CN110894263A - Polycarboxylate superplasticizer and preparation method and application thereof - Google Patents

Polycarboxylate superplasticizer and preparation method and application thereof Download PDF

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CN110894263A
CN110894263A CN201911035161.3A CN201911035161A CN110894263A CN 110894263 A CN110894263 A CN 110894263A CN 201911035161 A CN201911035161 A CN 201911035161A CN 110894263 A CN110894263 A CN 110894263A
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unsaturated carboxylic
solution
vopeg
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aqueous solution
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CN110894263B (en
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李亚杰
何新耀
刘东亚
李玉博
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Jiahua Chemical Shanghai Co Ltd
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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
    • 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
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
    • C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

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  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention provides a polycarboxylate superplasticizer and a preparation method thereof, wherein the polycarboxylate superplasticizer comprises the following raw materials: TPEG, VOPEG, reducing agent, chain transfer agent, unsaturated carboxylic acid, unsaturated carboxylic ester, initiator and Fe2+A compound; wherein, VOPEG is hydroxybutyl vinyl polyoxyethylene ether; TPEG is isoamylol polyoxyethylene ether; by using the above raw material componentsThe polycarboxylic acid water reducer with the alkane main chain of carboxylic acid groups and carboxylic ester groups and the hydrophilic polyether side chain comb-shaped molecular structure is obtained, the activity matching degree of VOPEG, unsaturated carboxylic acid and unsaturated carboxylic ester is better, the monomer content of VOPEG in the molecular main chain is effectively improved, and the content of other monomers in the molecular main chain is adjusted, so that the polycarboxylic acid water reducer has good dispersibility and slump retention property, the consistency of concrete can be reduced, and the application of the polycarboxylic acid water reducer in concrete containing poor-quality sandstone materials can be met.

Description

Polycarboxylate superplasticizer and preparation method and application thereof
Technical Field
The invention relates to the technical field of building materials, and particularly relates to a polycarboxylic acid water reducing agent, and a preparation method and application thereof.
Background
In recent years, with the rapid development of the construction industry, concrete has become the most used building material at present, and the concrete admixture is the fifth component of concrete except cement, sand, stone and water, and plays a very important role in the application of high-performance concrete.
The water reducing agent is used as one kind of concrete admixture and has the main function of hindering or destroying the flocculation structure of cement grains through surface activity, complexation, electrostatic repulsion force, stereo repulsion force, etc. to raise the workability and flowability of concrete greatly, save cement amount, reduce water consumption for mixing concrete and raise concrete strength. Therefore, with the development of the concrete industry, the water reducing agent is also continuously researched, developed and reformed, and the development process is as follows: the first generation water reducing agent is a common water reducing agent represented by lignosulfonate, the lignosulfonate is from the paper industry, the cost is low, but the water reducing rate is less than 10 percent, the water reducing agent is not used independently generally, but is compounded with other types of water reducing agents for use; the second-generation water reducing agent is a high-efficiency water reducing agent represented by a naphthalene series and a sulfamate series, and compared with the first-generation water reducing agent, the water reducing rate of the second-generation water reducing agent is improved by 10%, but the slump loss of concrete is large, so that the development and the application of the second-generation water reducing agent are limited; the polycarboxylate superplasticizer serving as a third-generation water reducer product rapidly occupies most markets due to the advantages of low mixing amount, high water reducing rate, high degree of freedom of molecular structure design, environmental friendliness and the like, and is widely applied to projects such as high-speed rails, roads, bridges, tunnels, high-rise buildings and the like.
The existing polycarboxylic acid water reducing agent is mostly characterized in that polyether macromonomer hydroxybutyl vinyl polyoxyethylene ether is introduced into a molecular main chain to improve the mud resistance function of the polycarboxylic acid water reducing agent. For example, chinese patent document CN105085822A discloses an anti-mud polycarboxylic acid water reducing agent and a normal temperature preparation method thereof, the preparation method specifically comprises the following steps: preparing a pre-solution: dissolving 200 parts of unsaturated fatty alcohol-polyoxyethylene ether macromonomer (comprising hydroxybutyl vinyl polyoxyethylene ether and prenol polyoxyethylene ether) and 0.5-5.0 parts of oxidant in 120 parts of water to prepare solution A; dissolving 0.5-5 parts of cationic quaternary ammonium salt and 1-10 parts of quaternary ammonium acrylate in 30 parts of water to prepare a solution B; dissolving 0.2-2.0 parts of reducing agent and 0.3-1.5 parts of chain transfer agent in 30 parts of water to prepare solution C; dissolving 10-30 parts of unsaturated carboxylic acid and/or derivatives thereof in 30 parts of water to prepare a solution D; polymerization reaction: and (2) under the conditions of stirring at the temperature of 20-40 ℃, sequentially dripping B, C, D solution into the solution A, wherein the dripping start time of B, C, D solution is 10min respectively and the dripping is finished within 1-4.0h, then carrying out constant temperature reaction for 1.0-3.0h at the temperature of 20-40 ℃, adding 18-40 parts of liquid alkali into the reaction liquid after the constant temperature reaction is finished, and adjusting the pH value to 5-7 to obtain the anti-mud polycarboxylic acid water reducer.
