CN108192039B - Rapid hardening super early strength polycarboxylate superplasticizer and preparation method thereof - Google Patents
Rapid hardening super early strength polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN108192039B CN108192039B CN201711468708.XA CN201711468708A CN108192039B CN 108192039 B CN108192039 B CN 108192039B CN 201711468708 A CN201711468708 A CN 201711468708A CN 108192039 B CN108192039 B CN 108192039B
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- deionized water
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 36
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000178 monomer Substances 0.000 claims abstract description 54
- -1 unsaturated alcohol amine ester Chemical class 0.000 claims abstract description 50
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 25
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000001488 sodium phosphate Substances 0.000 claims description 17
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 17
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 17
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 17
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 230000003111 delayed effect Effects 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 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 5
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 5
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 5
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 5
- HVCNQTCZNBPWBV-UHFFFAOYSA-N 2-hydroxy-2-sulfinoacetic acid Chemical compound OC(=O)C(O)S(O)=O HVCNQTCZNBPWBV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- CEFDWZDNAJAKGO-UHFFFAOYSA-N 2-hydroxy-2-sulfoacetic acid Chemical compound OC(=O)C(O)S(O)(=O)=O CEFDWZDNAJAKGO-UHFFFAOYSA-N 0.000 claims description 3
- ZHUWXKIPGGZNJW-UHFFFAOYSA-N 6-methylheptyl 3-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)CCS ZHUWXKIPGGZNJW-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- PUAHIVMZATZOHW-UHFFFAOYSA-L OC(C(=O)[O-])S(=O)O.[Na+].[Na+].OC(C(=O)[O-])S(=O)O Chemical compound OC(C(=O)[O-])S(=O)O.[Na+].[Na+].OC(C(=O)[O-])S(=O)O PUAHIVMZATZOHW-UHFFFAOYSA-L 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- IMLUMMDFXRZWGY-UHFFFAOYSA-L disodium 2-hydroxy-2-sulfoacetate Chemical compound [Na+].[Na+].[O-]C(=O)C(O)S(O)(=O)=O.[O-]C(=O)C(O)S(O)(=O)=O IMLUMMDFXRZWGY-UHFFFAOYSA-L 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- 125000005394 methallyl group Chemical group 0.000 claims description 3
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940035024 thioglycerol Drugs 0.000 claims description 3
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 2
- 239000004567 concrete Substances 0.000 abstract description 20
- 239000004568 cement Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000009415 formwork Methods 0.000 abstract description 6
- 238000006703 hydration reaction Methods 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 230000007306 turnover Effects 0.000 abstract description 3
- 238000005520 cutting process Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 101000908015 Homo sapiens Putative inactive carboxylesterase 4 Proteins 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 102100023322 Putative inactive carboxylesterase 4 Human genes 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- INRFMNKGJCROAZ-UHFFFAOYSA-N 2-hydroxy-2-sulfinylacetic acid Chemical compound OC(=O)C(O)=S=O INRFMNKGJCROAZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KLSBASGQHCAVHQ-UHFFFAOYSA-L disodium;2-hydroxy-2-sulfinatoacetate Chemical compound [Na+].[Na+].[O-]C(=O)C(O)S([O-])=O KLSBASGQHCAVHQ-UHFFFAOYSA-L 0.000 description 1
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 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
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
- C04B24/2658—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles containing polyether side chains
-
- 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
- C08F2/00—Processes of polymerisation
-
- 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)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a rapid hardening super early strength polycarboxylate superplasticizer and a preparation method thereof. The quick-hardening and super-early-strength polycarboxylate water reducer prepared by the invention designs molecular structures such as main and side chain groups and the like by a molecular cutting technology, adopts a polyether monomer with ultrahigh molecular weight as an active macromonomer, leads the molecular chain to form a structure with long side chains and short main chains, introduces a self-made small monomer of unsaturated alcohol amine ester, a small monomer containing N groups such as dimethylaminoethyl methacrylate and triacrylate, and the like with an early-strength function, and carries out solution polymerization at room temperature, so that the synthesized water reducer has an outstanding function of promoting cement hydration reaction, is applied to steam-cured concrete, low-temperature environment concrete and concrete with an early formwork removal requirement, can obviously shorten the plastering and initial setting time of a forming formwork, has an obvious early-strength effect, can accelerate the construction progress of the concrete, and improves the turnover rate of the formwork.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a rapid-hardening and super-early-strength polycarboxylate superplasticizer and a preparation method thereof.
