CN114213602B - Viscosity-reducing water reducer and preparation method thereof - Google Patents
Viscosity-reducing water reducer and preparation method thereof Download PDFInfo
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- CN114213602B CN114213602B CN202111641745.2A CN202111641745A CN114213602B CN 114213602 B CN114213602 B CN 114213602B CN 202111641745 A CN202111641745 A CN 202111641745A CN 114213602 B CN114213602 B CN 114213602B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 57
- 229920000570 polyether Polymers 0.000 claims abstract description 57
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 27
- 230000001603 reducing effect Effects 0.000 claims abstract description 25
- 150000002148 esters Chemical class 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 41
- -1 polyoxyethylene Polymers 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 26
- LQQCGEGRINLHDP-UHFFFAOYSA-N carboxyphosphoric acid Chemical compound OC(=O)OP(O)(O)=O LQQCGEGRINLHDP-UHFFFAOYSA-N 0.000 claims description 22
- 230000001105 regulatory effect Effects 0.000 claims description 17
- 238000005886 esterification reaction Methods 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005394 methallyl group Chemical group 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 28
- 239000006185 dispersion Substances 0.000 abstract description 9
- 239000004568 cement Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229950000688 phenothiazine Drugs 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011372 high-strength concrete Substances 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- DDKMFQGAZVMXQV-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CCl DDKMFQGAZVMXQV-UHFFFAOYSA-N 0.000 description 2
- FFKUDWZICMJVPA-UHFFFAOYSA-N 2-phosphonooxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OP(O)(O)=O FFKUDWZICMJVPA-UHFFFAOYSA-N 0.000 description 2
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 2
- SNTHOGUFMKMFMO-UHFFFAOYSA-N 3-phosphonooxybenzoic acid Chemical compound OC(=O)C1=CC=CC(OP(O)(O)=O)=C1 SNTHOGUFMKMFMO-UHFFFAOYSA-N 0.000 description 2
- VVWPSAPZUZXYCM-UHFFFAOYSA-N 9-methoxy-9-oxononanoic acid Chemical compound COC(=O)CCCCCCCC(O)=O VVWPSAPZUZXYCM-UHFFFAOYSA-N 0.000 description 2
- WFQULMYRWQMBKA-UHFFFAOYSA-N P(=O)#CCC(=O)O Chemical compound P(=O)#CCC(=O)O WFQULMYRWQMBKA-UHFFFAOYSA-N 0.000 description 2
- OSYQOBUUFRGFNG-UHFFFAOYSA-N Sebacic acid monomethyl ester Chemical compound COC(=O)CCCCCCCCC(O)=O OSYQOBUUFRGFNG-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UOBSVARXACCLLH-UHFFFAOYSA-N monomethyl adipate Chemical compound COC(=O)CCCCC(O)=O UOBSVARXACCLLH-UHFFFAOYSA-N 0.000 description 2
- IBMRTYCHDPMBFN-UHFFFAOYSA-N monomethyl glutaric acid Chemical compound COC(=O)CCCC(O)=O IBMRTYCHDPMBFN-UHFFFAOYSA-N 0.000 description 2
- JDRMYOQETPMYQX-UHFFFAOYSA-N monomethyl succinate Chemical compound COC(=O)CCC(O)=O JDRMYOQETPMYQX-UHFFFAOYSA-N 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 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 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- PBVZQAXFSQKDKK-UHFFFAOYSA-N 3-Methoxy-3-oxopropanoic acid Chemical compound COC(=O)CC(O)=O PBVZQAXFSQKDKK-UHFFFAOYSA-N 0.000 description 1
- MIIADZYPHVTLPR-UHFFFAOYSA-N 4-(methoxycarbonyl)-3-nitrobenzoic acid Chemical compound COC(=O)C1=CC=C(C(O)=O)C=C1[N+]([O-])=O MIIADZYPHVTLPR-UHFFFAOYSA-N 0.000 description 1
- FBXJLZYWIAOHFO-UHFFFAOYSA-N 4-phosphonooxybenzoic acid Chemical compound OC(=O)C1=CC=C(OP(O)(O)=O)C=C1 FBXJLZYWIAOHFO-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- BYBMHSADRRMVHY-UHFFFAOYSA-N 5-methoxy-3-methyl-5-oxopentanoic acid Chemical compound COC(=O)CC(C)CC(O)=O BYBMHSADRRMVHY-UHFFFAOYSA-N 0.000 description 1
- KOVPXZDUVJGGFU-UHFFFAOYSA-N 8-methoxy-8-oxooctanoic acid Chemical compound COC(=O)CCCCCCC(O)=O KOVPXZDUVJGGFU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- OXXOYNFTOCTMGG-UHFFFAOYSA-N acetic acid;6-amino-2-[[2-(2,6-diaminohexanoylamino)-3-(4-hydroxyphenyl)propanoyl]amino]hexanoic acid Chemical compound CC(O)=O.NCCCCC(N)C(=O)NC(C(=O)NC(CCCCN)C(O)=O)CC1=CC=C(O)C=C1 OXXOYNFTOCTMGG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RFUCOAQWQVDBEU-UHFFFAOYSA-N methyl 2-(hydroxymethyl)prop-2-enoate Chemical compound COC(=O)C(=C)CO RFUCOAQWQVDBEU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000012546 transfer 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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a viscosity-reducing water reducer, which comprises the following raw materials in parts by weight: 100-200 parts of low molecular weight polyether macromonomer; 1-10 parts of hydrophobic functional monomer; 5-30 parts of unsaturated acid; 1-10 parts of unsaturated ester; 0.5-8 parts of initiator; and water. The viscosity-reducing water reducer prepared by the invention can release more free water while maintaining a dispersion function, thereby increasing the fluidity of concrete and playing a good role in reducing viscosity.
