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CN115536787B - A sustained-release nanoemulsion polycarboxylate water reducer and its preparation method and application - Google Patents

A sustained-release nanoemulsion polycarboxylate water reducer and its preparation method and application Download PDF

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CN115536787B
CN115536787B CN202211285295.2A CN202211285295A CN115536787B CN 115536787 B CN115536787 B CN 115536787B CN 202211285295 A CN202211285295 A CN 202211285295A CN 115536787 B CN115536787 B CN 115536787B
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stirring
added
sequence
nanoemulsion
water reducer
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CN115536787A (en
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董勋
白晓成
郭强强
段勇
张光华
张万斌
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CCCC SHEC Dong Meng Engineering Co Ltd
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CCCC SHEC Dong Meng Engineering 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
    • C04B24/2688—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 Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a slow-release nano emulsion polycarboxylate water reducer and a preparation method and application thereof, wherein deionized water is sequentially added into a four-neck flask with a stirring and ventilation device, stirring is started, nitrogen is introduced, K12 and TX-10 are sequentially dissolved, polyether macromonomer is sequentially added to fully stir and dissolve and heat up to a certain temperature, acrylic acid and acrylic ester monomer are sequentially added while stirring, stirring is continued and heat up to fully emulsify the polyether macromonomer; and (3) dropwise adding an azodiisobutyronitrile aqueous solution into the reaction container, continuously carrying out heat preservation reaction, and cooling to room temperature to obtain the slow-release nano emulsion polycarboxylate superplasticizer. The invention synthesizes a crosslinking nanometer microsphere dispersoid by adopting emulsion polymerization technology, wherein benzyl acrylate is a hydrophobic monomer, hydroxy acrylate is a slow-release monomer, di-acrylic glycol ester is a crosslinking monomer, gradient hydrolysis is realized by utilizing the difference of hydrolysis speeds of three monomers, and carboxyl is released in sequence, so that the long-time water reducing and slump retaining effects are realized.

Description

Sustained-release nano emulsion polycarboxylate superplasticizer and preparation method and application thereof
Technical Field
The invention relates to the technical field of polycarboxylate superplasticizers, in particular to a slow-release nano emulsion polycarboxylate superplasticizer, a preparation method and application thereof.
Background
The polycarboxylate water reducer is a novel high-efficiency concrete water reducer which is developed successfully in the middle of the 80 th century, has low mixing amount, high water reducing rate and environment friendliness, and can obviously improve the strength and dispersion performance of concrete. With the construction of special projects such as ultra-long tunnels, the engineering world has higher and higher requirements on the concrete slump and fluidity. At present, due to the fact that traffic and transportation lines in an ultra-long tunnel are complex, accumulated water and pits on the road surface are serious, road conditions are extremely poor, and commercial concrete is transported in an ultra-long distance, ultra-high-rise concrete is transported, and the like, the concrete is required to have slump retention capacity of 4-6 hours or even longer, otherwise, smooth construction and concrete engineering quality are influenced. Therefore, there is an urgent need in the art for an ultra-long slow-release polycarboxylate-type water reducer that has good adaptability to meet the needs of large-scale construction.
The invention relates to a CN113121753A super-long slow-release type polycarboxylate water reducer and a preparation method and application thereof, wherein triethyl citrate or trimethyl citrate is introduced into polycarboxylate water reducer molecules, and as the triethyl citrate or trimethyl citrate contains three ester groups, the hydrolysis rate is relatively slow, so that long-time slow release of carboxylate radicals can be realized, and meanwhile, the hydrolysis release of citric acid also has a certain retarding effect, the synergistic effect of the two can ensure that the slump retaining performance of concrete is excellent, and the PCE containing carboxylate slowly releases carboxylate ions through gradual hydrolysis in an alkaline environment of cement paste, so that the fluidity is maintained. However, the strong retarding effect of the citrate also has an influence on the working performances of early final setting, segregation, bleeding and the like of the concrete in the later period, and meanwhile, the slow release adjustability is poor.
