adding of the mixed liquid is finished, finally supplementing 1.8g of azobisisobutyronitrile, carrying out heat preservation reaction for 1 hour to complete the reaction, after the heat preservation is finished, cooling to 35 ℃, adding 26.3g of liquid caustic soda with the mass fraction of 60%, cooling after uniform stirring, slicing and crushing to obtain the slump-retaining solid polycarboxylic acid water reducer.
Example 4
Adding 700g of isobutylene alcohol polyoxyethylene ether with the molecular weight of 3000 into a reaction kettle, and heating to 40 ℃ under stirring to enable the isobutylene alcohol polyoxyethylene ether to be in a molten state; preparing a mixed liquid consisting of 36.0g of acrylic acid, 78.0g of hydroxypropyl acrylate and 5.0g of sodium hypophosphite; adjusting the molten state of the isobutenol polyoxyethylene ether to 65 ℃, adding 1.9g of dimethyl azodiisobutyrate, uniformly stirring, then beginning to dropwise add the mixed liquid at a constant speed, wherein the dropwise adding time is 3h, when the mixed liquid is half dropwise added, continuing to add 1.9g of dimethyl azodiisobutyrate, after the dropwise adding of the mixed liquid is finished, finally supplementing 1.9g of dimethyl azodiisobutyrate, carrying out heat preservation reaction for 2h to complete the reaction, after the heat preservation is finished, cooling to 30 ℃, adding 14.8g of liquid alkali with the mass fraction of 60%, cooling after uniform stirring, slicing and crushing to obtain the slump-retaining solid polycarboxylic acid water reducer.
Example 5
Adding 700g of prenyl polyoxyethylene ether with the molecular weight of 3000 into a reaction kettle, and heating to 50 ℃ under stirring to enable the prenyl polyoxyethylene ether to be in a molten state; preparing a mixed liquid composed of 43.6g of methacrylic acid, 23.2g of maleic acid, 78.0g of hydroxypropyl acrylate and 5.9g of 3-mercaptopropionic acid; adjusting the prenyl alcohol polyoxyethylene ether in a molten state to 70 ℃, adding 2.8g of azobisisobutylimidazoline hydrochloride into the prenyl alcohol polyoxyethylene ether, uniformly stirring, then beginning to dropwise add the mixed liquid at a constant speed, wherein the dropwise adding time is 2 hours, when the mixed liquid is half dropwise added, continuously adding 2.8g of azobisisobutylimidazoline hydrochloride, after the dropwise adding of the mixed liquid is finished, finally supplementing 2.8g of azobisisobutylimidazoline hydrochloride, keeping the temperature for 1 hour to completely react, after the heat preservation is finished, cooling to 35 ℃, adding 25.6g of liquid alkali with the mass fraction of 60%, uniformly stirring, cooling, slicing and crushing to obtain the slump-retaining solid polycarboxylic acid water reducer.
Example 6
Adding 700g of isobutylene alcohol polyoxyethylene ether with the molecular weight of 3000 into a reaction kettle, and heating to 40 ℃ under stirring to enable the isobutylene alcohol polyoxyethylene ether to be in a molten state; preparing a mixed liquid consisting of 28.8g of acrylic acid, 7.1g of acrylamide and 6.0g of sodium bisulfite; adjusting the molten isobutylene alcohol polyoxyethylene ether to 65 ℃, adding 1.7g of azobisisobutyronitrile, uniformly stirring, then beginning to dropwise add the mixed liquid at a constant speed, wherein the dropwise adding time is 3 hours, when the mixed liquid is half dropwise added, continuously adding 1.7g of azobisisobutyronitrile, after the dropwise adding of the mixed liquid is finished, finally supplementing 1.7g of azobisisobutyronitrile, carrying out heat preservation reaction for 2 hours to complete the reaction, after the heat preservation is finished, cooling to 30 ℃, adding 16.2g of liquid caustic soda with the mass fraction of 60%, cooling after uniform stirring, slicing and crushing to obtain the slump-retaining solid polycarboxylic acid water reducer.
