CN111533852A - Solid polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Solid polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
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- CN111533852A CN111533852A CN202010408623.8A CN202010408623A CN111533852A CN 111533852 A CN111533852 A CN 111533852A CN 202010408623 A CN202010408623 A CN 202010408623A CN 111533852 A CN111533852 A CN 111533852A
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- polyether amine
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- polycarboxylic acid
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000007787 solid Substances 0.000 title claims abstract description 57
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 54
- 239000002253 acid Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 58
- 229920000570 polyether Polymers 0.000 claims abstract description 58
- 150000001412 amines Chemical class 0.000 claims abstract description 48
- -1 polysiloxane Polymers 0.000 claims abstract description 41
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 16
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 42
- 229920005646 polycarboxylate Polymers 0.000 claims description 22
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 20
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 20
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000008030 superplasticizer Substances 0.000 claims description 11
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 9
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- VGBJGPRWGHIFLO-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole;hydrochloride Chemical compound Cl.C1CN=CO1 VGBJGPRWGHIFLO-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 238000012662 bulk polymerization Methods 0.000 abstract description 15
- 239000000178 monomer Substances 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- CASPZMCSNJZQMV-UHFFFAOYSA-N ethane;2-methyloxirane Chemical compound CC.CC1CO1 CASPZMCSNJZQMV-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YDVJBLJCSLVMSY-UHFFFAOYSA-N carbamoyl cyanide Chemical compound NC(=O)C#N YDVJBLJCSLVMSY-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method 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
- C04B24/26—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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a solid polycarboxylic acid water reducing agent and a preparation method thereof, wherein the water reducing agent comprises the following raw material components in parts by weight: 100-140 parts of unsaturated polyether macromonomer, 12-35 parts of unsaturated carboxylic acid or unsaturated carboxylic acid derivative, 0.6-2.2 parts of non-reactive solubilizer, 0.6-1.92 parts of initiator and 0.6-1.6 parts of chain transfer agent. The non-reactive solubilizer is polyether amine modified polysiloxane and is prepared by reacting diepoxy terminated polysiloxane and polyether amine serving as raw materials in an organic solvent at 65-95 ℃ for 3-6 hours. The powdery solid polycarboxylic acid water reducing agent is obtained by bulk polymerization and cooling and crushing. The non-reactive solubilizer can increase the solubility of the reaction raw materials in the polymerization process, effectively reduce the viscosity of the system in the reaction process, increase the mass and heat transfer among the reaction raw materials, fully react the monomers, and has high macromonomer conversion rate, and the prepared solid polycarboxylic acid water reducer can achieve the water reducing performance of the water-based polycarboxylic acid water reducer.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a solid polycarboxylic acid water reducing agent and a preparation method thereof.
Background
The solid polycarboxylic acid water reducing agent has the advantages of high purity, low transportation cost, convenient storage and the like, is suitable for the engineering technical fields of dry powder mortar, grouting material and the like, and is a research hotspot in the field of concrete admixtures. At present, the preparation method of the solid polycarboxylic acid high-performance water reducing agent adopts spray drying and precipitation methods in industry, the former is easy to generate the phenomena of high viscosity, easy wall adhesion, easy combustion, easy crosslinking, no high temperature resistance and the like in the spray drying process, the water reducing rate of the obtained solid polycarboxylic acid water reducing agent is low, and the construction requirement can be met only under the condition of high mixing amount; the latter uses organic solvent, causing pollution to the environment. The solid polycarboxylic acid water reducing agent prepared by the bulk polymerization method has the advantages of simple process, low energy consumption, no pollution, high solid content of the obtained product, no separant or dispersant, and the like, and is a novel preparation method which is concerned in recent years.