Background
The polycarboxylate superplasticizer has the characteristics of high water reducing rate, high slump retention, low alkali, environmental protection and the like, and is widely applied to concrete engineering. However, the early strength of the common polycarboxylic acid water reducing agent is slowly developed, and particularly under the low-temperature condition, the common polycarboxylic acid water reducing agent is limited to be used in winter construction and cold environment, and the use of the common polycarboxylic acid water reducing agent in prefabricated parts is also limited. In order to improve the production efficiency of prefabricated parts and accelerate the turnover rate of templates, the polycarboxylate superplasticizer is required to have good water reducing and dispersing effects, and is also required to shorten the setting time of concrete and improve the early strength. Therefore, the development of the early-strength polycarboxylate superplasticizer has obvious technical and economic benefits. The technical approaches for realizing the quick setting and early strength functions of the polycarboxylate superplasticizer are two types: one is that the synthetic polymer has good quick-setting early strength performance, and the other is that the conventional polycarboxylic acid water reducing agent is synthesized, and the quick-setting early strength effect is achieved through compounding.
For a compound type early strength water reducing agent, a related report is provided, wherein CN 101289292A is prepared by compounding preferable early strength components such as triethanolamine, sodium thiocyanate, calcium nitrate and the like on the basis of a graft copolymerization polycarboxylic acid polymer, wherein the copolymerization polycarboxylic acid polymer is obtained by polymerizing methoxy polyethylene glycol acrylate and acrylic acid/methacrylic acid in an aqueous medium through a free radical initiator. CN1312324A is prepared by compounding 30-100 parts of modified waste polystyrene water reducing agent with 20-98 mol% of sulfonic acid group content, 5-20 parts of sodium sulfate and 40-70 parts of lignosulfonate. When the folded solid content is about 6%, the water reducing rate is 20-28%, and the ld compressive strength is improved by 41-48%. CN101024565A discloses an early strength composite water reducing agent obtained by compounding early strength components such as anhydrous calcium chloride, triethanolamine, sodium benzoate and the like, which can improve the compressive strength to a certain extent, but does not mention whether the early strength composite water reducing agent has a quick setting effect, contains chlorine salt and is rusted to reinforced concrete;
CN105199032A discloses a super early strength polycarboxylate superplasticizer, which is synthesized by taking various active macromonomers as raw materials, and cations are introduced into molecules, so that the adsorption of soil to an additive is reduced, the hydration of cement can be accelerated, the super early strength polycarboxylate superplasticizer has a super early strength effect, the polymerization temperature is 85-95 ℃, the temperature is higher, the super early strength superplasticizer is difficult to control, and the characteristic that a 4-hydroxybutyl vinyl polyoxyethylene ether macromonomer is easy to decompose at higher temperature is not considered. CN101357834B discloses an early strength type polycarboxylic acid plasticizer, which is prepared by copolymerizing methoxy polyethylene glycol carboxylic acid ester macromonomers with different molecular weights, (methyl) acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and random/block ether in an aqueous solution at 60-90 ℃.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a rapid-hardening and super-early-strength polycarboxylate superplasticizer.
The invention also aims to provide a preparation method of the rapid hardening and super early strength polycarboxylate superplasticizer.