Description
Technical Field
The invention relates to the technical field of building additives, in particular to a viscosity-reducing water reducer and a preparation method thereof.
Background
The polycarboxylic acid high-performance water reducer has the advantages of low mixing amount, high water reducing rate, good collapse protection performance, strong molecular structure adjustability and the like, and becomes the key point of research and development in the field of domestic and foreign concrete water reducers.
The application of modern high-strength concrete is spread in various civil engineering fields such as bridge engineering, building engineering, harbor ocean engineering, underground engineering and the like. The improvement of the strength of the concrete is mainly realized by reducing the water-cement ratio, which leads to the increase of the viscosity of the concrete, thereby causing a series of construction problems such as concrete stirring, transportation, pumping and the like, and greatly limiting the popularization and application of the high-strength and ultra-high-strength concrete.
Disclosure of Invention
Based on the viscosity reducing water reducer, the viscosity reducing water reducer and the preparation method thereof can reduce the viscosity of concrete and increase the fluidity of the concrete.
The viscosity reduction type water reducer comprises the following preparation raw materials in parts by weight:
the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
Preferably, the initiator comprises, in parts by weight:
0.5-3 parts of oxidant;
1-6 parts of reducing agent.
Preferably, the preparation raw materials of the viscosity-reducing water reducer further comprise, in parts by weight:
2-8 parts of chain transfer agent and carboxyl phosphoric acid;
the molar ratio of the polyether macromonomer to the carboxyl phosphoric acid is (1.0-1.2): 1.
Preferably, the unsaturated acid includes at least one of acrylic acid and methacrylic acid.
Preferably, the unsaturated ester includes at least one of vinyl acetate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
The invention also provides a preparation method of the viscosity-reducing water reducer, which comprises the following steps:
according to parts by weight, placing 100-200 parts of low molecular weight polyether macromonomer, 1-10 parts of hydrophobic functional monomer, 5-30 parts of unsaturated acid, 1-10 parts of unsaturated ester, 0.5-8 parts of initiator and water into a reactor for copolymerization reaction, and obtaining the viscosity-reducing water reducer after the reaction is finished; the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
Preferably, the preparation method of the viscosity-reducing water reducer comprises the following steps:
100-200 parts of the low molecular weight polyether macromonomer, 1-10 parts of the hydrophobic functional monomer, 2-8 parts of chain transfer agent and water are placed in a reactor according to parts by weight, and stirred and dissolved to obtain a first mixed solution;
dropwise adding 5-30 parts of mixed solution of unsaturated acid and 1-10 parts of unsaturated ester, 0.5-3 parts of oxidant and 1-6 parts of reducing agent into the first mixed solution to carry out copolymerization reaction, and after the dropwise adding is finished, carrying out heat preservation reaction to obtain a second mixed solution after the reaction is finished;
and (3) after the second mixed solution is cooled to room temperature, regulating the pH value of the second mixed solution to 6-7 by using alkali liquor, and obtaining the viscosity-reducing water reducer.
Preferably, the preparation method of the low molecular weight polyether macromonomer comprises the following steps:
and (3) placing the low molecular weight polyether macromonomer and carboxyl phosphoric acid into a first reactor to perform esterification reaction, and obtaining the phosphate end-capped low molecular weight polyether macromonomer after the reaction is finished.
