CN115521414A - Polycarboxylic slump retaining agent and preparation method and application thereof - Google Patents
Polycarboxylic slump retaining agent and preparation method and application thereof Download PDFInfo
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- CN115521414A CN115521414A CN202211201894.1A CN202211201894A CN115521414A CN 115521414 A CN115521414 A CN 115521414A CN 202211201894 A CN202211201894 A CN 202211201894A CN 115521414 A CN115521414 A CN 115521414A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002253 acid Substances 0.000 claims abstract description 53
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 33
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 29
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 28
- 239000004567 concrete Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- POLZHVHESHDZRD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(=O)OCCO POLZHVHESHDZRD-UHFFFAOYSA-N 0.000 claims abstract description 20
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 89
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 24
- 229920000570 polyether Polymers 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 229920005646 polycarboxylate Polymers 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000004359 castor oil Substances 0.000 claims description 7
- 235000019438 castor oil Nutrition 0.000 claims description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- -1 polyoxyethylene Polymers 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 238000009776 industrial production Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000003674 animal food additive Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 28
- 239000008399 tap water Substances 0.000 description 26
- 235000020679 tap water Nutrition 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 239000008030 superplasticizer Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001374849 Liparis atlanticus Species 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000012687 ideal copolymerization Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides a polycarboxylic acid slump retaining agent and a preparation method and application thereof, and relates to the technical field of concrete admixtures. Specifically, the feed additive is prepared from the following components in parts by mass: 280-320 parts of ethylene glycol monoethyl polyoxyethylene ether, 5-20 parts of hydroxyethyl methacrylate phosphate, 3-15 parts of acrylic acid, 20-40 parts of hydroxyethyl acrylate, 1-4 parts of an oxidant, 2-8 parts of a chain transfer agent, 0.1-1.5 parts of a reducing agent, 3-20 parts of a pH regulator and a plurality of water. The polycarboxylic acid slump retaining agent can be used together with a water reducing agent, so that the slump of concrete is kept for 4-5 h, and the slump retaining requirement of the concrete in long-distance transportation and high-temperature environments is met. The preparation method can realize industrial production, has the advantages of stable quality, simple and convenient process, low production energy consumption and the like, and can adjust the process based on the environmental temperature, so that the product has lower quality fluctuation rate.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, and particularly relates to a polycarboxylic acid slump retaining agent and a preparation method and application thereof.
Background
The polycarboxylate superplasticizer is a concrete dispersant product with the widest application range and the optimal performance at present, the application and research work of the polycarboxylate superplasticizer are widely concerned, the polycarboxylate superplasticizer has the unique characteristic of designability of a molecular structure, and the production process and the use effect of the polycarboxylate superplasticizer can be obviously improved by developing and improving the polyether macromonomer which is an important raw material of the polycarboxylate superplasticizer and continuously improving the synthesis technology of the polycarboxylate superplasticizer. Along with the quality of concrete gravel raw materials is continuously reduced, high-quality gravel resources are gradually consumed, the gravel resources in various places tend to be deteriorated, the mud content of used gravel is relatively high, the performance requirement of concrete is continuously improved, and the polycarboxylic acid water reducing agent technology is more and more difficult to meet the requirement. In order to solve the problems, a slump retaining agent is generally added during the compounding of the polycarboxylic acid water reducing agent so as to solve the problem of high slump loss of concrete.