CN104860572a discloses a polycarboxylic acid water reducer special for 6h slump retaining wet spraying concrete under hot conditions, the water reducer is composed of the following raw materials in percentage by weight: 5 to 15 percent of water-reducing type polycarboxylate water reducer, 50 to 70 percent of slow-releasing type polycarboxylate water reducer, 0.02 to 0.1 percent of water control agent, 8 to 15 percent of novel retarding slump retaining agent, 0.1 to 1 percent of viscosity regulator and 10 to 30 percent of water. The water reducer prepared by the method can obviously improve the effective dosage of the slow-release polycarboxylic acid water reducer at one time, and meanwhile, does not cause concrete segregation and bleeding, so that the amount of the water reducer in a concrete liquid phase is continuously supplemented, the working performance state of the concrete is controllable, and finally, the slump retaining function of wet-sprayed concrete for a very long time (6 h) is realized. The product has the effects of obviously prolonging the slump retention time, improving the volume stability, reducing the temperature rise, reducing the viscosity and the like on wet sprayed concrete, but the stability is influenced by the controllability of the performance and the adaptability of cement of the quality, the source and the like of the components such as the water-reducing type polycarboxylate water reducer, the slow-release polycarboxylate water reducer and the like.
The existing polycarboxylate water reducer has the defects of sensitivity to soil, controllable slow release, poor adaptability and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the application aims to provide a slow-release nano emulsion polycarboxylate water reducer, a preparation method and application thereof, and aims to overcome the defects of insufficient 4-8-hour slump ultra-long retention capacity of the existing polycarboxylate water reducer applied to concrete (especially machine-made sand concrete and the like). The polycarboxylate water reducer prepared by emulsion polymerization is firstly subjected to micelle dissociation, then is subjected to hydrolysis in a chemical process, and three acrylic esters are adopted to realize gradient hydrolysis, so that carboxylate radicals can be slowly released for a long time, the slump retaining performance of concrete is excellent due to synergistic effect, and carboxylate ions are slowly released by gradual hydrolysis of the polycarboxylate water reducer in a cement slurry alkaline environment, so that the effect of maintaining fluidity is achieved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The slow-release nano emulsion polycarboxylate superplasticizer adopts the following formula proportions by mass:
polyether macromonomer: 100 parts;
acrylic acid: 200-240 parts
Hydroxy acrylate: 110-140 parts
Benzyl acrylate: 80-110 parts
Glycol diacrylate: 10-20 parts;
emulsifier K12: 10-18 parts;
Emulsifier TX-10: 3.5-6 parts;
Aqueous azobisisobutyronitrile solution: 50-100 parts;
Thioglycollic acid: 0.5 to 1.0 part
Deionized water: 750-900 parts.
The nano emulsion polycarboxylate water reducer utilizes the hydrophobic difference of each monomer, forms a microsphere inner layer in the emulsification process, and is composed of a water reducer molecular chain segment mainly composed of benzyl acrylate with strong hydrophobicity, and a molecular chain segment mainly composed of di-acrylic acid glycol ester and hydroxyl acrylate, wherein the emulsification layer is composed of acrylic acid, a reactive emulsifier and a large monomer, so that a core-shell nano microsphere is formed, and the nano microsphere water reducer can realize gradient release and gradient hydrolysis under the alkaline environment of concrete, so that carboxyl group II is gradually released to play a role.
The preparation method of the slow-release nano emulsion polycarboxylate superplasticizer comprises the following synthesis steps:
(1) Adding deionized water into a reactor with stirring, starting stirring, and adding emulsifier K12, emulsifier TX-10 and polyether macromonomer into the reactor with stirring to fully stir and dissolve the components;
(2) After the temperature of the system (1) is raised to 50 ℃, adding acrylic acid while stirring, continuously adding 50% aqueous solution of hydroxyl acrylate, benzyl acrylate, glycol diacrylate and thioglycollic acid in sequence, and rapidly stirring while heating to 70+/-2 ℃, and keeping the temperature and stirring for 10 minutes to fully emulsify;
(3) And finally, dropwise adding an azodiisobutyronitrile aqueous solution into the reaction container in the step (2) within 0.5-1 hour, continuing to react at 70+/-2 ℃ for 4 hours under heat preservation, and then cooling to room temperature under stirring to obtain a milky emulsion, namely the slow-release nano emulsion polycarboxylate superplasticizer.
750-900 Parts of deionized water, 10-18 parts of emulsifier K, 3.5-6 parts of emulsifier TX-10 and 100 parts of polyether macromonomer in the step (1).