Example 7
Adding 700g of prenyl polyoxyethylene ether with the molecular weight of 3000 into a reaction kettle, and heating to 50 ℃ under stirring to enable the prenyl polyoxyethylene ether to be in a molten state; preparing a mixed liquid consisting of 43.2g of acrylic acid, 39.0g of hydroxyethyl methacrylate, 43.2g of hydroxypropyl methacrylate and 8.3g of sodium methallyl sulfonate; regulating prenyl alcohol polyoxyethylene ether in a molten state to 70 ℃, adding 2.0g of dimethyl azodiisobutyrate, uniformly stirring, then beginning to dropwise add the mixed liquid at a constant speed, wherein the dropwise adding time is 2 hours, when the mixed liquid is half dropwise added, continuously adding 2.0g of dimethyl azodiisobutyrate, after the dropwise adding of the mixed liquid is finished, finally supplementing 2.0g of dimethyl azodiisobutyrate, carrying out heat preservation reaction for 1 hour to complete the reaction, after the heat preservation is finished, cooling to 35 ℃, adding 17.7g of liquid alkali with the mass fraction of 60%, uniformly stirring, cooling, slicing and crushing to obtain the slump-retaining solid polycarboxylic acid water reducer.
Example 8
Adding 700g of isobutylene alcohol polyoxyethylene ether with the molecular weight of 3000 into a reaction kettle, and heating to 40 ℃ under stirring to enable the isobutylene alcohol polyoxyethylene ether to be in a molten state; preparing a mixed liquid composed of 43.2g of methacrylic acid, 46.4g of hydroxyethyl acrylate, 14.4g of hydroxypropyl methacrylate and 5.2g of 2-mercaptopropionic acid; adjusting the molten isobutylene polyoxyethylene ether to 65 ℃, adding 2.2g of azobisisobutylimidazoline hydrochloride into the molten isobutylene polyoxyethylene ether, uniformly stirring, then beginning to dropwise add the mixed liquid at a constant speed for 3 hours, continuing to add 2.2g of azobisisobutylimidazoline hydrochloride when half of the mixed liquid is added, finally supplementing 2.2g of azobisisobutylimidazoline hydrochloride after the dropwise addition of the mixed liquid is finished, keeping the temperature for 2 hours to completely react, cooling to 30 ℃ after the heat preservation is finished, adding 15.3g of liquid alkali with the mass fraction of 60%, cooling after uniform stirring, slicing and crushing to obtain the slump-retaining solid polycarboxylic acid water reducer.
Comparative example
The existing slump-retaining solid polycarboxylic acid water reducing agent sold on the market.
The implementation effect is as follows:
according to relevant regulations of GB 8076-2008 concrete admixture, tests are carried out to detect the expansion degree, the slump and the slump retentivity of the synthesized product. The concrete mixing ratio is shown in Table 1, and the test results are shown in Table 2.
TABLE 1 concrete mix proportion
| C | FA | K | S | G | W | Additive agent |
| 300 | 80 | 20 | 786 | 1086 | 170 | 0.26％× C |
Note: c is Jidong cement P.O 42.5.5 grade; FA is Huaneng I-grade fly ash; k is S95 grade mineral powder; s is natural river sand; g is crushed stone of 5-31.5mm, and is graded continuously; w is tap water; the admixture comprises the following components: 60% of a common solid polycarboxylic acid water reducing agent and 40% of a slump retaining agent solid polycarboxylic acid water reducing agent (w/w).
TABLE 2 concrete Performance test results
As can be seen from Table 2, the slump-retaining solid polycarboxylic acid water reducing agent synthesized by the invention is superior to the commercially available slump-retaining solid polycarboxylic acid water reducing agent, and has excellent slump-retaining performance in concrete.