At present, polycarboxylic acid water reducing agents and slump retaining agents in the market are mainly prepared from vinyl alcohol monomers TPEG (methyl allyl polyoxyethylene ether) or HPEG (allyl polyoxyethylene ether) macromonomer, unsaturated carboxylic acid and ester monomers which are subjected to copolymerization reaction under the action of an initiator to synthesize polycarboxylic acid compounds. With the continuous development of the domestic polyether macromonomer industry, the new macromonomer variety represented by EPEG (ethylene glycol monoethyl polyoxyethylene ether) is rapidly developed, and is one of the mainstream polyether macromonomer products in the market. The double bond in the molecular structure of the ethylene glycol monoethyl polyoxyethylene ether macromonomer is directly connected with an oxygen atom, so that the reaction activity of the double bond is obviously improved; due to the active reaction activity, when the copolymer is polymerized with unsaturated carboxylic acid such as acrylic acid and ester small monomers, the required reaction initial temperature is lower, and the dropwise reaction time is shorter (30-60 min); therefore, the polycarboxylic slump retaining agent prepared from the EPEG monomer is easy to cause uneven molecular weight distribution and even implosion phenomenon due to rapid temperature rise in the reaction process in industrial production, so that the laboratory formula of the six-carbon polycarboxylic slump retaining agent is easy to have the defect that the product performance cannot reach the performance of a laboratory sample during industrial scale-up production, and even waste products can be generated. Particularly, for the polycarboxylic acid slump retaining agent, a large amount of unsaturated ester monomers are needed in a reaction system, so that the self-heating phenomenon is more obvious in the copolymerization reaction process, the product quality fluctuation is large, and the repeatability is poor. In the prior patent technology, a plurality of preparation methods for preparing polycarboxylic acid water reducing agent or polycarboxylic acid slump retaining agent by using EPEG monomer are proposed, but the method in the patent is difficult to implement batch high-specification production in the actual industrial production process due to a plurality of practical factors.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention provides a polycarboxylic slump retaining agent which is mainly prepared by carrying out polymerization reaction on ethylene glycol polyoxyethylene ether (EPEG), ester monomers and acrylic monomers, can be matched with a water reducing agent in a certain proportion for use, can keep the slump of concrete for 4-5 h, meets the requirements of the concrete on slump retaining under long-distance transportation and high-temperature environments, and simultaneously effectively solves the problem of great slump loss caused by the difference of raw materials of the concrete.
The second purpose of the invention is to provide a preparation method of the polycarboxylic acid slump retaining agent, which can realize industrial production, has the advantages of stable quality, simple and convenient process, low production energy consumption and the like, can promote the large-scale production and application of the novel vinyl ether monomer polycarboxylic acid slump retaining agent, and promote the technical level of the polycarboxylic acid slump retaining agent to be improved.
The third purpose of the invention is to provide the application of the polycarboxylic slump retaining agent in the field of concrete.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the polycarboxylic slump retaining agent is prepared from the following components in parts by mass: 280-320 parts of ethylene glycol monoethyl polyoxyethylene ether, 5-20 parts of hydroxyethyl methacrylate phosphate, 3-15 parts of acrylic acid, 20-40 parts of hydroxyethyl acrylate, 1-4 parts of an oxidant, 2-8 parts of a chain transfer agent, 0.1-1.5 parts of a reducing agent, 3-20 parts of a pH regulator and a plurality of water.
Preferably, the composition is prepared from the following components in parts by mass: 290-310 parts of ethylene glycol monovinyl polyoxyethylene ether, 8-15 parts of hydroxyethyl methacrylate phosphate, 6-10 parts of acrylic acid, 28-35 parts of hydroxyethyl acrylate, 1.5-3 parts of oxidant, 4-6 parts of chain transfer agent, 0.2-1 part of reducing agent, 5-15 parts of pH regulator and 520-550 parts of water.
Preferably, the raw material components of the polycarboxylic slump retaining agent further comprise: 0.01-1 part of solubilizer; more preferably, the solubilizer comprises at least one of polyoxyethylene hydrogenated castor oil, urea and tween 80.
Preferably, the raw material components of the polycarboxylic acid slump retaining agent further comprise: 0.01-2.5 parts of catalyst; more preferably, the catalyst comprises at least one of an aqueous solution of ferrous sulfate and an aqueous solution of cuprous oxide; further preferably, the aqueous solution has a mass concentration of 1% and the water for preparation is distilled water.
Preferably, the oxidizing agent comprises at least one of hydrogen peroxide, ammonium persulfate, and sodium persulfate.
Preferably, the chain transfer agent comprises at least one of sodium hypophosphite, mercaptopropionic acid, and mercaptoethanol.
Preferably, the reducing agent comprises at least one of E51, VC, or rongalite.
Preferably, the pH adjuster includes at least one of sodium hydroxide, potassium hydroxide, and triethanolamine.
The preparation method of the polycarboxylic slump retaining agent comprises the following steps: ethylene glycol monoethyl polyoxyethylene ether, hydroxyethyl methacrylate phosphate, acrylic acid, hydroxyethyl acrylate, an oxidant, a chain transfer agent, a reducing agent and water are fully mixed for polymerization reaction, and after the reaction is finished, a pH regulator is added until the pH is 5-7, so that the polycarboxylic acid slump retaining agent is obtained.