Preferably, the preparation method of the hydrophobic functional monomer comprises the following steps:
placing unsaturated acid hydroxyalkyl ester and fatty diacid monomethyl ester in a second reactor to perform esterification reaction, and obtaining the hydrophobic functional monomer after the reaction is finished.
Preferably, the low molecular weight polyether macromonomer comprises at least one of methallyl polyoxyethylene and isopentenyl polyoxyethylene ether.
Compared with the prior art, the invention has the following beneficial effects:
compared with the water reducer prepared by the large molecular weight macromonomer, the viscosity reducing water reducer prepared by the invention can maintain the dispersion function, and meanwhile, the molecular weight of the viscosity reducing water reducer prepared by the low molecular weight polyether macromonomer can be reduced, so that the viscosity reducing water reducer has higher freedom of movement than that of a common water reducer in free water, and the molecular chain of the water reducer can be rapidly stretched, thereby rapidly absorbing and dispersing cement particles, reducing the viscosity of cement paste, and increasing the fluidity of concrete, and the prepared viscosity reducing water reducer has good viscosity reducing performance.
According to the invention, the hydrophobic functional monomer is introduced for copolymerization, and the hydrophobic functional monomer has lipophilicity, so that the HLB value (hydrophilic-hydrophobic balance value) of the water reducer can be reduced, the water film layer thickness of cement particles in concrete slurry can be reduced while the adsorption effect between the viscosity-reducing water reducer and the cement particles is maintained, the fluidity of the concrete is improved, and a good viscosity-reducing effect is achieved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The quantitative tests in the following examples were all set up with three replicates, and the data are the mean or mean ± standard deviation of the three replicates.
In addition, "and/or" throughout this document includes three schemes, taking a and/or B as an example, including a technical scheme, a technical scheme B, and a technical scheme that both a and B satisfy; in addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the combination of the technical solutions, when the technical solutions are contradictory or cannot be implemented, it is considered that the combination of the technical solutions does not exist, and the combination is not within the scope of protection claimed by the present invention.
The invention provides a viscosity-reducing water reducer, which comprises the following raw materials in parts by weight:
the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
Compared with the water reducer prepared by the large molecular weight macromonomer, the viscosity reducing water reducer prepared by the invention can maintain the dispersion function, and meanwhile, the molecular weight of the viscosity reducing water reducer prepared by the low molecular weight polyether macromonomer can be reduced, so that the viscosity reducing water reducer has higher freedom of movement than that of a common water reducer in free water, and the molecular chain of the water reducer can be rapidly stretched, thereby rapidly absorbing and dispersing cement particles, reducing the viscosity of cement paste, and increasing the fluidity of concrete, and the prepared viscosity reducing water reducer has good viscosity reducing performance.
According to the invention, the hydrophobic functional monomer is introduced for copolymerization, and the hydrophobic functional monomer has lipophilicity, so that the HLB value (hydrophilic-hydrophobic balance value) of the water reducer can be reduced, the water film layer thickness of cement particles in concrete slurry can be reduced while the adsorption effect between the viscosity-reducing water reducer and the cement particles is maintained, the fluidity of the concrete is improved, and a good viscosity-reducing effect is achieved.
In some embodiments, the initiator comprises, in parts by weight:
0.5-3 parts of oxidant;
1-6 parts of reducing agent.
Specifically, the oxidant and the reducing agent form a redox system as an initiator of the polymerization reaction, and the electron transfer between the oxidant and the reducing agent generates an initiator free radical. The initiation rate of redox system initiators is relatively fast.
The oxidant comprises any one of hydrogen peroxide, sodium persulfate and ammonium persulfate.
The reducing agent includes at least one of ascorbic acid, sodium formaldehyde sulfoxylate, and Bruggolite FF6 (a boulgeman reducing agent).
In some embodiments, the low molecular weight polyether macromonomer comprises at least one of a methylallyl polyoxyethylene and an isopentenyl polyoxyethylene ether.
In some embodiments, the viscosity reducing water reducer is prepared from the following raw materials in parts by weight:
2-8 parts of chain transfer agent and carboxyl phosphoric acid;
the molar ratio of the polyether macromonomer to the carboxyl phosphoric acid is (1.0-1.2): 1.
Specifically, when the molecular weight of the polyether macromonomer is 500-1500, the prepared water reducer has small molecular weight, the same acid consumption and small quantity of adsorption and dispersion groups, and the adsorption and dispersion effects of water reducer molecules on cement particles are reduced, so that the water reducer molecules can be selectively blocked by carboxyl phosphoric acid in side chains of the water reducer molecules, the adsorption effect of the phosphoric acid groups in the carboxyl phosphoric acid is strong, and the surface of the cement particles adsorbed by the phosphoric acid groups in the concrete are dispersed by electrostatic repulsion and steric hindrance to form a thin and denser water film layer, so that the fluidity of the concrete is improved.