The polyether macromonomer in the step (1) is one of methallyl polyoxyethylene ether (HPEG-2400), isopentenyl alcohol polyoxyethylene ether (TPEG-2400) and vinyl butanediol polyoxyethylene ether (EPEG-3000).
110-140 Parts of hydroxyl acrylate, 80-110 parts of benzyl acrylate, 10-20 parts of diacrylate diol ester and 0.5-1.0 part of thioglycollic acid in the step (2);
The hydroxy acrylate in the step (2) is one of hydroxyethyl acrylate or hydroxypropyl acrylate.
50-100 Parts of azodiisobutyronitrile aqueous solution in the step (3).
The azodiisobutyronitrile aqueous solution in the step (3) is an aqueous solution prepared from azodiisobutyronitrile and water, wherein the mass fraction of the aqueous solution is 50%;
The glycol diacrylate in the step (2) is one of ethylene glycol diacrylate, diethylene glycol diacrylate and polyethylene glycol diacrylate.
The slow-release nano emulsion polycarboxylate water reducer is applied to construction of super high-rise buildings and ultra-long distance transportation and concrete conveying.
The invention has the remarkable beneficial effects that:
The invention aims to provide a slow-release nano emulsion polycarboxylate water reducer and a preparation method thereof, which can basically keep fluidity of cement paste within 4-7 hours, and basically avoid loss of concrete slump within 4 hours. The emulsion polymerized nanometer polycarboxylate water reducer has the special nanometer microsphere structure, and the nanometer microsphere structure features that the hydrophobic difference of the monomers is utilized, and the inner layer of the microsphere consists of hydrophobic benzyl acrylate and double acrylic glycol ester and the outer layer of the microsphere consists of hydroxyl acrylate and has multilayer gradient microsphere capable of realizing gradient release and gradient hydrolysis. The nano microsphere water reducer is added into a concrete system, the nano microsphere is gradually dissociated from outside to inside after being subjected to surface adsorption such as cement particle adsorption and sand stone, the ester monomers are gradually hydrolyzed to release carboxyl, the later-stage benzyl acrylate and the di-acrylic glycol ester are released and hydrolyzed until all carboxyl and water reducer molecule chain segments are released after complete dissociation and hydrolysis, and the gradient hydrolysis mode enables the water reducer to gradually increase the fluidity along with the time extension cement flow in an alkaline environment of cement paste for 4-5 hours, and can still keep good fluidity for 6-7 hours. The characteristics can not only keep small slump loss of the concrete after long-time transportation and avoid evaporation of mixing water caused by ultra-long distance transportation at high temperature, but also play an important role in construction of ultra-high-rise buildings, ultra-long tunnel engineering and the like.
Drawings
Fig. 1 is a microscopic TEM image of a nanoemulsion polycarboxylate water reducer.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Adding 75g of deionized water into a four-neck flask with a stirring device in sequence, starting stirring and introducing nitrogen, sequentially adding 1g of K12 and 0.35g of TX-10 to be dissolved, continuously adding 10g of polyether macromonomer TPEG-2400 in sequence to fully stir and dissolve, heating to 50 ℃, adding 20g of acrylic acid while stirring, continuously adding 11g of hydroxyethyl acrylate, 8g of benzyl acrylate, 1g of ethylene glycol diacrylate and 0.05g of thioglycollic acid in sequence, rapidly stirring and heating to 70+/-2 ℃ while maintaining the temperature and stirring for 10 minutes to fully emulsify and disperse, beginning to dropwise adding 5g of azodiisobutyronitrile aqueous solution into a reaction container, adding the solution after 0.5-1 hour, continuously maintaining the temperature and reacting for 4 hours at 70+/-2 ℃, and cooling to room temperature under stirring to obtain the nano emulsion polycarboxylic acid water reducer.
Example 2
Sequentially adding 90g of deionized water into a four-neck flask with a stirring device, starting stirring, introducing nitrogen, sequentially adding 1.8g of K12 and 0.6g of TX-10 to be dissolved, continuously sequentially adding 10g of polyether macromonomer HPEG-2400 to be fully stirred and dissolved, heating to 50 ℃, then adding 24g of acrylic acid while stirring, continuously sequentially adding 14g of hydroxypropyl acrylate, 11g of benzyl acrylate, 1.6g of diglycol diacrylate and 0.1g of mercaptoacetic acid, rapidly stirring, heating to 70+/-2 ℃ while maintaining the temperature and stirring for 10 minutes to fully emulsify and disperse, beginning to dropwise add 10g of azodiisobutyronitrile aqueous solution into a reaction vessel, adding the solution at 0.5-1 hour, continuously maintaining the temperature and reacting for 4 hours at 70+/-2 ℃, and then cooling to room temperature under stirring to obtain the nano emulsion polycarboxylic acid water reducer.