Preferably, the preparation method comprises the following steps:
(1) Preparing an aqueous solution of ethylene glycol monovinyl polyoxyethylene ether, fully mixing the aqueous solution and the ethylene glycol monovinyl polyoxyethylene ether, and dividing the aqueous solution into two parts to obtain a first solution and a second solution respectively; mixing hydroxyethyl methacrylate phosphate, acrylic acid, hydroxyethyl acrylate and water to obtain a third solution; preparing an aqueous solution of a reducing agent to obtain a fourth solution;
(2) Fully mixing the first solution, an oxidant and a chain transfer agent, and then simultaneously dropwise adding the second solution, the third solution and the fourth solution into the first solution; and after the dropwise addition is finished, carrying out polymerization reaction, and adding a pH regulator to obtain the polycarboxylic acid slump retaining agent.
More preferably, in the step (1), a solubilizer is further added in the process of preparing the aqueous solution of the ethylene glycol monovinyl polyoxyethylene ether.
More preferably, in step (2), a catalyst is further added to the first solution before the dropwise addition is performed.
More preferably, in the step (2), the dropping time of the second solution is 40 to 45min, the dropping time of the third solution is 45 to 50min, and the dropping time of the fourth solution is 50 to 65min.
The polycarboxylic slump retaining agent is applied to the field of concrete.
Preferably, the polycarboxylic acid slump retaining agent and the polycarboxylic acid water reducing agent are compounded for use, and the addition ratio of the polycarboxylic acid slump retaining agent to the polycarboxylic acid water reducing agent is 1:1-2.5;
more preferably, the polycarboxylate superplasticizer is synthesized by any one polyether monomer of HPEG, TPEG or EPEG; the water reducing rate of the polycarboxylate superplasticizer is more than or equal to 25 percent.
Compared with the prior art, the invention has the beneficial effects that:
(1) The ethylene glycol monovinyl polyoxyethylene ether, the hydroxyethyl acrylate, a small amount of hydroxyethyl methacrylate phosphate and acrylic acid are subjected to copolymerization reaction, the initial water reducing rate of the synthesized polycarboxylic slump retaining agent is small, the polycarboxylic slump retaining agent is gradually released after 0.5 hour, and the release amount reaches the maximum after 2 to 3 hours; when the water reducing agent is used in a certain proportion, the slump constant of the concrete can be kept for 3-5 h, and the water reducing agent is particularly suitable for various concretes prepared from machine-made sand containing powder and heavy mud under a high-temperature environment.
(2) The invention adopts vinyl ether macromonomer to synthesize the polycarboxylic acid slump retaining agent, double bonds in the molecular structure of the polycarboxylic acid slump retaining agent are directly connected with oxygen atoms, so that the reaction activity of the double bonds is improved, a copolymerization product which is closer to an ideal copolymerization structure can be formed with acrylic acid and ester monomers, better adsorption dispersion and slump retaining performance are shown, and the effect is obvious especially on the conditions of poor quality and high mud content of sand and stone materials; on the other hand, the double bond in the vinyl ether macromonomer is a substituted structure, so that the space resistance of swinging of the polyether side chain is further reduced, the swinging of the polyether side chain is more free, and the moving range is larger; along with the increase of the swing freedom degree of the polyether side chain, the wrapping property and the winding property of the polyether side chain are improved, so that the polycarboxylic acid slump retaining agent has excellent workability, the use of concrete compound auxiliaries is reduced, and the polycarboxylic acid slump retaining agent has better synergistic compatibility with a carbon six-series water reducing agent.
(3) According to the invention, a small amount of hydroxyethyl methacrylate phosphate and hydroxyethyl acrylate are matched as polymerization raw materials, so that the synthesized polycarboxylic acid slump retaining agent has excellent long-acting slump retaining performance, and the slump retaining agent is uniform in release rate, so that the phenomenon of obvious post-release bleeding of the applied concrete is avoided.
(4) The preparation method of the polycarboxylic slump retaining agent provided by the invention is simple and easy to implement, is easy for industrial production, and is particularly suitable for the production of slump retaining agents of 5-10 tons and above weight levels; the process flow can be adjusted according to the environmental temperature change in different seasons, the process characteristics of polymerization of ethylene glycol monoethyl polyoxyethylene ether monomers under the low-temperature condition can be met, energy consumption is saved, the stability of products is ensured, and the method is particularly suitable for being used by small and medium-sized enterprises without ultrahigh-power refrigeration equipment.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The polycarboxylic slump retaining agent is prepared from the following components in parts by mass: ethylene glycol monovinyl polyoxyethylene ethers include, but are not limited to, 280, 285, 290, 295, 300, 305, 310, 315, 320 parts; hydroxyethyl methacrylate phosphates include, but are not limited to, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 parts; acrylic acid includes, but is not limited to, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts; hydroxyethyl acrylate includes, but is not limited to, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40 parts; oxidants include, but are not limited to, 1, 2, 3, 4 parts; chain transfer agents include, but are not limited to, 2, 3, 4, 5, 6, 7, 8 parts; reducing agents include, but are not limited to, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 parts; pH adjusters include, but are not limited to, 3, 5, 8, 10, 15, 20 parts; and water includes, but is not limited to, 520, 525, 530, 535, 540, 545, 550 parts.