The above description is only a preferred embodiment of the present invention, and although the present invention has been described by way of example, the present invention is not limited to the above embodiment. Various changes and modifications can be made by one skilled in the art within the spirit of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a slump-retaining solid polycarboxylic acid water reducing agent is characterized by comprising the following steps:
step 1, adding unsaturated polyoxyethylene ether into a reaction kettle, heating to 40-50 ℃ under stirring, and enabling the unsaturated polyoxyethylene ether to be in a molten state;
step 2, preparing a mixed liquid containing unsaturated carboxylic acid, unsaturated ester and a chain transfer agent;
step 3, adjusting the unsaturated polyoxyethylene ether in a molten state in the step 1 to 60-70 ℃, adding an initiator into the unsaturated polyoxyethylene ether, and stirring and dissolving the initiator completely;
step 4, dropwise adding the mixed liquid in the step 2 into the material in the step 3 at a constant speed;
step 5, when half of the mixed liquid in the step 2 is dripped, adding an initiator into the material in the step 4;
step 6, after the mixed liquid in the step 2 is dripped, adding an initiator, and continuing to react for a certain time;
step 7, after the heat preservation is finished, cooling to 30-40 ℃, adding liquid caustic soda, and adjusting the pH to 5-7;
and 8, introducing the product into a condensation slicing machine to obtain a polycarboxylate superplasticizer sheet, and then pouring the polycarboxylate superplasticizer sheet into a crusher to be crushed to obtain the slump-retaining solid polycarboxylate superplasticizer.
2. The slump-retaining solid polycarboxylic acid water reducing agent according to claim 1, characterized in that the unsaturated polyoxyethylene ether is one or two of isopentenol polyoxyethylene ether (TPEG) and isobutenol polyoxyethylene ether (HPEG), and the molecular weight is 3000.
3. The slump-retaining solid polycarboxylic acid water reducing agent according to claim 1, characterized in that the unsaturated carboxylic acid is one or more of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride and acrylamide, and the unsaturated ester is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; unsaturated polyoxyethylene ether: unsaturated carboxylic acid: the molar ratio of unsaturated ester is 1: 2.0-3.5: 2.0 to 4.0.
4. The slump-retaining solid polycarboxylic acid water reducing agent according to claim 1, characterized in that the chain transfer agent is one or more of sodium methallyl sulfonate, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, sodium hypophosphite and sodium bisulfite, and the dosage of the chain transfer agent is 0.5-1.2% of the mass of the unsaturated polyoxyethylene ether.
5. The slump-retaining solid polycarboxylic acid water reducing agent according to claim 1, wherein the initiator is one or more of dibenzoyl peroxide, azobisisobutyronitrile, azobisisobutyrimidazoline hydrochloride and dimethyl azobisisobutyrate; the initiator is 0.6-1.5% of the unsaturated polyoxyethylene ether, and is added evenly in three times according to the steps in claim 1.
6. The slump-retaining solid polycarboxylic acid water reducing agent according to claim 1, characterized in that the dropping time is 2-4 hours and the holding time is 1-2 hours.
7. The slump-retaining solid polycarboxylic acid water reducing agent according to claim 1, characterized in that the mass fraction of liquid caustic soda is 60%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111808240A (en) * | 2020-07-13 | 2020-10-23 | 山东华迪建筑科技有限公司 | Plastic-retaining polycarboxylic acid water reducing agent and preparation method thereof |
| CN112029048A (en) * | 2020-09-14 | 2020-12-04 | 安徽瑞和新材料有限公司 | Reactive extrusion preparation method of super-slow-release solid polycarboxylic acid water reducer |
| CN112851877A (en) * | 2020-12-31 | 2021-05-28 | 陕西友邦新材料科技有限公司 | Solid polycarboxylic acid water reducing agent and preparation method thereof |
| CN115340641A (en) * | 2021-05-12 | 2022-11-15 | 南京博特新材料有限公司 | High-adaptability solid polycarboxylate superplasticizer and preparation method thereof |
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| CN115340641A (en) * | 2021-05-12 | 2022-11-15 | 南京博特新材料有限公司 | High-adaptability solid polycarboxylate superplasticizer and preparation method thereof |
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