Although the polycarboxylic acid water reducing agent prepared by the method disclosed in the above document has an anti-mud function; however, in the above documents, hydroxybutyl vinyl polyoxyethylene ether, prenol polyoxyethylene ether and an oxidant are used as substrates, the polymerization reaction belongs to an exothermic reaction, and the double bond activity in the hydroxybutyl vinyl polyoxyethylene ether is relatively high, so that in the polymerization process, due to the relatively high concentration and temperature of the hydroxybutyl vinyl polyoxyethylene ether in the reaction system, the double bonds in the hydroxybutyl vinyl polyoxyethylene ether are easily inactivated, so that the content of the hydroxybutyl vinyl polyoxyethylene ether monomer in the prepared polycarboxylic acid water reducer is low, and the problems of poor slump retaining performance and poor flow performance of the polycarboxylic acid water reducer are caused, and the application of the polycarboxylic acid water reducer in concrete containing poor sandstone materials cannot be met.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems that the polycarboxylic acid water reducing agent in the prior art has poor fluidity, slump retention and the like and cannot meet the application defect in concrete containing poor-quality sandstone materials, and thus provides the polycarboxylic acid water reducing agent, and a preparation method and application thereof.
Therefore, the invention provides the following technical scheme:
the invention provides a polycarboxylate superplasticizer which comprises the following raw materials in parts by weight: 1000 parts of TPEG, 100-1000 parts of VOPEG, 3-7 parts of reducing agent, 5-10 parts of chain transfer agent, 25-300 parts of unsaturated carboxylic acid, 10-60 parts of unsaturated carboxylic ester, 10-30 parts of initiator and Fe2+0.01-0.1 part of compound;
wherein, the VOPEG is hydroxybutyl vinyl polyoxyethylene ether; the TPEG is isopentenol polyoxyethylene ether.
The number average molecular weight of the VOPEG is 400-2000; the number average molecular weight of the TPEG is 2000-3000.
Said Fe2+The compound being inorganic Fe2+Salts or organic Fe2+Salt;
preferably, the inorganic Fe2+The salt is ferrous chloride and/or ferrous sulfate, and the organic Fe2+The salt is ferrous acetate;
the initiator is hydrogen peroxide;
the chain transfer agent is at least one of mercaptoethanol and mercaptopropionic acid.
The unsaturated carboxylic acid is at least one of acrylic acid, methacrylic acid, itaconic acid and maleic acid;
the unsaturated carboxylic ester is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate and monoethyl maleate;
the reducing agent is at least one of ascorbic acid and sodium formaldehyde sulfoxylate.
The invention also provides a preparation method of the polycarboxylate superplasticizer, which comprises the following steps:
sequentially dropwise adding a mixed aqueous solution of a reducing agent and a chain transfer agent and a mixed aqueous solution of unsaturated carboxylic acid and unsaturated carboxylic ester into a mixed aqueous solution of TPEG and an initiator; VOPEG and Fe2+A mixed aqueous solution of the compound; and after the reaction is finished, adding alkali to adjust the pH value to be 6.0-7.0, thus obtaining the polycarboxylic acid water reducing agent.
Wherein a mixed aqueous solution of a reducing agent and a chain transfer agent and a mixed aqueous solution of an unsaturated carboxylic acid and an unsaturated carboxylic acid ester are droppedAdding mixed water solution of unsaturated carboxylic acid and unsaturated carboxylic ester, VOPEG and Fe at initial time interval of 5-15min2+The initial time interval for dripping the mixed aqueous solution of the compound is 25-35 min.
The VOPEG and Fe2+The mixed aqueous solution of the compound is added dropwise for 8-12min before the mixed aqueous solution of the unsaturated carboxylic acid and the unsaturated carboxylic ester.
The dropping time of the mixed aqueous solution of the reducing agent and the chain transfer agent is 130-160min, and the dropping speed is 5.9 multiplied by 103-7.1×103ml/min；
The dropping time of the mixed aqueous solution of the unsaturated carboxylic acid and the unsaturated carboxylic ester is 120-150min, and the dropping speed is 4.2 multiplied by 103-6.2×103ml/min；
The VOPEG and Fe2+The dropping time of the mixed water solution of the compound is 85-115min, and the dropping speed is 3.9 multiplied by 103-9.2×103ml/min。
The concentration of the reducing agent in the mixed aqueous solution of the reducing agent and the chain transfer agent is 0.003-0.008kg/L, and the concentration of the chain transfer agent is 0.005-0.015 kg/L;
the concentration of the unsaturated carboxylic acid in the mixed water solution of the unsaturated carboxylic acid and the unsaturated carboxylic ester is 0.05-0.5kg/L, and the concentration of the unsaturated carboxylic ester is 0.01-0.1 kg/L.