As a preferred embodiment, the raw material components of the polycarboxylic slump retaining agent further comprise: solubilizers include, but are not limited to, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 part; catalysts include, but are not limited to, 0.5, 1, 1.5, 2, 2.5 parts.
It should be noted that the weight parts of the raw material components may be implemented by the above-mentioned point values, or may be implemented by any real value in the numerical range composed of the above-mentioned point values.
The preparation method of the polycarboxylic slump retaining agent comprises the following steps: and fully mixing all the raw material components except the pH regulator, carrying out polymerization reaction, and adding the pH regulator until the pH is 5-7 after the reaction is finished to obtain the polycarboxylic acid slump retaining agent.
As a preferred embodiment, the preparation method can be carried out by the following specific steps:
(1) Preparing an aqueous solution of ethylene glycol monovinyl polyoxyethylene ether, fully mixing the aqueous solution and the ethylene glycol monovinyl polyoxyethylene ether, and dividing the aqueous solution into two parts to obtain a first solution and a second solution respectively; the mass ratio of the first solution to the second solution is 0.65-0.9: 0.1 to 0.35; as an optional embodiment, a solubilizer is further added to the aqueous solution of the ethylene glycol monovinyl polyoxyethylene ether;
according to the invention, a small amount of solubilizer is added when the EPEG monomer is dissolved, so that the EPEG monomer is mainly promoted to be dissolved more uniformly and fully at a low temperature, the homogeneity of the polyether solution (first solution) at the bottom of the kettle and the dropwise adding polyether solution (second solution) is ensured, the dropwise adding pipeline is prevented from being blocked, and better conditions are provided for copolymerization reaction; in addition, the solubilizer has a certain sterilization effect, so that the produced slump retaining agent can be stored for a long time without mildewing and smelling.
(2) Hydroxyethyl methacrylate phosphate, acrylic acid, hydroxyethyl acrylate, and water were mixed to obtain a third solution.
(3) Preparing an aqueous solution of a reducing agent to obtain a fourth solution; as an alternative embodiment, a small amount of chain transfer agent may be added to the fourth solution in this step, the amount of chain transfer agent added being not more than 50% of the total amount of chain transfer agent.
(4) Thoroughly mixing the first solution, an oxidant and a chain transfer agent; as an alternative implementation method, a catalyst is added after the sufficient mixing is performed in the step.
(5) Taking the first solution as a base solution, and simultaneously dropwise adding the second solution, the third solution and the fourth solution into the base solution; as an optional embodiment, the device for performing the dripping has at least two liquid outlets independently, that is, compared with a traditional single-channel dropper or other dripping or infusion devices, the device adopts a multichannel shower-like liquid outlet mode;
the carbon hexapolyether monomer has higher activity, so that the dripping time is shorter when the relevant water reducing agent or slump retaining agent is produced, the temperature is increased violently in the reaction process, the product is easy to be unstable, the performance has the defect of discount type, and the industrialization difficulty is increased; according to the invention, partial polyether is subjected to polymerization reaction in a dripping mode, so that the phenomenon of instantaneous severe temperature rise is relieved, and meanwhile, a traditional 'faucet' type dripping feeding pipe orifice is improved into a 'shower' type feeding port, so that the dripped material can be rapidly and uniformly dispersed in the material at the bottom of the kettle and participate in reaction, self-polymerization or implosion caused by mass aggregation of the material is avoided, the molecular weight distribution of the polymer is more uniform, the product performance is better, the product quality stability is higher, and the effect of strong industrial production controllability is achieved;
as a more preferred embodiment, the initial temperature of each reaction solution is controlled to 10 ℃ to 20 ℃ before the dropwise addition;
in a more preferred embodiment, the dropping time of the second solution is 40 to 45min, the dropping time of the third solution is 45 to 50min, and the dropping time of the fourth solution is 50 to 65min; meanwhile, the error of the dripping time of the solution is controlled within +/-2-3 min.