It should be noted that the raw material for preparing the viscosity-reducing water reducer may be a low molecular weight polyether macromonomer, or a low molecular weight polyether macromonomer after capping the low molecular weight polyether macromonomer with carboxyl phosphoric acid.
In some embodiments, the carboxyphosphoric acid comprises at least one of 2-carboxyphenylphosphoric acid, 3-carboxyphenylphosphoric acid, 4-carboxyphenylphosphoric acid, 3-phosphorylpropionic acid.
Specifically, the chain transfer agent enables free radicals of the polyether macromonomer, the hydrophobic functional monomer, the unsaturated acid and the unsaturated ester to undergo free radical transfer, so that the relative molecular mass of the produced viscosity-reducing water reducer is controlled.
In some embodiments, the chain transfer agent is preferably sodium hypophosphite.
The harmless sodium hypophosphite meets the environment-friendly requirement more than the harmful sulfhydryl chain transfer agent.
In some embodiments, the unsaturated acid includes at least one of acrylic acid and methacrylic acid.
In some embodiments, the unsaturated ester comprises at least one of vinyl acetate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
The invention also provides a preparation method of the viscosity-reducing water reducer, which comprises the following steps:
100 to 200 parts of low molecular weight polyether macromonomer, 1 to 10 parts of hydrophobic functional monomer, 5 to 30 parts of unsaturated acid, 1 to 10 parts of unsaturated ester, 0.5 to 8 parts of initiator and water are placed in a reactor to carry out copolymerization reaction, and the reaction is finished to obtain the viscosity-reducing water reducer; the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
Specifically, the initiator is firstly decomposed to generate initiator free radicals, and the initiator free radicals are respectively transferred to a low molecular weight polyether macromonomer, a hydrophobic functional monomer, unsaturated acid and unsaturated ester to be subjected to polymerization under the environmental condition of solvent water, so that the viscosity-reducing water reducer is obtained. The viscosity-reducing water reducer is added into concrete, and in the cement hydration process in the concrete, ester groups in the low molecular weight polyether macromonomer and the unsaturated ester can be hydrolyzed to release functional groups (hydroxyl, phosphate and carboxyl), so that the viscosity-reducing water reducer has good dispersion retention property, and the prepared viscosity-reducing water reducer has good water reducing property.
In some embodiments, the method of preparing the viscosity reducing water reducer includes the steps of:
100 parts by weight of S100, 100-200 parts by weight of low molecular weight polyether macromonomer, 1-10 parts by weight of hydrophobic functional monomer, 2-8 parts by weight of chain transfer agent and water are placed in a reactor, and stirred and dissolved to obtain a first mixed solution.
Specifically, when the molecular weight of the polyether macromonomer is 500-1500, the prepared water reducer has small molecular weight and small quantity of adsorption and dispersion groups, and the adsorption and dispersion effects of water reducer molecules on cement particles are reduced, so that carboxyl phosphoric acid can be used for blocking a side chain of the water reducer molecules, the adsorption effect of phosphoric acid groups in the carboxyl phosphoric acid is strong, and the phosphoric acid groups are adsorbed on the surfaces of the cement particles in concrete to disperse the cement particles through electrostatic repulsion and steric hindrance, so that a thin and dense water film layer is formed, and the fluidity of the concrete is improved.
In some embodiments, the step of capping the low molecular weight polyether macromonomer with the carboxyphosphoric acid comprises:
and (3) placing the low molecular weight polyether macromonomer and carboxyl phosphoric acid into a first reactor to perform esterification reaction, and obtaining the phosphate end-capped low molecular weight polyether macromonomer after the reaction is finished.
Specifically, the preparation method of the phosphate end capped low molecular weight polyether macromonomer comprises the following specific steps:
adding a low molecular weight polyether macromonomer, carboxyl phosphoric acid, a first catalyst and a first polymerization inhibitor into a first reactor, and reacting for 6-12 hours at a constant temperature of 110-130 ℃ to obtain the low molecular weight polyether macromonomer.
Specifically, the first catalyst is added to accelerate the esterification reaction between the low molecular weight polyether macromonomer and the carboxyl phosphoric acid, and the catalysis effect of the first catalyst is optimal at 110-130 ℃.
The first polymerization inhibitor is added to avoid the polymerization of the esterification reaction of the low molecular weight polyether macromonomer and the carboxyl phosphoric acid.
