CN115432953B - Polycarboxylate superplasticizer for micro-expansion type ultra-high performance concrete, and preparation method and application thereof - Google Patents

Polycarboxylate superplasticizer for micro-expansion type ultra-high performance concrete, and preparation method and application thereof Download PDF

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CN115432953B
CN115432953B CN202210945351.4A CN202210945351A CN115432953B CN 115432953 B CN115432953 B CN 115432953B CN 202210945351 A CN202210945351 A CN 202210945351A CN 115432953 B CN115432953 B CN 115432953B
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solution
acid
parts
water
water reducer
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CN115432953A (en
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王文荣
杨武
杨林
房艳伟
秦明强
石韧
叶舟
高玉军
王全超
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Cccc Shec Wuhan Port New Materials Co ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302Water reducers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention provides a polycarboxylate water reducer for micro-expansion type ultra-high performance concrete, and a preparation method and application thereof, wherein the water reducer comprises the following raw materials in parts by weight: 60-100 parts of isopentenyl alcohol polyoxyethylene ether, 10-20 parts of fulvic acid, 0.01-0.03 part of ferrous sulfate, 0.5-1.5 parts of reducing agent D-isoascorbic acid, 0.1-0.5 part of 3-mercaptopropionic acid, 5-15 parts of acrylic acid, 3-6 parts of dimethylaminoethyl methacrylate and 0.01-0.05 part of persulfate. The water reducer provided by the invention has the functions of ultra-high water reduction, high slump loss resistance, viscosity reduction, crack control and the like, can improve various properties of ultra-high-performance concrete, and is beneficial to promoting the application and development of the ultra-high-performance concrete.

Description

Polycarboxylate superplasticizer for micro-expansion type ultra-high performance concrete, and preparation method and application thereof
Technical Field
The invention relates to the technical field of polycarboxylate superplasticizers, in particular to a preparation method and application of a micro-expansion polycarboxylate superplasticizer.
Background
The ultra-high performance concrete is used as the new generation of concrete, and has great application prospect due to the outstanding advantages of high strength, high toughness, high durability and the like. However, due to the ultra-high glue material usage amount and ultra-low water-glue ratio, the concrete has small fluidity, large viscosity, difficult discharge of bubbles and easy occurrence of cracks, and the application and development of the concrete are greatly limited. The polycarboxylate water reducer is a third-generation product of the water reducer, has the advantages of high water reduction, high slump loss resistance, low mixing amount, low shrinkage and the like, and can better solve the common problems in concrete. Therefore, the molecular structure of the polycarboxylate water reducer can be designed, so that the polycarboxylate water reducer can solve the problem of ultra-high performance concrete, overcomes the defects of the polycarboxylate water reducer and widens the application and development of the polycarboxylate water reducer.
CN109970921a discloses a high water-reducing low-sensitivity polycarboxylate water reducer and a preparation method thereof, according to the technical scheme, benzene rings and carboxyl structures are introduced at the tail ends of branched chains of polycarboxylate water reducer molecules through using esterification products of unsaturated polyether monomers and compounds a for synthesizing the polycarboxylate water reducer, the steric hindrance effect of the branched chains of the polycarboxylate water reducer molecules is enhanced through the benzene ring structures, the branched chains of the polycarboxylate water reducer molecules have steric hindrance effect and electrostatic repulsion effect through the carboxyl structures, so that the water-reducing rate of the prepared polycarboxylate water reducer is higher, but the requirements of concrete on slump retaining performance and cracking resistance cannot be met.
CN106317342a discloses a slow-release early-strength polycarboxylate water reducer and a preparation method thereof, wherein the slow-release early-strength polycarboxylate water reducer is prepared by adopting raw materials such as methyl allyl polyoxyethylene ether, acrylic acid, amino unsaturated acid ester, slump-retaining monomer, chain transfer agent, reducing agent, hydrogen peroxide and the like through polymerization reaction. The water reducer can promote the formation of hydration products and improve the early strength of concrete on the premise of realizing slump retaining performance, but can not meet the requirements of ultra-high performance concrete on ultra-high water reducing and viscosity reducing performances and can not solve the problem of hydration cracking of the concrete.