CN 109721690A discloses a preparation method of a viscosity-reduction polycarboxylic acid series high-efficiency solid water reducer, which comprises the steps of carrying out free radical polymerization on raw materials of unsaturated carboxylic acid, unsaturated anhydride, unsaturated phosphate, prenyl polyoxyethylene ether, a reactive plasticizer and a glass transition temperature regulator under the action of an initiator and chain transfer to obtain a liquid polycarboxylic acid water reducer, and then carrying out cooling slicing and crushing to obtain a powdery solid polycarboxylic acid water reducer. The reactive plasticizer in the preparation method can reduce the acting force among polymer molecular chains and the viscosity of a reaction system, but the reactive plasticizer is consumed along with the progress of bulk polymerization, and the problems of large viscosity, difficult mass and heat transfer, cage wall effect and the like cannot be effectively solved at the later stage of the reaction.
CN 107739424A discloses a solid slump-retaining polycarboxylic acid water reducing agent and a preparation method thereof, wherein the solid slump-retaining polycarboxylic acid water reducing agent is prepared by bulk polymerization of isobutylene alcohol polyoxyethylene ether or prenol polyoxyethylene ether, acrylic acid, beta-carboxyethyl acrylate, maleic ester monomers and 2-acrylamide-2-methylpropyl phosphonic acid. According to the preparation method, 1-8% of water is used as a solvent, so that the risk of implosion caused by too fast local reaction in the polymerization process is reduced.
At present, patents on preparing solid polycarboxylic acid water reducing agents by bulk polymerization mainly focus on comonomer modification, copolymerization proportion, initiator and chain transfer agent dosage, initiator feeding mode and the like. The method does not provide an effective guidance scheme for the problems of large matrix viscosity, difficult heat dissipation, blocked segment rearrangement, embedded active terminals, low macromonomer conversion rate, serious acrylic acid auto-polymerization and the like in the bulk polymerization process. Furthermore, the bulk polymer is an oil-soluble system, while the commonly used comonomer acrylic acid is weakly ionic, and has limited solubility in an anhydrous environment, and the viscosity of the molten system further increases as the molecular weight of the product gradually increases as the reaction proceeds.
In addition, the problems of insufficient monomer reaction, low macromonomer conversion rate, poor performance of the obtained product and the like exist in the preparation of the solid polycarboxylic acid water reducing agent by bulk polymerization, so that the industrial development of the solid polycarboxylic acid water reducing agent prepared by the bulk polymerization method at present is not large-scale.
Disclosure of Invention
The invention aims to provide a novel solid polycarboxylate superplasticizer and a preparation method thereof, aiming at the problems of insufficient monomer reaction, low macromonomer conversion rate, poor product performance and the like in the existing solid polycarboxylate superplasticizer prepared by bulk polymerization.
The solid polycarboxylate superplasticizer provided by the invention is prepared from the following raw materials in parts by weight: 100-140 parts of unsaturated polyether macromonomer, 12-35 parts of unsaturated carboxylic acid or unsaturated carboxylic acid derivative, 0.6-2.2 parts of non-reactive solubilizer, 0.6-1.92 parts of initiator and 0.6-1.6 parts of chain transfer agent.
The non-reactive solubilizer is polyether amine modified polysiloxane and is prepared by reacting diepoxy terminated polysiloxane and polyether amine serving as raw materials in an organic solvent at 65-95 ℃ for 3-6 hours. Wherein the molar ratio of the diepoxy-terminated polysiloxane to the polyether amine is 1 (1-2.2). The weight average molecular weight of the diepoxy terminated polysiloxane is 1000-4000 g/mol. The weight average molecular weight of the polyether amine is 220-2000 g/mol. The polyether amine is one of single-ended polyether amine of polyethylene oxide, single-ended polyether amine of polypropylene oxide, single-ended polyether amine copolymerized by ethylene oxide and propylene oxide and double-ended polyether amine copolymerized by ethylene oxide and propylene oxide. The organic solvent is one or a combination of ethanol, isopropanol, isobutanol, ethylene glycol ethyl ether, ethylene glycol butyl ether and propylene glycol methyl ether according to a proportion.