(6) After the dropwise addition is finished, carrying out polymerization reaction for 45-75 min, and then adding a pH regulator to obtain the polycarboxylic acid slump retaining agent; as an alternative embodiment, the pH adjusting agent comprises a naoh solution at a concentration of 30%; as an optional embodiment, a solvent water is added after the pH regulator is added, so that the concentration of the polycarboxylic acid slump retaining agent is in a preset concentration range.
Example 1
(1) Adding 300g of normal-temperature tap water (14-18 ℃) into a reaction kettle, then adding 300g of ethylene glycol monovinyl polyoxyethylene ether and 0.8g of polyoxyethylene hydrogenated castor oil, stirring and dissolving uniformly to obtain an aqueous solution of unsaturated polyether, and marking as solution A;
(2) Taking out 200g of the solution A as solution B for later use;
(3) Weighing 8g of acrylic acid, 33g of hydroxyethyl acrylate, 12g of hydroxyethyl methacrylate phosphate and 77g of tap water, and preparing to obtain solution C;
(4) Weighing 0.4gE51 and 85g of tap water, and preparing to obtain solution D;
(5) Adding 5.4g of sodium hypophosphite and 2.5g of hydrogen peroxide into the bottom liquid of the reaction kettle in sequence, adding 1.5g of ferrous sulfate aqueous solution prepared by distilled water with the concentration of 1% after 5 minutes, starting to simultaneously dropwise add the liquid B, the liquid C and the liquid D into the reaction kettle after uniformly stirring, wherein the dropwise adding time of the liquid B is 40min, the dropwise adding time of the liquid C is 50min, and the dropwise adding time of the liquid D is 60min;
(6) After the end of the dropwise addition, the mixture was kept at a temperature of 1 hour, a 20g30% NaOH solution was added, and water was added to a concentration of 40%, whereby a polycarboxylic acid slump retaining agent of the present example was obtained.
The preparation process of example 1 is suitable for production in spring and autumn and in early winter when the temperature of tap water is 14-18 ℃. Before production, tap water is not required to be heated or refrigerated, the dropping reaction can be carried out by reducing the temperature of the solution to 10-14 ℃ when the monomer is dissolved, meanwhile, the temperature control is not required to be carried out in the dropping process, and the quality and the yield of the product can reach more than 98%.
Comparative example 1
Essentially the same as example 1, except that:
(3) Weighing 8g of acrylic acid, 45g of hydroxyethyl acrylate and 77g of tap water to prepare a solution C.
In this comparative example, the effect of hydroxyethyl methacrylate phosphate in the present invention was examined by replacing hydroxyethyl methacrylate phosphate with the same mass fraction of hydroxyethyl acrylate.
Example 2
(1) Adding 285g of normal-temperature tap water (19-24 ℃) into a reaction kettle, then adding 300g of ethylene glycol monovinyl polyoxyethylene ether and 0.5g of polyoxyethylene hydrogenated castor oil, stirring and dissolving uniformly to obtain an aqueous solution of unsaturated polyether, and marking as solution A;
(2) Taking out 195g of the solution A as solution B for later use;
(3) Weighing 7g of acrylic acid, 35g of hydroxyethyl acrylate, 11g of hydroxyethyl methacrylate phosphate and 77g of tap water to prepare a solution C;
(4) Weighing 0.53g of VC,1.5g of mercaptopropionic acid and 85g of tap water, and preparing to obtain solution D;
(5) Sequentially adding 3.4g of sodium hypophosphite and 2.9g of hydrogen peroxide into the bottom liquid of the reaction kettle, adding 1g of ferrous sulfate aqueous solution with the concentration of 1% prepared by using distilled water after 5 minutes, starting to simultaneously dropwise add the liquid B, the liquid C and the liquid D into the reaction kettle after uniform stirring, wherein the dropwise adding time of the liquid B is 45min, the dropwise adding time of the liquid C is 55min, and the dropwise adding time of the liquid D is 65min;
(6) After the completion of the dropwise addition, the mixture was kept warm for 40min, and 15g of a 30% NaOH solution was added to adjust the pH value, and water was added to a concentration of 40% to obtain a polycarboxylic acid slump retaining agent of the present example.
The preparation process of example 2 is suitable for production at a tap water temperature of 19 ℃ to 24 ℃. Before production, tap water is not required to be heated or refrigerated, the dropping reaction can be carried out by reducing the temperature of the solution to 15-20 ℃ when the monomer is dissolved, meanwhile, the temperature control is not required to be carried out in the dropping process, and the quality and the yield of the product can reach more than 97%.