The technical scheme of the invention is as follows:
a quick-hardening super-early-strength polycarboxylate superplasticizer is prepared from the following raw materials in parts by weight: 180-230 parts of polyether monomer with the molecular weight of 5000-6000, 15-19 parts of unsaturated monocarboxylic acid or derivative thereof, 5-12 parts of unsaturated alcohol amine ester small monomer, 2-5 parts of dimethylaminoethyl methacrylate, 2-5 parts of triallylamine, 0.7-2.0 parts of oxidant, 0.2-0.6 part of reducing agent, 0.6-1.2 parts of chain transfer agent, 14-18 parts of 32wt% sodium hydroxide aqueous solution, 1-5 parts of trisodium phosphate and a proper amount of deionized water, wherein the amount of the deionized water enables the solid content of the rapid-hardening super-early-strength polycarboxylic acid water reducer to reach 45-55%; the unsaturated alcohol amine ester small monomer is prepared by carrying out esterification reaction on acrylic acid and N, N-diethylethanolamine at a molar ratio of 2: 1-1.5 under the catalysis of phosphorous acid at 105-115 ℃, the polyether monomer is at least one of allyl polyoxyethylene polyether, methallyl polyoxyethylene polyether and isopentenol polyoxyethylene ether, the unsaturated monocarboxylic acid or derivative is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, acrylamide and methacrylamide, and the polyether monomer is used as a monomer.
In a preferred embodiment of the present invention, the preparation method of the unsaturated alcohol amine ester small monomer comprises the following steps:
(1) adding acrylic acid and N, N-diethylethanolamine into a reaction vessel provided with a condensing device;
(2) injecting nitrogen while stirring, heating to 55-60 ℃, adding p-phenylenediamine, and stirring for 20-30 min, wherein the p-phenylenediamine accounts for 1.0-1.5% of the total mass of the acrylic acid and the N, N-diethylethanolamine;
(3) continuously heating to 105-115 ℃, adding phosphorous acid, and reacting for 3-5 h at constant temperature, wherein the phosphorous acid accounts for 1.0-1.2% of the total amount of acrylic acid and N, N-diethylethanolamine;
(4) and after the reaction is stopped, carrying out reduced pressure distillation to obtain unreacted acrylic acid, thus obtaining the unsaturated alcohol amine ester small monomer.
In a preferred embodiment of the present invention, the oxidizing agent is at least one of ammonium persulfate, potassium persulfate, sodium persulfate, and hydrogen peroxide.
In a preferred embodiment of the present invention, the chain transfer agent is at least one of thioglycolic acid, mercaptoethanol, 3-mercaptopropionic acid, thioglycerol, isooctyl 3-mercaptopropionate, trisodium phosphate, dodecyl mercaptan, and thiomalic acid.
In a preferred embodiment of the present invention, the reducing agent is at least one of 2-hydroxy-2-sulfinato acetic acid, disodium 2-hydroxy-2-sulfinato acetic acid, 2-hydroxy-2-sulfonato acetic acid and disodium 2-hydroxy-2-sulfonato acetic acid.
The preparation method of the rapid hardening and super early strength polycarboxylate superplasticizer comprises the following steps:
(1) weighing the raw material components in parts by weight;
(2) dissolving unsaturated monocarboxylic acid or a derivative thereof in 10-15 parts by weight of deionized water to obtain a first solution; dissolving a reducing agent in 25-30 parts by weight of deionized water to obtain a second solution; dissolving a chain transfer agent in 25-30 parts by weight of deionized water to obtain a third solution;
(3) adding a polyether monomer, an unsaturated alcohol amine ester small monomer, dimethylaminoethyl methacrylate, triallylamine, an oxidant and the rest deionized water into a reaction vessel, and stirring at room temperature until the polyether monomer, the unsaturated alcohol amine ester small monomer, the dimethylaminoethyl methacrylate, the triallylamine, the oxidant and the rest deionized water are dissolved;
(4) simultaneously dropwise adding the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the dropwise adding is finished within 2-5 h, the dropwise adding of the second solution is delayed by 10-20 min compared with that of the first solution, the dropwise adding of the third solution is delayed by 10-30 min compared with that of the first solution, and after the dropwise adding is finished, the heat preservation reaction is carried out for 1-3 h;
(5) and (3) adding 1-5 parts by weight of trisodium phosphate into the material obtained in the step (4), and adjusting the pH value to 6.0-6.5 by using a proper amount of 32wt% sodium hydroxide aqueous solution to obtain the rapid hardening and super early strength polycarboxylate superplasticizer.