The preparation method of the polyether amine modified polysiloxane comprises the following steps: adding diepoxy terminated polysiloxane and polyetheramine into a four-neck flask according to the molar ratio of 1 (1-2.2), adding a certain amount of organic solvent, stirring, heating to 65-95 ℃, reacting at constant temperature for 3-6 hours, and removing the organic solvent from a reaction product through reduced pressure distillation to obtain carbonyl yellow transparent liquid, namely linear polyetheramine modified polysiloxane.
Wherein the molecular formula of the bis-epoxy-terminated polysiloxane is shown as the formula (I):
wherein n is an integer of 10 to 50.
The polyether amine can be single-end polyether amine shown as a formula (II) or double-end polyether amine shown as a formula (III):
the weight average molecular weight of the single-ended polyether amine is 600-2000. R is-H or-CH3When R is-H, the R is polyethylene oxide-based single-end polyether amine, and (x + y) is an integer of 13-45; when R is-CH3X is 0, y is an integer of 10 to 34, which is a single-ended polypropylene oxide-based polyetheramine; when R is-CH3And (x: y) is (1: 9) to (31: 10), which are single-ended polyetheramines based on ethylene oxide-propylene oxide copolymerization.
The weight average molecular weight of the double-ended polyether amine is 220-2000 g/mol. y: (x + z) is (2: 1) to (39: 6), which are double-ended polyetheramines based on ethylene oxide-propylene oxide copolymerization.
The unsaturated polyether macromonomer is methyl allyl polyoxyethylene ether or prenol polyoxyethylene ether, and the weight average molecular weight is 1600-3100 g/mol.
The unsaturated carboxylic acid is preferably acrylic acid or methacrylic acid. The unsaturated carboxylic acid derivative is preferably one or two of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The preparation method of the solid polycarboxylic acid water reducing agent comprises the following steps:
s1, heating the unsaturated polyether macromonomer to 60-75 ℃ in the reaction kettle, and stirring to completely melt the unsaturated polyether.
S2, mixing at least one of unsaturated carboxylic acid or unsaturated carboxylic acid derivative and chain transfer agent in a dropping tank, and stirring uniformly to obtain dropping liquid.
S3, adding an initiator into the reaction kettle in the step S1, keeping the reaction temperature between 55 and 75 ℃, starting to dropwise add the dropping liquid prepared in the step S2 after the initiator is dissolved, completing dropwise adding within 180 to 300 minutes, and preserving heat for 0.5 to 1 hour after completing dropwise adding.
The non-reactive solubilizer is polyether amine modified polysiloxane, and the addition mode of the polyether amine modified polysiloxane adopts one of the following three modes: (1) adding all the polyether amine modified polysiloxane into the dropping liquid of the step S2; (2) in step S3, all of the polyetheramine-modified polysiloxane was added before the initiator was added; (3) a portion of the polyetheramine-modified polysiloxane was added to the dropping liquid, and the remaining polyetheramine-modified polysiloxane was added before the initiator was added in step S3.
S4, after the heat preservation reaction is finished, discharging, cooling, crushing and grinding to obtain the solid polycarboxylic acid water reducing agent.
Preferably, in step S3, the initiator is added to the reaction kettle 1-3 times at different time periods; if the initiator is put into the reaction kettle at one time, the adding time is before the dropping liquid begins to drop; if the initiator is added into the reaction kettle twice, the adding time is respectively before the dropping liquid begins to drop and 60-120 minutes after the dropping liquid is dropped; and if the initiator is added into the reaction kettle for three times, the adding time is respectively before the dropping of the dropping liquid, 60-120 minutes after the dropping of the dropping liquid and 120-240 minutes after the dropping of the dropping liquid.
The initiator is one or two of persulfate, persulfate and sodium bisulfite redox system, azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyronitrile formamide, azodiisopropylamidine oxazoline hydrochloride, dibenzoyl peroxide and dimethylaniline. The chain transfer agent is one or two of mercaptoethanol, mercaptoacetic acid and mercaptopropionic acid.