In some embodiments, the first reactor is equipped with a condensing device to cool down the reactants after the phosphorylation reaction of the low molecular weight polyether macromonomer and the carboxyl group, which is convenient for subsequent preparation of the viscosity reducing water reducer.
In some embodiments, the temperature is reduced to 40 ℃ after the reaction is completed.
In some embodiments, the low molecular weight polyether macromonomer and the carboxyphosphoric acid can be protected with nitrogen to reduce byproducts of the esterification reaction of the low molecular weight polyether macromonomer and the carboxyphosphoric acid.
The molar ratio of the low molecular weight polyether macromonomer to the carboxyl phosphoric acid is (1.0-1.2): 1.
The first catalyst is used in an amount of 0.1 to 5% by mass of the low molecular weight polyether macromonomer.
The first polymerization inhibitor is used in an amount of 0.01 to 0.5 percent of the mass of the low molecular weight polyether macromonomer.
The first catalyst includes any one of concentrated sulfuric acid, heteropolyacid, stannous oxide and dibutyltin oxide.
The first polymerization inhibitor includes any one of para-hydroxyanisole, hydroquinone, para-tert-butylcatechol and phenothiazine.
S200, dropwise adding 5-30 parts of mixed solution of unsaturated acid and 1-10 parts of unsaturated ester, 0.5-3 parts of oxidant and 1-6 parts of reducing agent into the first mixed solution to carry out copolymerization reaction, and after the dropwise adding is finished, carrying out heat preservation reaction, and after the reaction is finished, obtaining a second mixed solution.
Further, the dripping time of the mixed solution of unsaturated acid and unsaturated ester, the oxidant and the reducing agent is preferably 1.5-3 h, the initial dripping temperature of the copolymerization reaction is preferably 20-40 ℃, and the time of the heat preservation reaction is preferably 0.5-1.5 h.
And S300, when the second mixed solution is cooled to room temperature, regulating the pH value of the second mixed solution to 6-7 by using alkali liquor, and obtaining the viscosity-reducing water reducer.
And adding alkali liquor to adjust the pH value of the viscosity-reducing water reducer to 5-7, so that the stability of the viscosity-reducing water reducer can be improved.
The lye is preferably any one of a 30wt.% sodium hydroxide solution, a 30wt.% calcium hydroxide solution and a 30wt.% barium hydroxide solution.
Specifically, the molecular weight of the low molecular weight polyether macromonomer is 500 to 1500.
In some embodiments, the method of preparing the hydrophobic functional monomer includes the steps of:
placing unsaturated acid hydroxyalkyl ester and fatty diacid monomethyl ester in a second reactor to perform esterification reaction, and obtaining the hydrophobic functional monomer after the reaction is finished.
Specifically, the preparation method of the hydrophobic functional monomer comprises the following specific steps:
adding unsaturated acid hydroxyalkyl ester, fatty diacid monomethyl ester, a catalyst and a polymerization inhibitor into a second reactor to perform esterification reaction, and performing constant-temperature reaction for 6-12 h at 110-130 ℃ to obtain the hydrophobic functional monomer after the reaction is finished.
In some embodiments, the unsaturated hydroxyalkyl acid esters include at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, methyl 2- (hydroxymethyl) acrylate, and 2-hydroxypropyl methacrylate.
In some embodiments, the fatty diacid monomethyl ester comprises at least one of 2-nitroterephthalic acid monomethyl ester, sebacic acid monomethyl ester, dodecanedioic acid monomethyl ester, malonic acid monomethyl ester, β -methylpentanedioic acid monomethyl ester, glutaric acid monomethyl ester, succinic acid monomethyl ester, suberic acid monomethyl ester, azelaic acid monomethyl ester, adipic acid monomethyl ester.
Wherein the molar ratio of the unsaturated acid hydroxyalkyl ester to the fatty diacid monomethyl ester is (1.0-1.2): 1.
Specifically, the second catalyst is added to accelerate the esterification reaction between unsaturated acid hydroxyalkyl ester and fatty diacid monomethyl ester, and the catalysis effect of the second catalyst is optimal at 110-130 ℃.
The addition of the second polymerization inhibitor can avoid the occurrence of the polymerization explosion in the esterification reaction of the unsaturated acid hydroxyalkyl ester and the fatty diacid monomethyl ester.
The second catalyst is used in an amount of 0.1 to 5% by mass of the unsaturated acid hydroxyalkyl ester.
The second polymerization inhibitor is used in an amount of 0.01 to 0.5 percent based on the mass of the unsaturated acid hydroxyalkyl ester.