The VOPEG and Fe2+The concentration of VOPEG in the mixed water solution of the compounds is 0.2-1.25kg/L, Fe2+The concentration of the compound was 0.17X 10-4-1.6×10-4kg/L；
The concentration of TPEG in the mixed aqueous solution of TPEG and initiator is 0.5-1.5kg/L, and the concentration of initiator is 0.01-0.05 kg/L.
The concentration of each substance in each solution mentioned above means the mass of each substance contained in each liter of water.
The invention also provides the application of the polycarboxylate superplasticizer or the polycarboxylate superplasticizer prepared by the preparation method of the polycarboxylate superplasticizer in concrete containing poor-quality sandstone raw materials.
The technical scheme of the invention has the following advantages:
1. the invention provides a polycarboxylate superplasticizer which comprises the following raw materials in parts by weight: 1000 parts of TPEG, 1000 parts of VOPEG100-2+0.01-0.1 part of compound; wherein, the VOPEG is hydroxybutyl vinyl polyoxyethylene ether; the TPEG is isopentenol polyoxyethylene ether. The inventor researches and discovers that by adopting the raw material components, the polycarboxylic acid water reducing agent with the comb-shaped molecular structure of the alkane main chain with carboxylic acid groups and carboxylic ester groups and the hydrophilic polyether side chain is obtained, because of the high copolymerization activity of the double bond in VOPEG and the position of the double bond is not isomeric, the activity matching degree of the VOPEG and unsaturated carboxylic acid and unsaturated carboxylic ester of small molecular monomers is better, and the weight portion of each raw material is limited, so that the monomer content of VOPEG in the molecular main chain is effectively improved, meanwhile, the content of the rest monomers in the molecular main chain is adjusted, so that the synthesized polycarboxylate superplasticizer side chain comb structure is more stretched, the degree of freedom is better, the wrapping property and the winding property of the side chain of the superplasticizer are improved, the dispersity of the polycarboxylate superplasticizer is improved, the fluidity of the polycarboxylate superplasticizer is improved, the adsorption of soil to water reducer molecules is reduced, and the slump retaining performance of the polycarboxylate superplasticizer is improved; but also can reduce the consistency of concrete; meanwhile, carboxyl groups introduced into the main chain can be adsorbed on the surface of cement particles; although the carboxylic ester group is not adsorbed on cement particles, the carboxylic ester group can be slowly hydrolyzed in the alkaline environment of cement to release a carboxyl group, so that the slump retaining performance is further improved; by adopting the raw material components, the polycarboxylate superplasticizer provided by the invention has good fluidity, dispersibility and slump retention property, and can reduce the consistency of concrete, thereby meeting the application of the polycarboxylate superplasticizer in concrete containing poor-quality sandstone materials.
2. According to the polycarboxylate water reducer provided by the invention, the molecular weights of VOPEG and TPEG are limited, the length of the side chain of the polycarboxylate water reducer is limited, the degree of freedom and the extension degree of the side chain of the polycarboxylate water reducer are further improved, and the slump retaining performance of the polycarboxylate water reducer is further improved.
3. The preparation method of the polycarboxylate superplasticizer provided by the invention comprises the following steps: sequentially dropwise adding a mixed aqueous solution of a reducing agent and a chain transfer agent and a mixed aqueous solution of unsaturated carboxylic acid and unsaturated carboxylic ester into a mixed aqueous solution of TPEG and an initiator; VOPEG and Fe2+A mixed aqueous solution of the compound; after the reaction is finished, adding alkali to adjust the pH value to 6.0-7.0 to obtain the polycarboxylic acid water reducer; by adopting the above-mentioned dropping sequence, and Fe2+The compound is introduced into a reaction system together with VOPEG in a dropwise adding mode, a Fenton system with super-strong initiation capability can be formed, the monomer content of VOPEG in a molecular main chain is further effectively improved, and meanwhile, the content of other monomers in the molecular main chain is adjusted, so that the side chain comb structure of the synthesized polycarboxylate superplasticizer is more extended, the degree of freedom is better, the wrapping property and the winding property of the side chain of the polycarboxylate superplasticizer are improved, the dispersity and the fluidity of the polycarboxylate superplasticizer are improved, the adsorption of soil to the molecules of the polycarboxylate superplasticizer is reduced, and the slump retaining performance of the polycarboxylate superplasticizer is further improved; but also can reduce the consistency of concrete; after the copolymerization reaction is finished, the pH value is neutralized to 6-7 by using alkali, so that the density degree of side chains in the comb-shaped structure of the polycarboxylate superplasticizer is improved and the slump-retaining performance of the polycarboxylate superplasticizer is improved. The polycarboxylate superplasticizer prepared by the preparation method provided by the invention has good fluidity, dispersibility and slump retention property, can reduce the consistency of concrete, and can meet the application of the polycarboxylate superplasticizer in concrete containing poor-quality sandstone materials.