Example 3
(1) Adding 250g of normal-temperature tap water (25-28 ℃) into a reaction kettle, adding 300g of ethylene glycol monovinyl polyoxyethylene ether and 0.1g of polyoxyethylene hydrogenated castor oil, stirring until the ethylene glycol monovinyl polyoxyethylene ether and the polyoxyethylene hydrogenated castor oil are dissolved, adding 50g of ice blocks, and continuously stirring uniformly to obtain an aqueous solution of unsaturated polyether, wherein the aqueous solution is marked as solution A;
(2) Taking out 200g of the liquid A as liquid B for later use;
(3) Weighing 6g of acrylic acid, 32g of hydroxyethyl acrylate, 14g of hydroxyethyl methacrylate phosphate and 78g of tap water, and preparing to obtain solution C;
(4) Weighing 0.8g of sodium formaldehyde sulfoxylate, 1.5g of mercaptoethanol and 90g of tap water, and preparing to obtain solution D;
(5) Sequentially adding 2.7g of sodium hypophosphite and 2.0g of ammonium persulfate into the bottom liquid of the reaction kettle, adding 0.5g of ferrous sulfate aqueous solution with the concentration of 1% prepared by using distilled water after 5 minutes, uniformly stirring, and then beginning to simultaneously dropwise add the liquid B, the liquid C and the liquid D into the reaction kettle, wherein the dropwise adding time of the liquid B is 45min, the dropwise adding time of the liquid C is 60min, and the dropwise adding time of the liquid D is 65min;
(6) After the completion of the dropwise addition, the mixture was kept warm for 1 hour, and 20g30% NaOH solution was added to adjust the pH, and water was added to a concentration of 40% to obtain a polycarboxylic acid slump retaining agent of the present example.
The preparation process of example 3 is suitable for production in summer when the temperature of tap water is 25 ℃ to 28 ℃. During production, most normal-temperature tap water is firstly adopted to dissolve the polyether monomer and properly cool the polyether monomer, and then a small amount of ice blocks are adopted to continuously cool the polyether monomer, so that the reaction is started when the temperature of the solution at the bottom of the reaction kettle is between 18 and 20 ℃, the temperature of the reaction is not required to be controlled in the dropping process, and the quality and the yield of the product can reach more than 97 percent. The preparation method of embodiment 3 can realize stable production under the condition of high water temperature by using a small amount of ice cubes, and can realize the purpose of further reducing production energy consumption and cost on the premise of ensuring the product quality.
Comparative example 2
Essentially the same as example 3, except that:
step (2) is not carried out, namely, all the solution A is used as the bottom solution of the reaction kettle in the step (5); nor does it involve any step in step (5) related to the addition of liquid B.
Under the condition of the same initial reaction temperature, when the reaction is performed for 5min to 30min at the earlier stage in the comparative example, the reaction self-heating phenomenon is obvious, and the reaction temperature is 3 ℃ to 5 ℃ higher than that of example 3, and the performance influence is detailed in the following test examples.
Example 4
(1) Heating 300g of normal-temperature tap water (5-13 ℃) in a heating kettle to 16-18 ℃, then transferring the tap water into a reaction kettle, starting stirring, adding 300g of ethylene glycol monoethyl polyoxyethylene ether and 1g of polyoxyethylene hydrogenated castor oil, and uniformly stirring to obtain solution A;
(2) Weighing 10g of acrylic acid, 35g of hydroxyethyl acrylate, 9g of hydroxyethyl methacrylate phosphate and 76g of tap water, and preparing to obtain solution C;
(3) Weighing 1g of sodium formaldehyde sulfoxylate and 90g of tap water, and preparing to obtain solution D;
(4) 4.8g of sodium hypophosphite and 1.9g of ammonium persulfate are sequentially added into the solution A at the bottom of the reaction kettle, 2.5g of ferrous sulfate aqueous solution with the concentration of 1% prepared by distilled water is added after 5 minutes, after uniform stirring, the solution C and the solution D are simultaneously dripped into the reaction kettle, the dripping time of the solution C is 50min, and the dripping time of the solution D is 60min;
(5) After the completion of the dropwise addition, the mixture was kept warm for 1 hour, 25g of a 30-% NaOH solution was added to adjust the pH, and water was added to a concentration of 40% to obtain a polycarboxylic acid slump retaining agent of the present example.
The preparation process of example 4 is suitable for production when the temperature of tap water is 5 to 13 ℃ in winter and early spring. Because the tap water temperature is too low, the polyether monomer is difficult to be completely dissolved, and the conversion rate of monomer polymerization is influenced, so that the production is carried out by heating the tap water to 15-17 ℃ in advance, the polyether monomer is relatively well dissolved at the tap temperature, the solution at the bottom of the reaction kettle can be cooled to 10-13 ℃, the reaction is just suitable for dropwise addition, and meanwhile, the heating energy consumption is minimized. The temperature of the reaction is not required to be controlled in the whole dripping process, and the quality and the yield of the product can reach more than 99 percent.