The invention has the beneficial effects that:
1. the quick-hardening and super-early-strength polycarboxylate water reducer prepared by the invention designs molecular structures such as main and side chain groups and the like by a molecular cutting technology, adopts a polyether monomer with ultrahigh molecular weight as an active macromonomer, leads the molecular chain to form a structure with long side chains and short main chains, introduces a self-made small monomer of unsaturated alcohol amine ester, a small monomer containing N groups such as dimethylaminoethyl methacrylate and triacrylate, and the like with an early-strength function, and carries out solution polymerization at room temperature, so that the synthesized water reducer has an outstanding function of promoting cement hydration reaction, is applied to steam-cured concrete, low-temperature environment concrete and concrete with an early formwork removal requirement, can obviously shorten the plastering and initial setting time of a forming formwork, has an obvious early-strength effect, can accelerate the construction progress of the concrete, and improves the turnover rate of the formwork.
2. The preparation method of the invention is completely carried out at normal pressure and normal temperature, and has simple operation and short production period
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
The preparation method of the unsaturated alcohol amine ester small monomer in the following embodiment comprises the following steps:
(1) adding acrylic acid and N, N-diethylethanolamine into a reaction vessel provided with a condensing device according to the mol ratio of 2.0: 1.2;
(2) injecting nitrogen while stirring, heating to 55 ℃, adding p-phenylenediamine, and stirring for 20min, wherein the p-phenylenediamine accounts for 1.0 percent of the total mass of the acrylic acid and the N, N-diethylethanolamine;
(3) continuously heating to 110 ℃, adding phosphorous acid, and reacting for 4 hours at constant temperature, wherein the phosphorous acid accounts for 1.2% of the total amount of the acrylic acid and the N, N-diethylethanolamine;
(4) and after the reaction is stopped, carrying out reduced pressure distillation to obtain unreacted acrylic acid, thus obtaining the unsaturated alcohol amine ester small monomer.
Example 1
(1) Weighing the following raw material components in parts by weight: 200 parts of allyl polyoxyethylene polyether with the molecular weight of 5000, 15 parts of acrylic acid, 4 parts of hydroxyethyl acrylate, 5 parts of unsaturated alcohol amine ester small monomer, 2 parts of dimethylamino ethyl methacrylate, 2 parts of triallylamine, 1.5 parts of ammonium persulfate, 0.2 part of 2-hydroxy-2-sulfinyl acetic acid, 0.6 part of thioglycolic acid, 14 parts of 32wt% sodium hydroxide aqueous solution, 1 part of trisodium phosphate and the balance of water, and the solid content is adjusted to 50%.
(2) Dissolving acrylic acid and hydroxyethyl acrylate in 15 parts by weight of deionized water to obtain a first solution; dissolving 2-hydroxy-2-sulfinato acetic acid in 30 parts by weight of deionized water to obtain a second solution; dissolving thioglycolic acid in 30 parts by weight of deionized water to obtain a third solution;
(3) adding allyl polyoxyethylene polyether, unsaturated alcohol amine ester small monomer, dimethylaminoethyl methacrylate, triallylamine, ammonium persulfate and the rest deionized water into a four-neck flask, and stirring at room temperature until the allyl polyoxyethylene polyether, the unsaturated alcohol amine ester small monomer, the dimethylaminoethyl methacrylate, the triallylamine, the ammonium persulfate and the rest deionized water are dissolved;
(4) simultaneously dropwise adding the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the dropwise adding of the first solution is completed within 2 hours, the dropwise adding time of the first solution is 100min, the dropwise adding time of the second solution is 110min, the dropwise adding time of the third solution is 120min, and after the dropwise adding is completed, the heat preservation reaction is carried out for 1 hour;
(5) and after the heat preservation is finished, adding trisodium phosphate, and then adjusting the pH value to 6.5 by using a 32wt% sodium hydroxide aqueous solution to obtain the rapid hardening and super early strength polycarboxylate superplasticizer PCE-1.
Example 2
(1) Weighing the following raw material components in parts by weight: 180 parts of methyl allyl polyoxyethylene polyether with the molecular weight of 5500, 12 parts of methacrylic acid, 5 parts of hydroxypropyl acrylate, 6 parts of unsaturated alcohol amine ester small monomer, 3 parts of dimethylaminoethyl methacrylate, 5 parts of triallylamine, 1.7 parts of potassium persulfate, 0.4 part of disodium 2-hydroxy-2-sulfinyl acetate, 0.8 part of mercaptoethanol, 15 parts of 32wt% sodium hydroxide aqueous solution, 3 parts of trisodium phosphate and the balance of water, and the solid content is adjusted to 50%.