CN 105601827a discloses a preparation method of a concrete water reducing agent with ultra-high water reducing performance, which comprises the steps of polymerizing an unsaturated carboxylic acid monomer A, an unsaturated phosphoric acid monomer B, an ultraviolet active special monomer C and an auxiliary initiation monomer D in toluene solution by adopting an initiator through thermal initiation to obtain a macromolecule F with ultraviolet activity; adding the prepared solid active macromolecule F into deionized water for dissolution, and slowly dripping N-vinyl pyrrolidone (N-VP) and a monomer A under the irradiation of ultraviolet light for graft polymerization reaction to obtain the final water reducer molecule. The molecular side chain of the water reducer has double stabilization effects of electrostatic repulsion and steric hindrance, the water reducing capacity is greatly improved, but the performance requirements of ultra-high performance concrete on viscosity reduction, slump retaining, early strength and the like cannot be met, and the problem of hydration cracking of the concrete can be solved.
Disclosure of Invention
The invention provides a polycarboxylic acid water reducer for micro-expansion type ultra-high performance concrete, a preparation method and application thereof, and the prepared polycarboxylic acid water reducer for the expansion type ultra-high performance concrete has the functions of high viscosity reduction, water reduction, slump retention, crack resistance and the like.
The technical scheme of the invention is that the polycarboxylate water reducer for micro-expansion type ultra-high performance concrete comprises the following raw materials: isopentenol polyoxyethylene ether, fulvic acid, ferrous sulfate, a reducing agent D-isoascorbic acid, 3-mercaptopropionic acid, acrylic acid, dimethylaminoethyl methacrylate and persulfate.
Further, the stabilizer comprises 60-100 parts by weight of prenyl alcohol polyoxyethylene ether, 10-20 parts by weight of fulvic acid, 0.5-1.5 parts by weight of ferrous sulfate, 0.5-1.5 parts by weight of reducing agent D-isoascorbic acid, 0.1-0.5 part by weight of 3-mercaptopropionic acid, 5-15 parts by weight of acrylic acid, 3-6 parts by weight of dimethylaminoethyl methacrylate and 0.01-0.05 part by weight of persulfate.
Further, the molecular weight of the isopentenyl alcohol polyoxyethylene ether is 3000-8000.
Further, the persulfate is one of ammonium persulfate, sodium persulfate and potassium persulfate.
The invention also relates to a method for preparing the polycarboxylate superplasticizer, which comprises the following specific steps:
s1, adding isopentenol polyoxyethylene ether and fulvic acid into water for dissolution, and adding a ferrous sulfate solution after dissolution is completed to obtain a first solution;
s2, adding a reducing agent D-isoascorbic acid and 3-mercaptopropionic acid into water, and uniformly mixing to obtain a second solution;
s3, adding acrylic acid and dimethylaminoethyl methacrylate into water, and uniformly mixing to obtain a third solution;
s4, adding persulfate into the first solution, uniformly stirring, then dropwise adding the second solution and the third solution into the first solution, reacting at constant temperature for a period of time, and naturally cooling to room temperature;
and S5, finally adding liquid alkali to adjust the pH value to 6.5-7.5, and obtaining the micro-expansion type polycarboxylate superplasticizer for the ultra-high-performance concrete.
Further, the second solution and the third solution in the step S4 are added dropwise at the same time, the second solution is controlled to be added dropwise 20-30 min earlier than the third solution, the adding time of the second solution is 60-90min, and the adding time of the third solution is 90-120min.
Further, in the step S4, the stirring time is 50-70 min, and the stirring speed is 65+ -10 rpm.
Further, the reaction temperature in S4 is 20-50 ℃ and the reaction time is 1-3h.
The invention also relates to application of the water reducer in preparing ultra-high performance concrete, wherein the addition amount of the water reducer accounts for 2-3% of the dosage of the adhesive material.
The invention has the following beneficial effects:
1. the invention adopts pentenol polyoxyethylene ether with high water reduction and high viscosity reduction, acrylic acid, fulvic acid and a dimethylaminoethyl methacrylate monomer with viscosity reduction, water reduction and slump retention to carry out free radical self-polymerization reaction, thereby preparing the polycarboxylic acid water reducer for the expansion type ultra-high performance concrete with the functions of high viscosity reduction, water reduction, slump retention, crack resistance and the like.