In this example, since the ambient temperature and the tap water temperature were low, the rate of self-heating was slow during the reaction, and therefore, the production was carried out without adding a part of the polyether monomer dropwise. In addition, adopt in this embodiment to preheat earlier the running water, carry out the mode that the monomer dissolved production again, compare in dissolving the monomer and then carry out the mode efficiency that heats up higher, the energy consumption is lower.
Test examples
The concrete raw materials used in this test example included: (1) cement: sea snail PO42.5 grade ordinary portland cement; (2) fine aggregate: guizhou machine-made sand; (3) coarse aggregate: crushed stone in Guizhou mountain in 5-20 mm size; (4) blending water: tap water.
The concrete formulation used in this test example is shown in table 1 below.
TABLE 1 (unit: kg/m) 3 )
| Cement | Fine aggregate | Coarse aggregate | Water (W) |
| 370 | 972 | 920 | 170 |
The concrete admixture is prepared by mixing the above examples and comparative examples with a water reducing agent, and the preparation scheme comprises the following steps: the polycarboxylic acid slump retaining agent and the water reducing agent prepared in the examples and the comparative examples are compounded into a 10% solution according to the mass ratio of 4:6 for use. The water reducing agent is a polycarboxylic acid high-performance water reducing agent C6-A prepared by EPEG polyether monomer by Guizhou stone doctor science and technology GmbH, and relevant parameters are shown in Table 2.
TABLE 2 Water reducing agent Performance parameter Table
| Solids content | pH value | Water reducing rate | Chloride ion content |
| 45％ | 6.5±1 | ≥28％ | ≤0.6％ |
The performance test of the concrete admixture was carried out according to the regulations described in GB8076-2008 "concrete admixture" and GB/T50080-2016 "Standard test method for Performance of ordinary concrete admixture". The results of the performance tests are shown in table 3 below. Two additional comparative examples are also given in table 3; wherein, the comparative example 1 is polyether type slump retaining agent DST-BTJ-3 produced by TPEG monomer of Guangdong optimized chemical Co., ltd; comparative example 2 is a commercially available TPEG polyether type slump retaining agent.
TABLE 3 Performance test results Table
As can be seen from Table 3, the slump retaining agents produced by synthesizing ethylene glycol monovinyl ether in examples 1 to 4 and comparative example 1 are superior to those produced by synthesizing vinyl alcohol TPEG monomer in concrete in slump retaining property and workability. The embodiment 1 and the comparative example 1 are compared, the embodiment 1 has better performance, and the effect of the co-matching copolymerization of the hydroxyethyl acrylate and the hydroxyethyl methacrylate phosphate is better. Compared with the comparative example 3 and the comparative example 2, the slump retaining performance of the example 3 is obviously excellent in the comparative example 2, which shows that the problem of performance fluctuation of the product caused by over-fast temperature rise in the early stage of the reaction is effectively relieved by adopting a production mode of partially dropwise adding the kettle bottom liquid when the ambient temperature is higher. Compared with the comparative example 2 and the example 8978 in which the liquid zxft 8978 (monomer solution) is completely placed at the bottom of the reaction kettle, the slump retaining performance of the example 4 is obviously superior to that of the comparative example 2, because the initial reaction temperature and the environmental environment are lower in the example 4, and the temperature rise intensity is obviously weakened in the reaction process, so that the influence on the product quality is smaller.
In conclusion, the slump retaining agent for synthesizing the polycarboxylic acid by using the ethylene glycol monovinyl ether provided by the invention can be used for selecting a formula and a process according to the environmental temperature and the reaction tap water temperature, and has strong industrial production feasibility. The product produced according to the embodiment of the invention has small fluctuation rate of quality and obvious slump retaining performance.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the teachings of the foregoing embodiments without departing from the spirit or scope of the present invention, or equivalents may be substituted for some or all of the features thereof; the modifications or the substitutions do not cause the essence of the corresponding technical solutions to depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. The polycarboxylic slump retaining agent is characterized by comprising the following components in parts by mass:
280-320 parts of ethylene glycol monovinyl polyoxyethylene ether, 5-20 parts of hydroxyethyl methacrylate phosphate, 3-15 parts of acrylic acid, 20-40 parts of hydroxyethyl acrylate, 1-4 parts of oxidant, 2-8 parts of chain transfer agent, 0.1-1.5 parts of reducing agent, 3-20 parts of pH regulator and water.