Compared with the prior art, the invention has the advantages that:
according to the preparation method of the solid polycarboxylate water reducer, the polyether amine modified polysiloxane is used as a non-reactive solubilizer, so that the solubility of reaction raw materials is increased, the viscosity of a system in the polymerization reaction process is effectively reduced, the mass transfer and heat transfer among the reaction raw materials are increased, monomers are fully reacted, the conversion rate of the large monomers is high, and the prepared solid polycarboxylate water reducer can achieve the water reducing performance of the water-based polycarboxylate water reducer.
The principle of action of the non-reactive solubilizer in the invention is as follows: the linear polyether amine modified polysiloxane synthesized by adopting the diepoxy terminated polysiloxane and the polyether amine as raw materials has an amphiphilic structure. The polyether amine modified polysiloxane is used as a non-reactive solubilizer for preparing the solid polycarboxylic acid water reducer by bulk polymerization. In the polyether amine modified polysiloxane molecule, a polysiloxane chain segment with strong hydrophobicity is used as a hydrophobic segment, and a polyoxyethylene polyoxypropylene ether group is used as a hydrophilic segment, so that the compatibility of the oil-soluble macromonomer and the water-soluble copolymerized unsaturated carboxylic acid in the anhydrous environment of bulk polymerization is improved, and the viscosity of a reaction system in the reaction process is effectively reduced.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1
The solid polycarboxylic acid water reducing agent is prepared from the following raw materials in parts by mass: 127 parts of prenyl alcohol polyoxyethylene ether with the weight-average molecular weight of 2400, 16.2 parts of acrylic acid, 1.02 parts of non-reactive solubilizer, 0.72 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.72 part of azodiisobutyronitrile and 0.96 part of chain transfer agent mercaptopropionic acid.
The preparation method of the non-reactive solubilizer comprises the following steps: reacting diepoxy terminated polysiloxane with the weight-average molecular weight of 1000g/mol and epoxy ethane-propylene oxide copolymerized double-ended polyether amine with the weight-average molecular weight of 220g/mol in isopropanol at the temperature of 85 ℃ for 4 hours according to the molar ratio of 1:1.1, and removing the isopropanol through reduced pressure distillation to obtain linear polyether amine modified polysiloxane to be synthesized and used in the next step.
The preparation method of the solid polycarboxylic acid water reducing agent comprises the following steps: (1) putting the prenyl alcohol polyoxyethylene ether into a reaction kettle (the reaction kettle can be a 500ml four-neck flask), heating to 60 ℃, and starting stirring to completely melt the prenyl alcohol polyoxyethylene ether; (2) 16.2 parts of acrylic acid and 0.96 part of mercaptopropionic acid are fully and uniformly stirred in a dripping tank to prepare dripping liquid; (3) after the prenyl alcohol polyoxyethylene ether in the reaction kettle in the step (1) is completely melted, cooling to 55 ℃, then adding 1.02 parts of non-reactive solubilizer, 0.72 part of ammonium persulfate, 0.1 part of sodium bisulfite and 0.24 part of azobisisobutyronitrile into the reaction kettle, continuously stirring, after the initiator is dissolved, beginning to dropwise add the dropwise added liquid prepared in the step (2) by using a constant flow pump, wherein the total dropwise adding time is 180 minutes, 0.24 part of azobisisobutyronitrile is added into the bottom of the kettle for the second time when the dropwise added liquid is dropwise added for 90 minutes, 0.24 part of azobisisobutyronitrile is added into the bottom of the kettle for the third time when the dropwise added liquid is dropwise added for 120 minutes, and after the dropwise adding of the added liquid is finished, carrying out heat preservation and aging reaction for 1 hour; (4) and after the heat preservation reaction is finished, discharging, and after the product is cooled and hardened, crushing and grinding to obtain the solid polycarboxylic acid water reducing agent.