2. The polycarboxylate water reducer molecule provided by the invention has an ultra-long pentenol polyoxyethylene ether side chain, so that the ultra-high steric hindrance is provided, and the cement hydration is promoted more favorably than a shorter polyether side chain, so that the early strength of UHPC is improved; meanwhile, the polyether side chain consists of hydrophilic hydroxyl, carboxyl and hydrophobic organic alkyl, and compared with a single epoxy ethane side chain, the polyether side chain is more beneficial to the extension of the side chain, further enhances the steric hindrance effect, reduces the hydrophilicity of the whole polycarboxylic acid molecule and is beneficial to reducing the viscosity of the UHPC mixture.
3. The polycarboxylate water reducer is synthesized under an acidic condition, is regulated to a neutral environment by liquid alkali, a large number of carboxyl groups and hydroxyl groups in a molecular side chain can quickly react with cement to provide an excellent water reducing effect, and in addition, after the polymerization reaction of the dimethylaminoethyl methacrylate in the raw material and a molecular main chain of the water reducer, the dimethylaminoethyl methacrylate is grafted to the molecular side chain of the polycarboxylate water reducer, and the ester groups can be hydrolyzed in an alkaline environment of concrete to release carboxyl groups, so that the slump retaining capacity of the water reducer is improved.
4. After the fulvic acid and the pentenol polyoxyethylene ether in the raw materials are subjected to copolymerization reaction, a large number of aromatic rings and alicyclic rings are provided on the side chains of the polycarboxylic acid water reducer molecules, and a large number of carboxyl, hydroxyl, methoxy and other groups are connected on the rings, so that the steric hindrance effect of the water reducer molecules is enhanced by the groups with hydrophilic and hydrophobic functions, and the prepared product has higher water reducing capacity and better slump retaining capacity.
5. Furthermore, the fulvic acid with a large number of acid functional groups (carboxyl, ketocarbonyl and hydroxyl) is introduced in the synthesis process of the polycarboxylate water reducer molecules, so that the water reducer molecules show acidic properties, and the water reducer molecules still carry a large number of different charges although pH adjustment exists in the later stage.
6. The polycarboxylate water reducer has the advantages of simple synthesis process, easily controlled conditions, no pollution, high performance and low blending amount, and solves the problems of complex production process, serious pollution and difficult performance adjustment of the existing compound blending expansion agent while reducing water and retaining slump.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
The main raw materials involved in the water reducer are as follows: isopentenol polyoxyethylene ether, fulvic acid, ferrous sulfate, D-isoascorbic acid, 3-mercaptopropionic acid, acrylic acid, dimethylaminoethyl methacrylate and potassium persulfate, wherein the weight ratio of each component is 100:10:0.01:0.5:0.1:5:3:0.01.
the preparation method of the water reducer comprises the following specific steps:
1) Adding D-isoascorbic acid and 3-mercaptopropionic acid into water, and uniformly mixing to obtain a solution A;
2) Uniformly mixing acrylic acid, dimethylaminoethyl methacrylate and water to obtain a solution B;
3) Adding isopentenol polyoxyethylene ether, fulvic acid and water into a reaction vessel, heating to 30 ℃, and stirring until the raw materials are fully dissolved; then adding potassium persulfate and ferrous sulfate, and simultaneously dripping solution A and solution B, wherein the solution A is dripped completely at 60min, and the mixed solution B is dripped completely at 90 min. After the dripping is finished, stirring for 60min at a stirring speed of 65rpm, then preserving heat at 30 ℃ for 1.5 hours, cooling to below 20 ℃, adding liquid alkali to adjust the pH value to 6.5, and obtaining the polycarboxylic acid water reducer P-1 for micro-expansion type ultra-high performance concrete.
Example 2:
the main raw materials involved in the water reducer are as follows: isopentenol polyoxyethylene ether, fulvic acid, ferrous sulfate, D-isoascorbic acid, 3-mercaptopropionic acid, acrylic acid, dimethylaminoethyl methacrylate and potassium persulfate, wherein the weight ratio of each component is 100:10:0.01:0.5:0.1:5:4.5:0.01.