2. The polycarboxylic acid slump retaining agent as claimed in claim 1, which is prepared from the following components in parts by mass:
290-310 parts of ethylene glycol monovinyl polyoxyethylene ether, 8-15 parts of hydroxyethyl methacrylate phosphate, 6-10 parts of acrylic acid, 28-35 parts of hydroxyethyl acrylate, 1.5-3 parts of oxidant, 4-6 parts of chain transfer agent, 0.2-1 part of reducing agent, 5-15 parts of pH regulator and 520-550 parts of water.
3. The polycarboxylic acid slump retaining agent as claimed in claim 1, wherein the polycarboxylic acid slump retaining agent is characterized by further comprising the following raw material components in parts by weight: 0.01-1 part of solubilizer; preferably, the solubilizer comprises at least one of polyoxyethylene hydrogenated castor oil, urea and tween 80.
4. The polycarboxylic acid slump retaining agent as claimed in claim 1, wherein the polycarboxylic acid slump retaining agent is characterized by further comprising the following raw material components in parts by weight: 0.5-2.5 parts of a catalyst; preferably, the catalyst comprises at least one of an aqueous solution of ferrous sulfate and an aqueous solution of cuprous oxide;
more preferably, the mass concentration of the aqueous solution is 1%, and the water for preparation is distilled water.
5. The polycarboxylic acid slump retaining agent according to claim 1, wherein the polycarboxylic acid slump retaining agent comprises at least one of the following characteristics (a) to (d):
(a) The oxidant comprises at least one of hydrogen peroxide, ammonium persulfate and sodium persulfate;
(b) The chain transfer agent comprises at least one of sodium hypophosphite, mercaptopropionic acid and mercaptoethanol;
(c) The reducing agent comprises at least one of E51, VC or rongalite;
(d) The pH regulator comprises at least one of sodium hydroxide, potassium hydroxide and triethanolamine.
6. The method for preparing a polycarboxylic acid slump retaining agent according to any one of claims 1 to 5, comprising the steps of:
ethylene glycol monoethyl polyoxyethylene ether, hydroxyethyl methacrylate phosphate, acrylic acid, hydroxyethyl acrylate, an oxidant, a chain transfer agent, a reducing agent and water are fully mixed for polymerization reaction, and after the reaction is finished, a pH regulator is added until the pH is 5-7, so that the polycarboxylic acid slump retaining agent is obtained.
7. The method for preparing the polycarboxylic acid slump retaining agent according to claim 6, wherein the method comprises the following steps:
(1) Preparing an aqueous solution of ethylene glycol monovinyl polyoxyethylene ether, fully mixing the aqueous solution and the ethylene glycol monovinyl polyoxyethylene ether, and dividing the mixture into two parts to obtain a first solution and a second solution respectively; mixing hydroxyethyl methacrylate phosphate, acrylic acid, hydroxyethyl acrylate and water to obtain a third solution; preparing an aqueous solution of a reducing agent to obtain a fourth solution;
(2) Fully mixing the first solution, an oxidant and a chain transfer agent, and then simultaneously dropwise adding the second solution, the third solution and the fourth solution into the first solution; and after the dropwise addition is finished, carrying out polymerization reaction, and adding a pH regulator to obtain the polycarboxylic acid slump retaining agent.
8. The method for preparing the polycarboxylic acid slump retaining agent according to claim 7, wherein in the step (1), a solubilizer is added in the process of preparing the aqueous solution of the ethylene glycol monovinyl polyoxyethylene ether;
and/or, in the step (2), before the dropwise addition, a catalyst is further added to the first solution.
9. The method for preparing a polycarboxylic acid slump retaining agent according to claim 7, wherein in the step (2), the dropping time of the second solution is 40min to 45min, the dropping time of the third solution is 45min to 50min, and the dropping time of the fourth solution is 50min to 65min.
10. Use of the polycarboxylic acid slump retaining agent as claimed in any one of claims 1 to 5 in the field of concrete;
preferably, the polycarboxylic acid slump retaining agent and the polycarboxylic acid water reducing agent are compounded for use, and the addition ratio of the polycarboxylic acid slump retaining agent to the polycarboxylic acid water reducing agent is 1:1-2.5;
more preferably, the polycarboxylate water reducer is synthesized by any one polyether monomer of HPEG, TPEG or EPEG.
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