4. The preparation method of the polycarboxylate superplasticizer provided by the invention limits the dropping time of the solution: the initial time interval of dripping the mixed aqueous solution of the reducing agent and the chain transfer agent and the mixed aqueous solution of the unsaturated carboxylic acid and the unsaturated carboxylic ester is 5-15min, and the mixed aqueous solution of the unsaturated carboxylic acid and the unsaturated carboxylic ester, VOPEG and Fe2+The initial time interval of the dropwise adding of the mixed aqueous solution of the compound is 25-35 min; further adjusting the content of each monomer in the molecular main chain, so that the synthesized polycarboxylate superplasticizer has a more extended side chain comb structure and better degree of freedom,and the fluidity, the dispersibility and the slump retention of the concrete are further improved, the consistency of the concrete is further reduced, and the application of the concrete in the concrete containing poor-quality sandstone materials can be met.
5. The preparation method of the polycarboxylate superplasticizer provided by the invention controls the VOPEG and the Fe2+The content of each monomer VOPEG, TPEG, carboxylic acid and carboxylic ester in the molecular main chain is further adjusted after the mixed aqueous solution of the compound is dripped 8-12min earlier than the mixed aqueous solution of the unsaturated carboxylic acid and the unsaturated carboxylic ester, so that the fluidity, the dispersibility and the slump retention of the polycarboxylic acid water reducer are effectively improved.
6. The application of the polycarboxylate superplasticizer provided by the invention in concrete containing poor-quality sandstone raw materials can effectively solve the problems of poor fluidity and slump retaining performance and the like when the common polycarboxylate superplasticizer is applied to the concrete containing poor-quality sandstone raw materials.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
TPEG (isopentenol polyoxyethylene ether) is purchased from Michelson chemical Co., Ltd, and has a number average molecular weight of 2000-3000;
VOPEG (hydroxybutyl vinyl polyoxyethylene ether) is available from the company Michelson chemical Co., Ltd. and has a number average molecular weight of 400-;
the common TPEG type water reducer mother liquor is purchased from Jilin Zhongxin chemical group Limited company with the model of ZX-51C high-performance polycarboxylic acid water reducer.
Example 1
The embodiment provides a polycarboxylic acid water reducing agent and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of solution a: dissolving 100kg of acrylic acid, 100kg of methacrylic acid, 5kg of hydroxypropyl acrylate and 5kg of hydroxyethyl acrylate in 800L of water, and uniformly mixing for later use;
preparation of solution B: dissolving 1.5 kgL-ascorbic acid, 1.5kg sodium formaldehyde sulfoxylate, 4kg mercaptoethanol and 4kg mercaptopropionic acid in 1000L of water, and mixing;
preparation of solution C: dissolving 0.01kg ferrous sulfate and 500kg VOPEG (number average molecular weight of 400) in 400L water, and mixing uniformly for later use;
preparation of solution D: 1000kg of TPEG (the number average molecular weight is 2400) and 30kg of hydrogen peroxide are dissolved in 1000L of water and are uniformly mixed for later use;
adding the solution D into a reaction kettle, then dropwise adding the solution B under the stirring state at 20 ℃, starting dropwise adding the solution A when the solution B is dropwise added for 10min, and starting dropwise adding the solution C when the solution A is dropwise added for 30 min; wherein the dripping time of the solution A, the solution B and the solution C is 130min, 140min and 88min respectively; and after the three solutions are all dripped, continuously reacting for 55min, and then regulating the pH value of the solution after polymerization reaction to 7.0 by using trihydroxypropyl hydroxyethyl ethylenediamine to obtain the polycarboxylic acid water reducer.