the preparation method of the water reducer comprises the following specific steps:
1) Adding D-isoascorbic acid and 3-mercaptopropionic acid into water, and uniformly mixing to obtain a solution A;
2) Uniformly mixing acrylic acid, dimethylaminoethyl methacrylate and water to obtain a solution B;
3) Adding isopentenol polyoxyethylene ether, fulvic acid and water into a reaction vessel, heating to 30 ℃, and stirring until the raw materials are fully dissolved; then adding potassium persulfate and ferrous sulfate, and simultaneously dripping solution A and solution B, wherein the solution A is dripped completely at 60min, and the mixed solution B is dripped completely at 90 min. After the dripping is finished, stirring for 60min at a stirring speed of 65rpm, then preserving heat at 30 ℃ for 1.5 hours, cooling to below 20 ℃, adding liquid alkali to adjust the pH value to 6.5, and obtaining the polycarboxylic acid water reducer P-2 for micro-expansion type ultra-high performance concrete.
Example 3:
the main raw materials involved in the water reducer are as follows: isopentenol polyoxyethylene ether, fulvic acid, ferrous sulfate, D-isoascorbic acid, 3-mercaptopropionic acid, acrylic acid, dimethylaminoethyl methacrylate and potassium persulfate, wherein the weight ratio of each component is 100:10:0.01:0.5:0.1:5:6:0.01.
the preparation method of the water reducer comprises the following specific steps:
1) Adding D-isoascorbic acid and 3-mercaptopropionic acid into water, and uniformly mixing to obtain a solution A;
2) Uniformly mixing acrylic acid, dimethylaminoethyl methacrylate and water to obtain a solution B;
3) Adding isopentenol polyoxyethylene ether, fulvic acid and water into a reaction vessel, heating to 30 ℃, and stirring until the raw materials are fully dissolved; then adding potassium persulfate and ferrous sulfate, and simultaneously dripping solution A and solution B, wherein the solution A is dripped completely at 60min, and the mixed solution B is dripped completely at 90 min. After the dripping is finished, stirring for 60min at a stirring speed of 65rpm, then preserving heat at 30 ℃ for 1.5 hours, cooling to below 20 ℃, adding liquid alkali to adjust the pH value to 6.5, and obtaining the polycarboxylic acid water reducer P-3 for micro-expansion type ultra-high performance concrete.
Example 4
The main raw materials involved in the water reducer are as follows: isopentenol polyoxyethylene ether, fulvic acid, ferrous sulfate, D-isoascorbic acid, 3-mercaptopropionic acid, acrylic acid, dimethylaminoethyl methacrylate and potassium persulfate, wherein the weight ratio of each component is 100:15:0.01:0.5:0.1:5:4.5:0.01.
the preparation method of the water reducer comprises the following specific steps:
1) Adding D-isoascorbic acid and 3-mercaptopropionic acid into water, and uniformly mixing to obtain a solution A;
2) Uniformly mixing acrylic acid, dimethylaminoethyl methacrylate and water to obtain a solution B;
3) Adding isopentenol polyoxyethylene ether, fulvic acid and water into a reaction vessel, heating to 30 ℃, and stirring until the raw materials are fully dissolved; then adding potassium persulfate and ferrous sulfate, and simultaneously dripping solution A and solution B, wherein the solution A is dripped completely at 60min, and the mixed solution B is dripped completely at 90 min. After the dripping is finished, stirring for 60min at a stirring speed of 65rpm, then preserving heat at 30 ℃ for 1.5 hours, cooling to below 20 ℃, adding liquid alkali to adjust the pH value to 6.5, and obtaining the polycarboxylic acid water reducer P-4 for micro-expansion type ultra-high performance concrete.
Example 5
The main raw materials involved in the water reducer are as follows: isopentenol polyoxyethylene ether, fulvic acid, ferrous sulfate, D-isoascorbic acid, 3-mercaptopropionic acid, acrylic acid, dimethylaminoethyl methacrylate and potassium persulfate, wherein the weight ratio of each component is 100:20:0.01:0.5:0.1:5:4.5:0.01.
the preparation method of the water reducer comprises the following specific steps:
1) Adding D-isoascorbic acid and 3-mercaptopropionic acid into water, and uniformly mixing to obtain a solution A;
2) Uniformly mixing acrylic acid, dimethylaminoethyl methacrylate and water to obtain a solution B;
3) Adding isopentenol polyoxyethylene ether, fulvic acid and water into a reaction vessel, heating to 30 ℃, and stirring until the raw materials are fully dissolved; then adding potassium persulfate and ferrous sulfate, and simultaneously dripping solution A and solution B, wherein the solution A is dripped completely at 60min, and the mixed solution B is dripped completely at 90 min. After the dripping is finished, stirring for 60min at a stirring speed of 65rpm, then preserving heat at 30 ℃ for 1.5 hours, cooling to below 20 ℃, adding liquid alkali to adjust the pH value to 6.5, and obtaining the polycarboxylic acid water reducer P-5 for micro-expansion type ultra-high performance concrete.