Example 2
The solid polycarboxylic acid water reducing agent is prepared from the following raw materials in parts by mass: 145 parts of prenyl alcohol polyoxyethylene ether with the weight-average molecular weight of 1800, 15.8 parts of acrylic acid, 2.4 parts of hydroxyethyl acrylate, 0.85 part of non-reactive solubilizer, 1.74 parts of azodiisoheptonitrile and 1.06 parts of thioglycolic acid as a chain transfer agent.
The preparation method of the non-reactive solubilizer comprises the following steps: reacting diepoxy terminated polysiloxane with the weight-average molecular weight of 2000g/mol and polyethylene oxide single-ended polyether amine with the weight-average molecular weight of 1000g/mol in ethylene glycol butyl ether according to the molar ratio of 1:2.1 at 95 ℃ for 5 hours, and removing the solvent through reduced pressure distillation to obtain linear polyether amine modified polysiloxane to be synthesized and used in the next step.
The preparation method of the solid polycarboxylic acid water reducing agent comprises the following steps: (1) putting the prenyl polyoxyethylene ether into a reaction kettle, heating to 60 ℃, and starting stirring; (2) fully and uniformly stirring 15.8 parts of acrylic acid, 2.4 parts of hydroxyethyl acrylate and 1.06 parts of thioglycollic acid to prepare dropping liquid; (3) after the prenyl alcohol polyoxyethylene ether in the reaction kettle in the step (1) is completely melted, keeping the temperature at 60 ℃, then adding 0.85 part of non-reactive solubilizer into the reaction kettle, adding 0.58 part of azobisisoheptonitrile for the first time, continuing stirring, beginning to dropwise add the dropwise added liquid prepared in the step (2) by using a constant flow pump after an initiator is dissolved, wherein the total dropwise adding time is 200 minutes, after 60 minutes of dropwise adding of the dropwise added liquid, adding 0.58 part of azobisisoheptonitrile into the bottom of the kettle for the second time, after 150 minutes of dropwise adding of the dropwise added liquid, adding 0.58 part of azobisisoheptonitrile into the bottom of the kettle for the third time, and after the dropwise adding of the dropwise added liquid is finished, preserving the temperature and carrying out an aging reaction for 40 minutes; (4) and after the heat preservation reaction is finished, discharging, and after the product is cooled and hardened, crushing and grinding to obtain the solid polycarboxylic acid water reducing agent.
Example 3
The solid polycarboxylic acid water reducing agent is prepared from the following raw materials in parts by mass: 120 parts of methyl allyl polyoxyethylene ether with the weight-average molecular weight of 2800, 14.8 parts of acrylic acid, 1.02 parts of methyl methacrylate and 3.2 parts of hydroxyethyl methacrylate, and the non-reactive solubilizer comprises 1.44 parts of potassium persulfate, 0.86 part of sodium bisulfite, 0.84 part of azo-isobutyryl cyano formamide and 0.82 part of mercaptopropionic acid.
The preparation method of the non-reactive solubilizer comprises the following steps: reacting diepoxy-terminated polysiloxane with the weight-average molecular weight of 4000g/mol and single-ended polyether amine of polypropylene oxide with the weight-average molecular weight of 600g/mol in a mixed solution of ethylene glycol butyl ether and propylene glycol methyl ether according to the molar ratio of 1:2.2 at the temperature of 80 ℃ for 3 hours, and removing the solvent through reduced pressure distillation to obtain linear polyether amine modified polysiloxane to be synthesized and used in the next step.