Example 3
Adding 80g of deionized water into a four-neck flask with a stirring device in sequence, starting stirring, introducing nitrogen, sequentially adding 1.3g of K12 and 0.5g of TX-10 to be dissolved, continuously adding 10g of polyether macromonomer EPEG-3000 in sequence to fully stir and dissolve, heating to 50 ℃, adding 22g of acrylic acid while stirring, continuously adding 12g of hydroxyethyl acrylate, 9g of benzyl acrylate, 1.5g of propylene glycol diacrylate and 0.08g of thioglycollic acid in sequence, rapidly stirring, heating to 70+/-2 ℃ while maintaining the temperature and stirring for 10 minutes to fully emulsify and disperse, beginning to dropwise add 8g of azodiisobutyronitrile aqueous solution into a reaction vessel, adding the azodiisobutyronitrile aqueous solution at 0.5-1 hour, continuously maintaining the temperature and reacting for 4 hours at 70+/-2 ℃, and cooling to room temperature under stirring to obtain the nano emulsion polycarboxylic acid water reducer.
Example 4
Adding 80g of deionized water into a four-neck flask with a stirring device in sequence, starting stirring, introducing nitrogen, sequentially adding 1.3g of K12 and 0.5g of TX-10 to be dissolved, continuously adding 10g of polyether macromonomer EPEG-3000 in sequence to fully stir and dissolve, heating to 50 ℃, adding 18g of acrylic acid while stirring, continuously adding 11g of hydroxyethyl acrylate, 10g of benzyl acrylate, 2.0g of polyethylene glycol diacrylate and 0.08g of thioglycollic acid in sequence, rapidly stirring, heating to 70+/-2 ℃ while stirring for 10 minutes while maintaining the temperature to fully emulsify and disperse, beginning to dropwise add 8g of azodiisobutyronitrile aqueous solution into a reaction vessel, adding the azodiisobutyronitrile aqueous solution for 0.5-1 hour, continuously maintaining the temperature at 70+/-2 ℃ for 4 hours, and cooling to room temperature while stirring to obtain the nano emulsion polycarboxylic acid water reducer.
Testing the fluidity of cement paste:
The net pulp fluidity of the cement was determined according to GBT8077-2012, concrete admixture homogeneity test method. The cement ratio is fixed to be 0.29, and the PCE doping amount (folding fixation) is 0.25 percent of the cement mass. The fluidity was measured every 1 hour for a total of 7 hours. Table 1 is a test result of the cement dispersing effect of the prepared nano emulsion polycarboxylate water reducer.
TABLE 1 cement paste fluidity with time
FIGS. 1a and 1b are, respectively, microscopic topographies of the nanoemulsion polycarboxylate water reducer of the examples.
The foregoing is a further elaboration of the present invention, and it is not intended that the invention be limited to the specific embodiments shown, but rather that a number of simple deductions or substitutions be made by one of ordinary skill in the art without departing from the spirit of the invention, all shall be deemed to fall within the scope of the invention as defined by the claims which are filed herewith.