The second catalyst includes any one of concentrated sulfuric acid, heteropolyacid, stannous oxide and dibutyltin oxide.
The second polymerization inhibitor comprises any one of para-hydroxyanisole, hydroquinone, para-tertiary butyl catechol and phenothiazine.
In some embodiments, the temperature is reduced to 40 ℃ after the reaction is completed.
In some embodiments, nitrogen may be used to protect the molecular weight unsaturated acid hydroxyalkyl esters and fatty diacid monomethyl esters, reducing byproducts of the esterification reaction of the unsaturated acid hydroxyalkyl esters and fatty diacid monomethyl esters.
1. Preparation of low molecular weight polyether macromonomer A
1. Preparation of low molecular weight polyether macromonomer A1:
adding 0.11mol of isopentenyl polyoxyethylene ether-1200, 0.1mol of 3-carboxyphenyl phosphoric acid, 0.5 mass percent of concentrated sulfuric acid and 0.05 mass percent of para-hydroxyanisole into a first reactor provided with a condensing device, keeping the temperature at 120 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished, thus obtaining the low molecular weight polyether macromonomer A1.
2. Preparation of low molecular weight polyether macromonomer A2:
adding 0.11mol of isopentenyl polyoxyethylene ether-800, 0.1mol of 3-phosphoryl propionic acid, 0.5 mass percent of concentrated sulfuric acid and 0.05 mass percent of tertiary butyl catechol into a first reactor provided with a condensing device, keeping the temperature at 120 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished, thus obtaining the low molecular weight polyether macromonomer A2.
3. Preparation of low molecular weight polyether macromonomer A3:
adding 0.11mol of methyl allyl polyoxyethylene ether-1500, 0.1mol of 2-carboxyphenyl phosphoric acid, 0.4 mass percent of dibutyl tin oxide and 0.05 mass percent of phenothiazine into a first reactor provided with a condensing device, keeping the temperature at 120 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished, thus obtaining the low molecular weight polyether macromonomer A3.
2. Preparation of hydrophobic monomer B
1. Preparation of hydrophobic monomer B1
0.10mol of monomethyl sebacate, 0.11mol of hydroxyethyl acrylate, 0.5 mass percent of dibutyl tin oxide and 0.05 mass percent of phenothiazine are added into a first reactor provided with a condensing device, the temperature is kept constant for 6 hours at 120 ℃ under the protection of nitrogen, and the temperature is reduced to 40 ℃ after the reaction is finished, so that the hydrophobic monomer B1 is obtained.
2. Preparation of hydrophobic monomer B2
Adding 0.10mol of monomethyl glutarate, 0.12mol of hydroxyethyl methacrylate, 0.6 mass percent of concentrated sulfuric acid and 0.05 mass percent of phenothiazine into a first reactor provided with a condensing device, keeping the temperature at 120 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain the hydrophobic monomer B2.
3. Preparation of hydrophobic monomer B3
0.10mol of methyl hydrogen adipate, 0.11mol of 3-chloro-2-hydroxypropyl methacrylate, 0.5 mass percent of stannous oxide and 0.05 mass percent of p-tert-butyl catechol are added into a first reactor provided with a condensing device, the temperature is kept at 120 ℃ for 6 hours under the protection of nitrogen, and the temperature is reduced to 40 ℃ after the reaction is finished, so that the hydrophobic monomer B3 is obtained.
3. Preparation of viscosity-reducing water reducer
Example 1
200 parts of phosphoric acid end-capped low molecular weight ether macromonomer A1, 4 parts of hydrophobic functional monomer B1, 3 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, 20 parts of mixed solution of acrylic acid and 2 parts of vinyl acetate, 1 part of ascorbic acid solution and 3 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is regulated to 20-40 ℃ for reaction, the dropwise addition time is 1.5-3 h, the temperature is kept for 0.5-1.5 h after the dropwise addition, the temperature is reduced to room temperature after the reaction is finished, and the pH is regulated to 6-7 by liquid alkali, thus obtaining the viscosity-reducing water reducer.
Example 2
200 parts of phosphoric acid end-capped low molecular weight ether macromonomer A2, 4 parts of hydrophobic functional monomer B2, 3.5 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, 20 parts of mixed solution of acrylic acid and 2 parts of ethyl acrylate, 1 part of sodium formaldehyde sulfoxylate and 2.5 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is regulated to 20-40 ℃ for reaction, the dropwise addition time is 1.5-3 h, the temperature is kept for 0.5-1.5 h after the dropwise addition is finished, the temperature is reduced to room temperature after the reaction is finished, and the pH is regulated to 6-7 by liquid alkali, thus obtaining the viscosity-reducing water reducer.