The preparation method of the solid polycarboxylic acid water reducing agent comprises the following steps: (1) putting the methyl allyl polyoxyethylene ether into a reaction kettle, heating to 65 ℃, and starting stirring; (2) fully and uniformly stirring 14.8 parts of acrylic acid, 1.02 parts of methyl methacrylate, 3.2 parts of hydroxyethyl methacrylate, 0.72 part of non-reactive solubilizer and 0.82 part of mercaptopropionic acid to prepare a dropping liquid; (3) after the methyl allyl polyoxyethylene ether in the reaction kettle in the step (1) is completely melted, cooling to 60 ℃, then adding 0.72 part of non-reactive solubilizer, 0.86 part of potassium persulfate, 0.12 part of sodium bisulfite and 0.42 part of azobisisobutyronitrile formamide into the reaction kettle, continuing stirring, after the initiator is dissolved, beginning to dropwise add the dropping liquid prepared in the step (2) by using a constant flow pump, wherein the total dropwise adding time is 240 minutes, after the dropping liquid is dropwise added for 150 minutes, adding 0.42 part of azobisisobutyronitrile formamide into the bottom of the kettle for the second time, and after the dropwise adding of the dropping liquid is finished, preserving heat and carrying out an aging reaction for 0.5 hour; (4) and after the heat preservation reaction is finished, discharging, and after the product is cooled and hardened, crushing and grinding to obtain the solid polycarboxylic acid water reducing agent.
Example 4
The solid polycarboxylic acid water reducing agent is prepared from the following raw materials in parts by mass: 140 parts of methyl allyl polyoxyethylene ether with the weight-average molecular weight of 3000, 22.6 parts of acrylic acid, 2.62 parts of ethyl acrylate, 3.56 parts of hydroxypropyl methacrylate, 2.54 parts of non-reactive solubilizer, 0.72 part of dibenzoyl peroxide, 0.96 part of azobisisoheptonitrile, 0.82 part of mercaptopropionic acid and 0.18 part of mercaptoethanol.
The preparation method of the non-reactive solubilizer comprises the following steps: reacting diepoxy terminated polysiloxane with the weight-average molecular weight of 1200g/mol and epoxy ethane-epoxy propane copolymerized single-ended polyether amine with the weight-average molecular weight of 600g/mol in isopropanol at 65 ℃ for 6 hours according to the molar ratio of 1:1.2, and removing the isopropanol through reduced pressure distillation to obtain linear polyether amine modified polysiloxane to be synthesized and used in the next step.
The preparation method of the solid polycarboxylic acid water reducing agent comprises the following steps: (1) putting the methyl allyl polyoxyethylene ether into a reaction kettle (the reaction kettle can be a 500ml four-neck flask), heating to 70 ℃, and starting stirring; (2) simultaneously, 22.6 parts of acrylic acid, 2.62 parts of ethyl acrylate, 3.56 parts of hydroxypropyl methacrylate, 0.72 part of non-reactive solubilizer, 0.82 part of chain transfer agent mercaptopropionic acid and 0.18 part of mercaptoethanol are fully and uniformly stirred to prepare dropping liquid; (3) after the methyl allyl polyoxyethylene ether in the reaction kettle in the step (1) is completely melted, cooling to 65 ℃, then adding 0.72 part of dibenzoyl peroxide and 1.82 parts of non-reactive solubilizer into the reaction kettle, continuing stirring, after the initiator is dissolved, beginning to dropwise add the dropping liquid prepared in the step (2) by using a constant flow pump, wherein the total dropwise adding time is 300 minutes, after dropping the dropping liquid for 120 minutes, firstly adding 0.60 part of azobisisoheptonitrile into the kettle bottom, after dropping the dropping liquid for 180 minutes, secondly adding 0.16 part of azobisisoheptonitrile into the kettle bottom, after dropping the dropping liquid for 240 minutes, thirdly adding 0.16 part of azobisisoheptonitrile into the kettle bottom, and after the dropping liquid is completely dropped, preserving heat and ageing for 1 hour; (4) and after the heat preservation reaction is finished, discharging, and after the product is cooled and hardened, crushing and grinding to obtain the solid polycarboxylic acid water reducing agent.
Comparative example 1
The non-reactive solubilizer in example 1 was removed and the amount of other monomers and preparation were the same as in example 1.