Example 2
The embodiment provides a polycarboxylic acid water reducing agent and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of solution a: 20kg of acrylic acid, 5kg of methacrylic acid, 15kg of hydroxypropyl acrylate and 15kg of monoethyl maleate are dissolved in 500L of water and uniformly mixed for later use;
preparation of solution B: 3 kgL-ascorbic acid, 4kg sodium formaldehyde sulfoxylate, 2.5kg mercaptoethanol and 2.5kg mercaptopropionic acid are dissolved in 900L of water and mixed uniformly for later use;
preparation of solution C: dissolving 0.08kg of ferrous chloride and 100kg of VOPEG (number average molecular weight of 1000) in 500L of water, and uniformly mixing for later use;
preparation of solution D: 1000kg of TPEG (number average molecular weight of 2000) and 10kg of hydrogen peroxide are dissolved in 900L of water and are uniformly mixed for later use;
adding the solution D into a reaction kettle, then dropwise adding the solution B under the stirring state at 20 ℃, starting dropwise adding the solution A when the solution B is dropwise added for 15min, and starting dropwise adding the solution C when the solution A is dropwise added for 25 min; wherein the dripping time of the solution A, the solution B and the solution C is respectively 120min, 135min and 85 min; and after the three solutions are all dripped, continuously reacting for 55min, and then regulating the pH value of the solution after polymerization reaction to 6.0 by using trihydroxypropyl hydroxyethyl ethylenediamine to obtain the polycarboxylic acid water reducer.
Example 3
The embodiment provides a polycarboxylic acid water reducing agent and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of solution a: dissolving 200kg of acrylic acid, 100kg of itaconic acid, 30kg of hydroxypropyl acrylate and 30kg of hydroxyethyl acrylate in 600L of water, and uniformly mixing for later use;
preparation of solution B: 3 kgL-ascorbic acid, 2kg of sodium formaldehyde sulfoxylate, 5kg of mercaptoethanol and 5kg of mercaptopropionic acid are dissolved in 800L of water and are uniformly mixed for later use;
preparation of solution C: dissolving 0.1kg of ferrous acetate and 1000kg of VOPEG (number average molecular weight of 2000) in 800L of water, and uniformly mixing for later use;
preparation of solution D: 1000kg of TPEG (the number average molecular weight is 3000) and 20kg of hydrogen peroxide are dissolved in 800L of water and are uniformly mixed for standby;
adding the solution D into a reaction kettle, then dropwise adding the solution B under the stirring state at 20 ℃, starting dropwise adding the solution A when the solution B is dropwise added for 5min, and starting dropwise adding the solution C when the solution A is dropwise added for 35 min; wherein the dripping time of the solution A, the solution B and the solution C is 130min, 135min and 87min respectively; and after the three solutions are all dripped, continuously reacting for 55min, and then regulating the pH value of the solution after polymerization reaction to 6.5 by using trihydroxypropyl hydroxyethyl ethylenediamine to obtain the polycarboxylic acid water reducer.
Example 4
The embodiment provides a polycarboxylic acid water reducing agent and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of solution a: dissolving 100kg of acrylic acid, 5kg of hydroxypropyl acrylate and 5kg of hydroxyethyl acrylate in 800L of water, and uniformly mixing for later use;
preparation of solution B: dissolving 1.5 kgL-ascorbic acid, 1.5kg sodium formaldehyde sulfoxylate, 4kg mercaptoethanol and 4kg mercaptopropionic acid in 1000L of water, and mixing;
preparation of solution C: 0.01kg ferrous sulfate and 500kg VOPEG (number average molecular weight is 800) are dissolved in 600L water and mixed evenly for standby;
preparation of solution D: 1000kg of TPEG (with the number average molecular weight of 2200) and 30kg of hydrogen peroxide are dissolved in 650L of water and are uniformly mixed for later use;
adding the solution D into a reaction kettle, then dropwise adding the solution B under the stirring state at 20 ℃, starting dropwise adding the solution A when the solution B is dropwise added for 10min, and starting dropwise adding the solution C when the solution A is dropwise added for 30 min; wherein the dripping time of the solution A, the solution B and the solution C is respectively 150min, 160min and 112 min; and after the three solutions are all dripped, continuously reacting for 55min, and then regulating the pH value of the solution after polymerization reaction to 7.0 by using trihydroxypropyl hydroxyethyl ethylenediamine to obtain the polycarboxylic acid water reducer.
Example 5
The embodiment provides a polycarboxylic acid water reducing agent and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of solution a: dissolving 100kg of acrylic acid and 50kg of hydroxypropyl acrylate in 800L of water, and uniformly mixing for later use;
preparation of solution B: dissolving 1.5 kgL-ascorbic acid, 1.5kg sodium formaldehyde sulfoxylate, 4kg mercaptoethanol and 4kg mercaptopropionic acid in 1000L of water, and mixing;
preparation of solution C: 0.05kg of ferrous sulfate and 500kg of VOPEG (number average molecular weight of 1500) are dissolved in 400L of water and are uniformly mixed for later use;
preparation of solution D: 1000kg of TPEG (number average molecular weight of 2800) and 30kg of hydrogen peroxide are dissolved in 2000L of water and are uniformly mixed for later use;
adding the solution D into a reaction kettle, then dropwise adding the solution B under the stirring state at 20 ℃, starting dropwise adding the solution A when the solution B is dropwise added for 10min, and starting dropwise adding the solution C when the solution A is dropwise added for 30 min; wherein the dripping time of the solution A, the solution B and the solution C is 130min, 140min and 90min respectively; and after the three solutions are all dripped, continuously reacting for 55min, and then regulating the pH value of the solution after polymerization reaction to 7.0 by using trihydroxypropyl hydroxyethyl ethylenediamine to obtain the polycarboxylic acid water reducer.