Example 6
The main raw materials involved in the water reducer are as follows: the weight ratio of the isopentenyl alcohol polyoxyethylene ether, ferrous sulfate, D-isoascorbic acid, 3-mercaptopropionic acid, acrylic acid, dimethylaminoethyl methacrylate and potassium persulfate is 100:0.01:1:0.1:5:3:0.01.
the preparation method of the water reducer comprises the following specific steps:
1) Adding D-isoascorbic acid and 3-mercaptopropionic acid into water, and uniformly mixing to obtain a solution A;
2) Uniformly mixing acrylic acid, dimethylaminoethyl methacrylate and water to obtain a solution B;
3) Adding isopentenol polyoxyethylene ether and water into a reaction vessel, heating to 30 ℃, and stirring until the raw materials are fully dissolved; then adding potassium persulfate and ferrous sulfate, and simultaneously dripping solution A and solution B, wherein the solution A is dripped completely at 60min, and the mixed solution B is dripped completely at 90 min. After the dripping is finished, stirring for 60min at a stirring speed of 65rpm, then preserving heat at 30 ℃ for 1.5 hours, cooling to below 20 ℃, adding liquid alkali to adjust the pH value to 6.5, and obtaining the polycarboxylate water reducer P-6.
Comparative example 1
A commercially available polycarboxylate water reducer, designated Q, was used as a comparative example. The polycarboxylic acid water reducer for micro-expansive ultra-high performance concrete of examples 1-6 of the invention and the commercial polycarboxylic acid water reducer of comparative example are tested for expansion degree and emptying time according to GB/T50080-2016 general concrete mixture performance test method standard, compression resistance and flexural strength at different ages according to GB/T50081-2002 general concrete mechanical performance test method standard, limited expansion rate according to GB23439-2009 concrete expansion agent, and cracking condition according to GB/T50082-2009 general concrete long-term performance and durability test method standard.
The mixing ratio of the ultra-high performance concrete adopted in the test is as follows: 14.6kg of cement, 6.4kg of silica fume, 6.3kg of coarse sand, 10.5kg of medium sand, 4.2kg of fine sand, 3.5kg of steel fiber, 3.5kg of water and 0.42kg of water reducing agent (folding and fixing). The test results are shown in Table 1:
table 1: results of ultra-high Performance concrete Performance test for each sample
As can be seen from the index results in Table 1, compared with the comparative examples, the ultra-high performance concrete prepared by using examples 1 to 5 of the invention has more excellent fluidity, slump retention and viscosity reduction, the compression resistance and the breaking strength of different ages are higher than those of the comparative examples, the micro-expansion performance of the examples obviously improves the shrinkage resistance of the concrete, the cracking risk of the concrete can be effectively reduced, and the preparation process of the example 6 has larger influence on the working performance because no fulvic acid is added.
While the above is directed to embodiments of the present invention, it is to be understood that many modifications and variations may be made by those skilled in the art in light of the inventive concepts herein without departing from the spirit and scope of the invention. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.

Claims (8)

1. The polycarboxylate water reducer for the micro-expansion type ultra-high performance concrete is characterized by comprising the following raw materials in parts by weight: 60-100 parts of isopentenyl alcohol polyoxyethylene ether, 10-20 parts of fulvic acid, 0.01 part of ferrous sulfate, 0.5-1.5 parts of reducing agent D-isoascorbic acid, 0.1-0.5 part of 3-mercaptopropionic acid, 5-15 parts of acrylic acid, 3-6 parts of dimethylaminoethyl methacrylate and 0.01-0.05 part of persulfate;
the preparation method comprises the following specific preparation steps:
s1, adding isopentenol polyoxyethylene ether and fulvic acid into water for dissolution, and adding a ferrous sulfate solution after dissolution is completed to obtain a first solution;
s2, adding a reducing agent D-isoascorbic acid and 3-mercaptopropionic acid into water, and uniformly mixing to obtain a second solution;
s3, adding acrylic acid and dimethylaminoethyl methacrylate into water, and uniformly mixing to obtain a third solution;
s4, adding persulfate into the first solution, uniformly stirring, then dropwise adding the second solution and the third solution into the first solution, reacting at constant temperature for a period of time, and naturally cooling to room temperature;
and S5, finally adding liquid alkali to adjust the pH value to 6.5-7.5, and obtaining the polycarboxylic acid water reducer for the micro-expansion type ultra-high-performance concrete.