Comparative example 2
The non-reactive solubilizer in example 1 was replaced with deionized water of the same mass, and the amounts of other monomers and the preparation process were the same as in example 1.
And (3) performance testing:
gel permeation chromatography, viscosity of a melting system in the bulk polymerization process and performance test of concrete are carried out on the solid polycarboxylate water reducing agent obtained in the embodiments 1 to 4, the commercially available water-based polycarboxylate water reducing agent, the commercially available solid polycarboxylate water reducing agent prepared by bulk polymerization and the solid polycarboxylate water reducing agent prepared in the comparative examples 1 to 2. The molecular weight of the above samples and their molecular weight distribution were determined using a U.S. Waters2414 Gel Permeation Chromatography (GPC) system. The viscosity of the melting system in the synthesis process is tested by adopting an NDJ-9S rotational viscometer of Shanghai Pinxuan scientific instruments Co. The concrete performance test is carried out according to the standard of the test method for the performance of common concrete mixtures (GB/T50080-2002). Referring to the following experimental data table, table 1 shows the molecular weights and molecular weight distributions of the samples tested by gel permeation chromatography. Table 2 shows the viscosity of the melt system as a function of the reaction time in the bulk polymerization. Table 3 shows the concrete performance test data, using the tensile-process-based cement, with the bending-fixing admixture amount of the water reducing agent being 0.18% of the mass of the cementitious material.
TABLE 1 molecular weights and molecular weight distributions
| Sample (I) | Weight average molecular weight (Mw) | Molecular weight distribution (PDI) | Monomer conversion/% |
| Water-based polycarboxylic acid water reducing agent | 38784 | 1.46 | 92.7 |
| Commercial solid polycarboxylic acid water reducing agent | 40568 | 2.43 | 83.3 |
| Comparative example 1 | 40122 | 2.23 | 84.5 |
| Comparative example 2 | 40023 | 2.16 | 85.2 |
| Example 1 | 39526 | 1.43 | 91.3 |
| Example 2 | 38786 | 1.53 | 92.8 |
| Example 3 | 37118 | 1.56 | 90.3 |
| Example 4 | 39563 | 1.58 | 90.8 |
TABLE 2 viscosity of the melt system as a function of the reaction time in the bulk polymerization
TABLE 3 concrete Performance test results
The test results show that the solid polycarboxylate superplasticizer prepared by the method has high macromonomer conversion rate and excellent performance, and can achieve the water reducing performance of the water-based polycarboxylate superplasticizer. According to the comparative example, the addition of the non-reactive solubilizer can reduce the viscosity of a reaction system in the polymerization process and increase the mass and heat transfer among reaction raw materials, the molecular weight and the molecular weight distribution of the prepared solid polycarboxylate water reducer are similar to those of the water-based PCE molecular structure, and the application performance of concrete is close to that of the common water-based polycarboxylate water reducer. The non-reactive solubilizer can increase the solubility of reaction raw materials in the polymerization process, effectively reduce the viscosity of the system in the reaction process, and the water reducing performance of the prepared solid polycarboxylate water reducer can reach the performance of aqueous mother liquor, thereby avoiding the problems of reducing the water reducing performance, flammability, explosiveness and the like of the solid polycarboxylate water reducer prepared by a high-temperature spray drying method.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The solid polycarboxylic acid water reducing agent is characterized by comprising the following raw materials in parts by weight: 100-140 parts of unsaturated polyether macromonomer, 12-35 parts of unsaturated carboxylic acid or unsaturated carboxylic acid derivative, 0.6-2.2 parts of non-reactive solubilizer, 0.6-1.92 parts of initiator and 0.6-1.6 parts of chain transfer agent, wherein the non-reactive solubilizer is polyether amine modified polysiloxane.
2. The solid polycarboxylate superplasticizer according to claim 1, wherein the polyether amine modified polysiloxane is prepared by reacting diepoxy terminated polysiloxane and polyether amine as raw materials in an organic solvent at 65-95 ℃ for 3-6 hours.