Example 6
The embodiment provides a polycarboxylic acid water reducing agent and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of solution a: dissolving 100kg of acrylic acid and 50kg of hydroxypropyl acrylate in 800L of water, and uniformly mixing for later use;
preparation of solution B: dissolving 6kg of ascorbic acid, 4kg of mercaptoethanol and 4kg of mercaptopropionic acid in 1000L of water, and uniformly mixing for later use;
preparation of solution C: 0.03kg of ferrous sulfate and 500kg of VOPEG (number average molecular weight of 1800) are dissolved in 400L of water and are uniformly mixed for later use;
preparation of solution D: 1000kg of TPEG (number average molecular weight is 2600) and 30kg of hydrogen peroxide are dissolved in 1500L of water and are uniformly mixed for later use;
adding the solution D into a reaction kettle, then dropwise adding the solution B under the stirring state at 20 ℃, starting dropwise adding the solution A when the solution B is dropwise added for 10min, and starting dropwise adding the solution C when the solution A is dropwise added for 25 min; wherein the dripping time of the solution A, the solution B and the solution C is 130min, 140min and 97min respectively; and after the three solutions are all dripped, continuously reacting for 55min, and then regulating the pH value of the solution after polymerization reaction to 7.0 by using trihydroxypropyl hydroxyethyl ethylenediamine to obtain the polycarboxylic acid water reducer.
Example 7
The embodiment provides a polycarboxylic acid water reducing agent and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of solution a: dissolving 100kg of acrylic acid and 50kg of hydroxypropyl acrylate in 800L of water, and uniformly mixing for later use;
preparation of solution B: 6 kgL-ascorbic acid and 6kg mercaptoethanol are dissolved in 1000L of water and mixed evenly for standby;
preparation of solution C: 0.01kg ferrous sulfate and 500kg VOPEG (number average molecular weight of 600) are dissolved in 400L water and mixed evenly for standby;
preparation of solution D: 1000kg of TPEG (the number average molecular weight is 2400) and 30kg of hydrogen peroxide are dissolved in 1000L of water and are uniformly mixed for later use;
adding the solution D into a reaction kettle, then dropwise adding the solution B under the stirring state at 20 ℃, starting dropwise adding the solution A when the solution B is dropwise added for 10min, and starting dropwise adding the solution C when the solution A is dropwise added for 30 min; wherein the dripping time of the solution A, the solution B and the solution C is 140min, 150min and 102min respectively; and after the three solutions are all dripped, continuously reacting for 55min, and then regulating the pH value of the solution after polymerization reaction to 7.0 by using trihydroxypropyl hydroxyethyl ethylenediamine to obtain the polycarboxylic acid water reducer.
Comparative example 1
The comparative example provides a polycarboxylate superplasticizer and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of solution a: dissolving 100kg of acrylic acid, 100kg of methacrylic acid, 5kg of hydroxypropyl acrylate and 5kg of hydroxyethyl acrylate in 800L of water, and uniformly mixing for later use;
preparation of solution B: dissolving 1.5 kgL-ascorbic acid, 1.5kg sodium formaldehyde sulfoxylate, 4kg mercaptoethanol and 4kg mercaptopropionic acid in 1000L of water, and mixing;
preparation of solution C: 0.01kg ferrous sulfate and 500kg VOPEG (number average molecular weight is 400) are dissolved in 400L water and mixed evenly for standby;
preparation of solution D: 1000kg of TPEG (the number average molecular weight is 2400) and 30kg of hydrogen peroxide are dissolved in 1000L of water and are uniformly mixed for later use;
adding the solutions C and D into a reaction kettle, then dropwise adding the solution B at 20 ℃ under a stirring state, and starting dropwise adding the solution A when the solution B is dropwise added for 10min, wherein the dropwise adding time of the solution A and the dropwise adding time of the solution B are 130min and 140min respectively; and after the three solutions are all dripped, continuously reacting for 55min, and then regulating the pH value of the solution after polymerization reaction to 7.0 by using trihydroxypropyl hydroxyethyl ethylenediamine to obtain the polycarboxylic acid water reducer.