Claims (5)

1.一种缓释型纳米乳液聚羧酸减水剂的制备方法，其特征在于，在带有搅拌装置的四口烧瓶中加入75g的去离子水，开动搅拌并通入氮气，依次加入1g的K12 和0.35g的TX-10待溶解后，继续依次加入10g聚醚大单体TPEG-2400使其充分搅拌溶解并升温至 50℃后，再边搅拌边加入20g丙烯酸，继续依次加入丙烯酸羟乙酯11g、丙烯酸苄醇酯8g、双丙烯酸乙二醇酯1g、巯基乙酸0.05g，边快速搅拌边升温至70±2℃保温搅拌 10 分钟使其充分乳化分散后，开始向反应容器中滴加偶氮二异丁腈水溶液5g，并于0.5~1小时加完，继续70±2℃下保温反应 4 小时，然后在搅拌下进行冷却至室温，得到一种纳米乳液聚羧酸减水剂。1. A method for preparing a sustained-release nanoemulsion polycarboxylate water reducer, characterized in that 75g of deionized water is added to a four-necked flask with a stirring device, stirring is started and nitrogen is introduced, 1g of K12 and 0.35g of TX-10 are added in sequence to be dissolved, 10g of polyether macromonomer TPEG-2400 is added in sequence to fully stir and dissolve and the temperature is raised to 50°C, 20g of acrylic acid is added while stirring, 11g of hydroxyethyl acrylate, 8g of benzyl acrylate, 1g of ethylene glycol diacrylate, and 0.05g of thioglycolic acid are added in sequence, the temperature is raised to 70±2°C while stirring rapidly, and the temperature is kept warm and stirred for 10 minutes to fully emulsify and disperse, and then 5g of azobisisobutyronitrile aqueous solution is added dropwise to the reaction container, and the addition is completed in 0.5-1 hour, and the reaction is continued at 70±2°C for 4 hours, and then cooled to room temperature under stirring to obtain a nanoemulsion polycarboxylate water reducer. 2.一种缓释型纳米乳液聚羧酸减水剂的制备方法，其特征在于，在带有搅拌装置的四口烧瓶中加入90g的去离子水，开动搅拌并通入氮气，依次加入1.8g的K12 和0.6g的TX-10待溶解后，继续依次加入10g聚醚大单体HPEG-2400使其充分搅拌溶解并升温至50℃后，再边搅拌边加入24g丙烯酸，继续依次加入丙烯酸羟丙酯14g、丙烯酸苄醇酯11g、双丙烯酸二乙二醇酯1.6g、巯基乙酸0.1g，边快速搅拌边升温至70±2℃保温搅拌 10 分钟使其充分乳化分散后，开始向反应容器中滴加偶氮二异丁腈水溶液10g，并于0.5~1小时加完，继续70±2℃下保温反应 4 小时，然后在搅拌下进行冷却至室温，得到一种纳米乳液聚羧酸减水剂。2. A method for preparing a sustained-release nanoemulsion polycarboxylate water reducer, characterized in that 90g of deionized water is added to a four-necked flask with a stirring device, stirring is started and nitrogen is introduced, 1.8g of K12 and 0.6g of TX-10 are added in sequence and dissolved, 10g of polyether macromonomer HPEG-2400 is added in sequence to fully stir and dissolve and the temperature is raised to 50°C, 24g of acrylic acid is added while stirring, 14g of hydroxypropyl acrylate, 11g of benzyl acrylate, 1.6g of diethylene glycol diacrylate, and 0.1g of thioglycolic acid are added in sequence, the temperature is raised to 70±2°C while stirring rapidly, and the mixture is kept warm and stirred for 10 minutes to fully emulsify and disperse, 10g of azobisisobutyronitrile aqueous solution is added dropwise to the reaction container, and the addition is completed within 0.5-1 hour, the reaction is continued at 70±2°C for 4 hours, and then cooled to room temperature under stirring to obtain a nanoemulsion polycarboxylate water reducer. 3.一种缓释型纳米乳液聚羧酸减水剂的制备方法，其特征在于，在带有搅拌装置的四口烧瓶中加入80g的去离子水，开动搅拌并通入氮气，依次加入1.3g的K12 和0.5g的TX-10待溶解后，继续依次加入10g聚醚大单体EPEG-3000使其充分搅拌溶解并升温至 50℃后，再边搅拌边加入22g丙烯酸，继续依次加入丙烯酸羟乙酯12g、丙烯酸苄醇酯9g、双丙烯酸丙二醇酯1.5g、巯基乙酸0.08g，边快速搅拌边升温至70±2℃保温搅拌 10 分钟使其充分乳化分散后，开始向反应容器中滴加偶氮二异丁腈水溶液8g，并于0.5~1小时加完，继续70±2℃下保温反应 4 小时，然后在搅拌下进行冷却至室温，得到一种纳米乳液聚羧酸减水剂。