Example 3
200 parts of phosphoric acid end-capped low molecular weight ether macromonomer A3, 4 parts of hydrophobic functional monomer B2, 4 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, 24 parts of mixed solution of acrylic acid and 2 parts of vinyl acetate, 1 part of Bruggolite FF6 and 2.5 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is regulated to 20-40 ℃ for reaction, the dropwise adding time is 1.5-3 h, the temperature is kept for 0.5-1.5 h after the dropwise adding is finished, the temperature is reduced to room temperature after the reaction is finished, and the pH is regulated to 6-7 by liquid alkali, thus obtaining the viscosity-reducing water reducer.
Example 4
200 parts of phosphoric acid end-capped low molecular weight ether macromonomer A3, 4 parts of hydrophobic functional monomer B3, 4 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, 24 parts of mixed solution of acrylic acid and 2 parts of glycidyl methacrylate, 1 part of ascorbic acid solution and 2.5 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is regulated to 20-40 ℃ for reaction, the dropwise addition time is 1.5-3 h, the temperature is kept for 0.5-1.5 h after the dropwise addition is finished, the temperature is reduced to room temperature after the reaction is finished, and the pH is regulated to 6-7 by liquid alkali, thus obtaining the viscosity-reducing water reducer.
Comparative example 1
200 parts of isopentenyl polyoxyethylene ether-2400, 4 parts of hydrophobic functional monomer B1, 3 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, 20 parts of mixed solution of acrylic acid and 2 parts of vinyl acetate, 1 part of ascorbic acid solution and 3 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is regulated to 20-40 ℃ for reaction, the dropwise addition time is 1.5-3 h, the temperature is kept for 0.5-1.5 h after the dropwise addition, the temperature is reduced to room temperature after the reaction is finished, and the pH value is regulated to 6-7 by liquid alkali, thus obtaining the water reducer.
Comparative example 2
200 parts of isopentenyl polyoxyethylene ether-2400, 3 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, 20 parts of mixed solution of acrylic acid and 2 parts of vinyl acetate, 1 part of ascorbic acid solution and 3 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is regulated to 20-40 ℃ for reaction, the dropwise adding time is 1.5-3 h, the temperature is kept for 0.5-1.5 h after the dropwise adding is finished, the temperature is reduced to room temperature after the reaction is finished, and the pH value is regulated to 6-7 by liquid alkali, thus obtaining the water reducer.
Comparative example 3
200 parts of methyl allyl polyoxyethylene ether, 4 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 24 parts of acrylic acid and 2 parts of vinyl acetate and 1 part of BrUggolit are added into the reactor in a dropwise manner TM FF6,2.5 parts of hydrogen peroxide solution, regulating the temperature to 20-40 ℃ for reaction, dripping for 1.5-3 h, preserving heat for 0.5-1.5 h after dripping, cooling to room temperature after reaction, and regulating with liquid caustic sodaAnd (5) adjusting the pH to 6-7 to obtain the water reducing agent.
GPC (gel permeation chromatography) tests were carried out on the viscosity-reducing water reducers of examples 1 to 4 and the water reducers of comparative examples 1 to 3, and the test results are shown in Table 1.
When the mixing amount of the water reducer is adjusted by adopting red lion cement to ensure that the expansion degree of the concrete is 650+/-30 mm, the performances of the water reducer with different molecular weights, such as initial slump and 1h slump, initial slump and 1h expansion degree, emptying time of a 0h inverted slump barrel, compressive strength of each age and the like, of the concrete are tested according to GB 8076-2008 concrete admixture.
The concrete mixing ratio is as follows: cement 380kg/m 3 80kg/m of fly ash 3 50kg/m of mineral powder 3 750kg/m of sand 3 980kg/m stone 3 145kg/m of water 3 。
The concrete test results are shown in table 2.
TABLE 1 GPC test results
| Sample of | Mn | Mw | PDI | Conversion rate |
| Comparative example 1 | 31918 | 75202 | 1.89 | 88.65 |
| Comparative example 2 | 35912 | 74461 | 1.99 | 87.29 |
| Comparative example 3 | 31270 | 62723 | 2.14 | 86.77 |
| Example 1 | 25459 | 41183 | 1.91 | 87.75 |
| Example 2 | 29270 | 42723 | 1.87 | 88.77 |
| Example 3 | 22140 | 39870 | 1.69 | 91.28 |
| Example 4 | 22201 | 38255 | 1.73 | 92.95 |
Table 2 results of concrete performance test
The results in Table 1 show that both Mn (weight average molecular weight) and Mw (number average molecular weight) of the viscosity-reducing water reducer prepared by the invention are lower than those of the viscosity-reducing water reducer prepared by using a conventional 2400-molecular-weight macromer, which shows that the viscosity-reducing water reducer prepared by the invention is successful.