Comparative example 2
The comparative example provides a polycarboxylate superplasticizer and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of solution a: dissolving 100kg of acrylic acid, 100kg of methacrylic acid, 5kg of hydroxypropyl acrylate and 5kg of hydroxyethyl acrylate in 800L of water, and uniformly mixing for later use;
preparation of solution B: dissolving 1.5 kgL-ascorbic acid, 1.5kg sodium formaldehyde sulfoxylate, 4kg mercaptoethanol and 4kg mercaptopropionic acid in 1000L of water, and mixing;
preparation of solution C: dissolving 100kg of sodium hydroxide in 200L of water, and uniformly mixing for later use;
preparation of solution D: 1500kg of VOPEG (the number average molecular weight is 400) and 30kg of hydrogen peroxide are dissolved in 1000L of water and are uniformly mixed for later use;
adding the solution D into a reaction kettle, then adding 0.01kg of ferrous sulfate at 12 ℃ under a stirring state, then beginning to dropwise add the solution B, and beginning to dropwise add the solutions A and C when the solution B is dropwise added for 5min, wherein the dropwise adding time of the solutions A and C and the dropwise adding time of the solution B are 45min and 55min respectively; after the three solutions are all dripped, the reaction is continued for 20min, the temperature of the reaction system is controlled not to exceed 15 ℃ in the whole process, and the pH value of the reaction system is not lower than 5.5. And then regulating the pH value of the solution after the polymerization reaction to 7.0 by using trihydroxypropyl hydroxyethyl ethylenediamine to obtain the polycarboxylic acid water reducing agent.
Comparative example 3
The comparative example provides a polycarboxylate superplasticizer and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of solution a: dissolving 100kg of acrylic acid, 100kg of methacrylic acid, 5kg of hydroxypropyl acrylate and 5kg of hydroxyethyl acrylate in 800L of water, and uniformly mixing for later use;
preparation of solution B: dissolving 1.5 kgL-ascorbic acid, 1.5kg sodium formaldehyde sulfoxylate, 4kg mercaptoethanol and 4kg mercaptopropionic acid in 1000L of water, and mixing;
preparation of solution C: dissolving 100kg of sodium hydroxide in 200L of water, and uniformly mixing for later use;
preparation of solution D: 1500kg of VOPEG (the number average molecular weight is 400) and 30kg of hydrogen peroxide are dissolved in 1000L of water and are uniformly mixed for later use;
adding the solution D into a reaction kettle, then adding 0.01kg of ferrous sulfate at the temperature of 20 ℃ under a stirring state, then beginning to dropwise add the solution B, and beginning to dropwise add the solutions A and C when the solution B is dropwise added for 5min, wherein the dropwise adding time of the solutions A and C and the dropwise adding time of the solution B are respectively 120min and 130 min; and after the three solutions are all dripped, continuously reacting for 20min, and then regulating the pH value of the solution after polymerization reaction to 7.0 by using trihydroxypropyl hydroxyethyl ethylenediamine to obtain the polycarboxylic acid water reducer.
Examples of the experiments
The polycarboxylate water reducers obtained in the above examples 1 to 7 and comparative examples 1 to 3, and a conventional TPEG high performance polycarboxylate water reducer (as comparative example 4) purchased from Jilin Zhongxin chemical group Co., Ltd. under model number ZX-51C were subjected to a net slurry test, a concrete test and a performance test of mortar consistency.
Wherein, the clear paste test is in accordance with GB/T8077-; and (3) testing the mortar consistency according to a detection method of a mortar consistency test in JGJ/T70-2009 'test method standard for basic performance of building mortar'. The specific test results are shown in Table 1.
TABLE 1 measurement results of viscosity, neat paste test and concrete test
Figure BDA0002250063640000151
Figure BDA0002250063640000161
As can be seen from the data in the above table, when the addition amount of the polycarboxylic acid water reducing agent is 0.20% of the weight of cement in the cement paste, the initial fluidity of the cement paste with the water cement ratio of 0.29 can be 200-280mm, and the fluidity increase in 1 hour is 260-300 mm; when the addition amount in the concrete is 0.40 percent of the weight of the cement, the initial slump of the newly mixed concrete is 240mm, the slump in 3 hours is 195 mm and 215mm, and the consistency is 70-80; the water reducing agent concrete of the comparative example 1 and the comparative example 3 has small initial slump and very large slump loss in 3 hours, which shows that the water reducing and slump retaining performances are not ideal, the fluidity is poor and the mortar consistency is high; the slump of the water reducing agent of the comparative example 4 is reduced very quickly, the slump loss of concrete is large in 3 hours, and the net slurry fluidity is low in 1 hour, which indicates that the slump retaining performance is not ideal, the fluidity is poor and the mortar consistency is high; as can be seen from comparative examples 2 and 3, although the performance of the water reducing agent of comparative example 2 is close to that of the polycarboxylic acid water reducing agent of the invention, the production difficulty is high because harsh conditions such as ultralow temperature, quick dropwise addition, control of the pH value of a reaction system to be not less than 5.5 and the like are required.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (11)

1. The polycarboxylate superplasticizer is characterized by comprising the following raw materials in parts by weight: 1000 parts of TPEG, 1000 parts of VOPEG100-2+0.01-0.1 part of compound;
wherein, the VOPEG is hydroxybutyl vinyl polyoxyethylene ether; the TPEG is isopentenol polyoxyethylene ether.