3. A method for preparing a sustained-release nanoemulsion polycarboxylate water reducer, characterized in that 80g of deionized water is added to a four-necked flask with a stirring device, stirring is started and nitrogen is introduced, 1.3g of K12 and 0.5g of TX-10 are added in sequence and dissolved, 10g of polyether macromonomer EPEG-3000 is added in sequence to fully stir and dissolve and the temperature is raised to 50°C, 22g of acrylic acid is added while stirring, 12g of hydroxyethyl acrylate, 9g of benzyl acrylate, 1.5g of propylene glycol diacrylate, and 0.08g of thioglycolic acid are added in sequence, the temperature is raised to 70±2°C while stirring rapidly, and the mixture is kept warm and stirred for 10 minutes to fully emulsify and disperse, 8g of azobisisobutyronitrile aqueous solution is added dropwise to the reaction container, and the addition is completed in 0.5-1 hour, the reaction is continued at 70±2°C for 4 hours, and then cooled to room temperature under stirring to obtain a nanoemulsion polycarboxylate water reducer. 4.一种缓释型纳米乳液聚羧酸减水剂的制备方法，其特征在于，在带有搅拌装置的四口烧瓶中加入80g的去离子水，开动搅拌并通入氮气，依次加入1.3g的K12 和0.5g的TX-10待溶解后，继续依次加入10g聚醚大单体EPEG-3000使其充分搅拌溶解并升温至 50℃后，再边搅拌边加入18g丙烯酸，继续依次加入丙烯酸羟乙酯11g、丙烯酸苄醇酯10g、双丙烯酸聚乙二醇酯2.0g、巯基乙酸0.08g，边快速搅拌边升温至70±2℃保温搅拌 10 分钟使其充分乳化分散后，开始向反应容器中滴加偶氮二异丁腈水溶液8g，并于0.5~1小时加完，继续70±2℃下保温反应 4 小时，然后在搅拌下进行冷却至室温，得到一种纳米乳液聚羧酸减水剂。4. A method for preparing a sustained-release nanoemulsion polycarboxylate water reducer, characterized in that 80 g of deionized water is added to a four-necked flask with a stirring device, stirring is started and nitrogen is introduced, 1.3 g of K12 and 0.5 g of TX-10 are added in sequence and dissolved, 10 g of polyether macromonomer EPEG-3000 is added in sequence to fully stir and dissolve and the temperature is raised to 50°C, 18 g of acrylic acid is added while stirring, 11 g of hydroxyethyl acrylate, 10 g of benzyl acrylate, 2.0 g of polyethylene glycol diacrylate, and 0.08 g of thioglycolic acid are added in sequence, the temperature is raised to 70±2°C while stirring rapidly, and the mixture is kept warm and stirred for 10 minutes to fully emulsify and disperse, 8 g of azobisisobutyronitrile aqueous solution is added dropwise to the reaction container, and the addition is completed in 0.5 to 1 hour, the reaction is continued at 70±2°C for 4 hours, and then cooled to room temperature under stirring to obtain a nanoemulsion polycarboxylate water reducer. 5.基于权利要求1-4任一项所述方法制备的一种缓释型纳米乳液聚羧酸减水剂，其特征在于，所述缓释型纳米乳液聚羧酸减水剂应用于超高层建筑、超长距离运输和输送混凝土的施工。5. A sustained-release nanoemulsion polycarboxylate water-reducing agent prepared by the method according to any one of claims 1 to 4, characterized in that the sustained-release nanoemulsion polycarboxylate water-reducing agent is used in the construction of super high-rise buildings, ultra-long distance transportation and delivery of concrete.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110951009A (en) * 2019-11-19 2020-04-03 湖北工业大学 Solid sheet-shaped polycarboxylate superplasticizer and method for preparing same by core-shell emulsion method
CN113121753A (en) * 2021-04-22 2021-07-16 陕西科技大学 Ultra-long slow-release polycarboxylate superplasticizer, preparation method and application

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CN113929832B (en) * 2020-06-29 2023-02-14 博特建材（天津）有限公司 Polyfunctional group superplasticizer for ultrahigh-performance concrete and preparation method thereof
CN113788917B (en) * 2021-09-03 2022-05-13 武汉三源特种建材有限责任公司 Anti-mud functional monomer, anti-mud polycarboxylic acid water reducer, and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110951009A (en) * 2019-11-19 2020-04-03 湖北工业大学 Solid sheet-shaped polycarboxylate superplasticizer and method for preparing same by core-shell emulsion method
CN113121753A (en) * 2021-04-22 2021-07-16 陕西科技大学 Ultra-long slow-release polycarboxylate superplasticizer, preparation method and application

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