3. The solid polycarboxylate superplasticizer according to claim 2, wherein the molar ratio of the diepoxy-terminated polysiloxane to the polyetheramine is 1 (1-2.2), and the weight average molecular weight of the diepoxy-terminated polysiloxane is 1000-4000 g/mol; the weight average molecular weight of the polyether amine is 220-2000 g/mol; the polyether amine is one of single-ended polyether amine of polyethylene oxide, single-ended polyether amine of polypropylene oxide, single-ended polyether amine copolymerized by ethylene oxide and propylene oxide and double-ended polyether amine copolymerized by ethylene oxide and propylene oxide.
4. The solid polycarboxylic acid water reducer according to claim 2, characterized in that said organic solvent is one or more of ethanol, isopropanol, isobutanol, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol methyl ether in a proportional combination.
5. The solid polycarboxylate superplasticizer according to claim 2, wherein the unsaturated polyether macromonomer is methyl allyl polyoxyethylene ether or prenol polyoxyethylene ether, and the weight average molecular weight is 1600-3100 g/mol; the unsaturated carboxylic acid is acrylic acid or methacrylic acid; the unsaturated carboxylic acid derivative is one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
6. A method for preparing a solid polycarboxylic acid water reducing agent according to any one of claims 1 to 5, characterized by comprising the steps of:
s1, heating the unsaturated polyether macromonomer in the reaction kettle to be completely molten;
s2, mixing and stirring at least one of unsaturated carboxylic acid or unsaturated carboxylic acid derivative and a chain transfer agent uniformly to obtain a dropping liquid;
s3, adding an initiator into the reaction kettle in the step S1, keeping the reaction temperature between 55 and 75 ℃, starting to dropwise add the dropping liquid prepared in the step S2 after the initiator is dissolved, finishing dropwise adding within 180 to 300 minutes, and preserving heat for 0.5 to 1 hour after completing dropwise adding;
the non-reactive solubilizer is polyether amine modified polysiloxane, and the addition mode of the polyether amine modified polysiloxane adopts one of the following three modes: (1) adding all the polyether amine modified polysiloxane into the dropping liquid of the step S2; (2) in step S3, all of the polyetheramine-modified polysiloxane was added before the initiator was added; (3) adding a part of the polyether amine modified polysiloxane into the dropping liquid in the step S2, and adding the rest of the polyether amine modified polysiloxane before adding the initiator in the step S3;
s4, after the heat preservation reaction is finished, discharging, cooling, crushing and grinding to obtain the solid polycarboxylic acid water reducing agent.
7. The preparation method of the solid polycarboxylate superplasticizer according to claim 6, wherein in step S1, the unsaturated polyether macromonomer is heated to 60-75 ℃, and stirred to completely melt the unsaturated polyether.
8. The method for preparing a solid polycarboxylic acid water reducing agent according to claim 6, characterized in that in step S3, the initiator is added to the reaction kettle in 1-3 times at different time periods; if the initiator is put into the reaction kettle at one time, the adding time is before the dropping liquid begins to drop; if the initiator is added into the reaction kettle twice, the adding time is respectively before the dropping liquid begins to drop and 60-120 minutes after the dropping liquid is dropped; and if the initiator is added into the reaction kettle for three times, the adding time is respectively before the dropping of the dropping liquid, 60-120 minutes after the dropping of the dropping liquid and 120-240 minutes after the dropping of the dropping liquid.
9. The method for preparing the solid polycarboxylate superplasticizer according to claim 6, wherein the initiator is one or two of persulfate, persulfate and sodium bisulfite redox system, azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyronitrile formamide, azobisdiisopropylamidine oxazoline hydrochloride, dibenzoyl peroxide and dimethylaniline.
10. The method for preparing the solid polycarboxylate superplasticizer according to claim 6, wherein the chain transfer agent is one or two of mercaptoethanol, mercaptoacetic acid and mercaptopropionic acid.
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