2. The polycarboxylate superplasticizer as recited in claim 1, wherein: the molecular weight of the isopentenyl alcohol polyoxyethylene ether is 3000-8000.
3. The polycarboxylate superplasticizer as recited in claim 1, wherein: the persulfate is one of ammonium persulfate, sodium persulfate and potassium persulfate.
4. The polycarboxylate superplasticizer as recited in claim 1, wherein: and S4, simultaneously dripping the second solution and the third solution, and controlling the second solution to be dripped before the third solution for 20-30 min, wherein the dripping time of the second solution is 60-90min, and the dripping time of the third solution is 90-120min.
5. The polycarboxylate superplasticizer as recited in claim 1, wherein: and S4, stirring for 50-70 min at 65+ -10 rpm.
6. The polycarboxylate superplasticizer as recited in claim 1, wherein: the reaction temperature in S4 is 20-50 ℃ and the reaction time is 1-3h.
7. The application of the water reducer according to any one of claims 1-6 in preparing ultra-high performance concrete.
8. The use according to claim 7, characterized in that: the addition amount of the modified asphalt is 2-3wt% of the dosage of the adhesive in the concrete.
CN202210945351.4A 2022-08-08 2022-08-08 Polycarboxylate superplasticizer for micro-expansion type ultra-high performance concrete, and preparation method and application thereof Active CN115432953B (en)

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CN105271893A (en) * 2015-10-23 2016-01-27 上海三瑞高分子材料股份有限公司 Slump-retaining water reducer and preparation method thereof
CN105542886A (en) * 2014-11-03 2016-05-04 太原市天鼎恒砼外加剂科技发展有限公司 Coal water slurry dispersant and preparation method thereof
CN106977129A (en) * 2017-04-10 2017-07-25 河北润砼新材料科技有限公司 Anti- mud collapse protective poly-carboxylic acid high efficiency water reducing agent and preparation method thereof
CN109400825A (en) * 2018-11-28 2019-03-01 山西格瑞特建筑科技股份有限公司 A kind of low responsive type polycarboxylate water-reducer and preparation method thereof with anti-mud effect
CN111548221A (en) * 2020-06-03 2020-08-18 郑州大学 Fulvic acid water-soluble fertilizer crystal inhibitor and preparation method thereof
CN114014991A (en) * 2021-10-29 2022-02-08 四川华西绿舍建材有限公司 Calcium silicate hydrate crystal nucleus early-strength polycarboxylate superplasticizer and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009007188A (en) * 2007-06-26 2009-01-15 Denki Kagaku Kogyo Kk Cement admixture and cement composition
CN105542886A (en) * 2014-11-03 2016-05-04 太原市天鼎恒砼外加剂科技发展有限公司 Coal water slurry dispersant and preparation method thereof
CN105271893A (en) * 2015-10-23 2016-01-27 上海三瑞高分子材料股份有限公司 Slump-retaining water reducer and preparation method thereof
CN106977129A (en) * 2017-04-10 2017-07-25 河北润砼新材料科技有限公司 Anti- mud collapse protective poly-carboxylic acid high efficiency water reducing agent and preparation method thereof
CN109400825A (en) * 2018-11-28 2019-03-01 山西格瑞特建筑科技股份有限公司 A kind of low responsive type polycarboxylate water-reducer and preparation method thereof with anti-mud effect
CN111548221A (en) * 2020-06-03 2020-08-18 郑州大学 Fulvic acid water-soluble fertilizer crystal inhibitor and preparation method thereof
CN114014991A (en) * 2021-10-29 2022-02-08 四川华西绿舍建材有限公司 Calcium silicate hydrate crystal nucleus early-strength polycarboxylate superplasticizer and preparation method thereof

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