Comparative example 1 the phosphoric acid-terminated low molecular weight ether macromer (isopentenyl polyoxyethylene ether-1200) was replaced with isopentenyl polyoxyethylene ether-2400 relative to example 1, and as can be seen from the data of example 1 and comparative example 1 in table 2, the dosage and evacuation time of example 1 were both lower than those of comparative example 1, indicating that the introduction of the low molecular weight ether macromer was beneficial to improving the fluidity of concrete, and the viscosity-reducing water reducer prepared had good viscosity-reducing properties.
The results in Table 2 show that comparative example 2 does not incorporate a hydrophobic functional monomer, and that the viscosity of the concrete is higher, indicating that the incorporation of a hydrophobic monomer is beneficial for improving the viscosity of the slurry.
The mixing amount and the emptying time of the examples 1-4 are lower than those of the comparative examples 1-3, which shows that the special low molecular weight water reducer for the high-strength concrete prepared by the invention has better dispersibility and dispersion retention property, and the fluidity of the concrete is greatly improved.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. The viscosity-reducing water reducer is characterized by comprising the following raw materials in parts by weight:
the molecular weight of the low molecular weight polyether macromonomer is 500-1500;
the low molecular weight polyether macromonomer comprises at least one of methallyl polyoxyethylene and isopentenyl polyoxyethylene ether;
the preparation raw materials of the viscosity-reducing water reducer comprise the following components in parts by weight:
2-8 parts of chain transfer agent and carboxyl phosphoric acid;
the mol ratio of the low molecular weight polyether macromonomer to the carboxyl phosphoric acid is (1.0-1.2) 1;
the preparation method of the low molecular weight polyether macromonomer comprises the following steps:
and placing the low molecular weight polyether macromonomer and carboxyl phosphoric acid into a first reactor for esterification reaction, and obtaining the phosphate end-capped low molecular weight polyether macromonomer after the reaction is finished.
2. The viscosity reducing water reducing agent of claim 1, wherein the initiator comprises, in parts by weight:
0.5-3 parts of oxidant;
1-6 parts of reducing agent.
3. The viscosity reducing water reducing agent of claim 1, wherein the unsaturated acid comprises at least one of acrylic acid and methacrylic acid.
4. The viscosity reducing water reducing agent of claim 1, wherein the unsaturated esters comprise at least one of vinyl acetate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
5. A method for preparing the viscosity-reducing water reducer according to claim 1, comprising the steps of:
according to parts by weight, placing 100-200 parts of low molecular weight polyether macromonomer, 1-10 parts of hydrophobic functional monomer, 5-30 parts of unsaturated acid, 1-10 parts of unsaturated ester, 0.5-8 parts of initiator and water into a reactor for copolymerization reaction, and obtaining the viscosity-reducing water reducer after the reaction is finished; the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
6. The method for preparing the viscosity-reducing water reducer according to claim 5, comprising the steps of:
100-200 parts of the low molecular weight polyether macromonomer, 1-10 parts of the hydrophobic functional monomer, 2-8 parts of chain transfer agent and water are placed in a reactor according to parts by weight, and stirred and dissolved to obtain a first mixed solution;
dropwise adding 5-30 parts of mixed solution of unsaturated acid and 1-10 parts of unsaturated ester, 0.5-3 parts of oxidant and 1-6 parts of reducing agent into the first mixed solution to carry out copolymerization reaction, and after the dropwise adding is finished, carrying out heat preservation reaction to obtain a second mixed solution after the reaction is finished;
and (3) after the second mixed solution is cooled to room temperature, regulating the pH value of the second mixed solution to 6-7 by using alkali liquor, and obtaining the viscosity-reducing water reducer.
7. The method for preparing a viscosity-reducing water reducer according to claim 5, wherein the method for preparing the hydrophobic functional monomer comprises the steps of:
placing unsaturated acid hydroxyalkyl ester and fatty diacid monomethyl ester in a second reactor to perform esterification reaction, and obtaining the hydrophobic functional monomer after the reaction is finished.
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| CN112708055A (en) * | 2020-10-30 | 2021-04-27 | 科之杰新材料集团(贵州)有限公司 | Ester ether copolymerization viscosity-reducing hydration regulator and preparation method thereof |
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