2. The polycarboxylate water reducer as set forth in claim 1, characterized in that the number average molecular weight of VOPEG is 400-2000; the number average molecular weight of the TPEG is 2000-3000.
3. The polycarboxylate superplasticizer according to claim 1 or 2, characterized in thatSaid Fe2+The compound being inorganic Fe2+Salts or organic Fe2+Salt;
preferably, the inorganic Fe2+The salt is ferrous chloride and/or ferrous sulfate, and the organic Fe2+The salt is ferrous acetate;
the initiator is hydrogen peroxide;
the chain transfer agent is at least one of mercaptoethanol and mercaptopropionic acid.
4. The polycarboxylate water reducer according to any one of claims 1-3, characterized in that the unsaturated carboxylic acid is at least one of acrylic acid, methacrylic acid, itaconic acid and maleic acid;
the unsaturated carboxylic ester is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate and monoethyl maleate;
the reducing agent is at least one of ascorbic acid and sodium formaldehyde sulfoxylate.
5. A preparation method of the polycarboxylic acid water reducing agent disclosed by any one of claims 1 to 4 is characterized by comprising the following steps:
adding a mixed aqueous solution of a reducing agent and a chain transfer agent, a mixed aqueous solution of an unsaturated carboxylic acid and an unsaturated carboxylic ester, VOPEG and Fe dropwise into a mixed aqueous solution of TPEG and an initiator2+A mixed aqueous solution of the compound; and after the reaction is finished, adding alkali to adjust the pH value to be 6.0-7.0, thus obtaining the polycarboxylic acid water reducing agent.
6. The method for preparing a polycarboxylic acid water reducing agent according to claim 5, characterized in that the initial time interval for dropping the mixed aqueous solution of the reducing agent and the chain transfer agent and the mixed aqueous solution of the unsaturated carboxylic acid and the unsaturated carboxylic acid ester is 5-15min, and the mixed aqueous solution of the unsaturated carboxylic acid and the unsaturated carboxylic acid ester, VOPEG and Fe2+The initial time interval for dripping the mixed aqueous solution of the compound is 25-35 min.
7. Preparation of the polycarboxylate water reducer according to claim 5 or 6Method, characterized in that said VOPEG and Fe2+The mixed aqueous solution of the compound is added dropwise for 8-12min before the mixed aqueous solution of the unsaturated carboxylic acid and the unsaturated carboxylic ester.
8. The preparation method of the polycarboxylate water reducer as defined in claim 7, wherein the dropping time of the mixed aqueous solution of the reducing agent and the chain transfer agent is 130-160min, and the dropping speed is 5.9X 103-7.1×103ml/min；
The dropping time of the mixed aqueous solution of the unsaturated carboxylic acid and the unsaturated carboxylic ester is 120-150min, and the dropping speed is 4.2 multiplied by 103-6.2×103ml/min；
The VOPEG and Fe2+The dropping time of the mixed water solution of the compound is 85-115min, and the dropping speed is 3.9 multiplied by 103-9.2×103ml/min。
9. The preparation method of the polycarboxylate water reducer as claimed in claim 8, characterized in that the concentration of the reducing agent in the mixed aqueous solution of the reducing agent and the chain transfer agent is 0.003-0.008kg/L, and the concentration of the chain transfer agent is 0.005-0.015 kg/L;
the concentration of the unsaturated carboxylic acid in the mixed water solution of the unsaturated carboxylic acid and the unsaturated carboxylic ester is 0.05-0.5kg/L, and the concentration of the unsaturated carboxylic ester is 0.01-0.1 kg/L.
10. The preparation method of the polycarboxylate water reducer according to any one of claims 5-9, wherein VOPEG and Fe2+The concentration of VOPEG in the mixed water solution of the compounds is 0.2-1.25kg/L, Fe2+The concentration of the compound was 0.17X 10-4-1.6×10-4kg/L；
The concentration of TPEG in the mixed aqueous solution of TPEG and initiator is 0.5-1.5kg/L, and the concentration of initiator is 0.01-0.05 kg/L.
11. The application of the polycarboxylate superplasticizer prepared by the preparation method of the polycarboxylate superplasticizer according to any one of claims 1 to 4 or the polycarboxylate superplasticizer according to any one of claims 5 to 10 in concrete containing poor-quality sand raw materials.
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