(2) Dissolving methacrylic acid and hydroxypropyl acrylate in 15 parts by weight of deionized water to obtain a first solution; dissolving disodium 2-hydroxy-2-sulfinato acetate in 30 parts by weight of deionized water to obtain a second solution; dissolving mercaptoethanol in 30 parts by weight of deionized water to obtain a third solution;
(3) adding methyl allyl polyoxyethylene polyether, unsaturated alcohol amine ester small monomer, dimethylaminoethyl methacrylate, triallylamine, potassium persulfate and the rest deionized water into a four-neck flask, and stirring at room temperature until the methyl allyl polyoxyethylene polyether, the unsaturated alcohol amine ester small monomer, the dimethylaminoethyl methacrylate, the triallylamine, the potassium persulfate and the rest deionized water are dissolved;
(4) simultaneously dropwise adding the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the dropwise adding of the first solution is finished within 3 hours, the dropwise adding time of the first solution is 150min, the dropwise adding time of the second solution is 170min, the dropwise adding time of the third solution is 180min, and after the dropwise adding is finished, the heat preservation reaction is carried out for 1.5 hours;
(5) and after the heat preservation is finished, adding trisodium phosphate, and then adjusting the pH value to 6.0 by using a 32wt% sodium hydroxide aqueous solution to obtain the rapid hardening and super early strength polycarboxylate superplasticizer PCE-2.
Example 3
(1) Weighing the following raw material components in parts by weight: 230 parts of prenyl alcohol polyoxyethylene ether with the molecular weight of 5000, 10 parts of acrylic acid, 8 parts of hydroxypropyl methacrylate, 10 parts of unsaturated alcohol amine ester small monomer, 4 parts of dimethylaminoethyl methacrylate, 4 parts of triacrylate, 1.8 parts of sodium persulfate, 0.6 part of 2-hydroxy-2-sulfonic acid acetic acid, 1.0 part of 3-mercaptopropionic acid, 16 parts of 32wt% sodium hydroxide aqueous solution, 2 parts of trisodium phosphate and the balance of water, and the solid content is adjusted to 50%.
(2) Dissolving acrylic acid and hydroxypropyl methacrylate in 15 parts by weight of deionized water to obtain a first solution; dissolving 2-hydroxy-2-sulfonic acid acetic acid in 30 parts by weight of deionized water to obtain a second solution; dissolving 3-mercaptopropionic acid in 30 parts by weight of deionized water to obtain a third solution;
(3) adding prenol polyoxyethylene ether, unsaturated alcohol amine ester small monomer, dimethylaminoethyl methacrylate, triallylamine, sodium persulfate and the rest deionized water into a four-neck flask, and stirring at room temperature until the prenol polyoxyethylene ether, the unsaturated alcohol amine ester small monomer, the dimethylaminoethyl methacrylate, the triallylamine, the sodium persulfate and the rest deionized water are dissolved;
(4) simultaneously dropwise adding the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the dropwise adding of the first solution is completed within 4 hours, the dropwise adding time of the first solution is 220min, the dropwise adding time of the second solution is 230min, the dropwise adding time of the third solution is 240min, and after the dropwise adding is completed, the heat preservation reaction is carried out for 2 hours;
(5) and after the heat preservation is finished, adding trisodium phosphate, and adjusting the pH value to 6.5 by using a 32wt% sodium hydroxide aqueous solution to obtain the rapid hardening and super early strength polycarboxylate superplasticizer PCE-3.
Example 4
(1) Weighing the following raw material components in parts by weight: 210 parts of methyl allyl polyoxyethylene polyether with molecular weight of 6000, 10 parts of methacrylic acid, 6 parts of acrylamide, 12 parts of unsaturated alcohol amine ester small monomer, 5 parts of dimethylaminoethyl methacrylate, 3 parts of triallylamine, 2.0 parts of hydrogen peroxide, 0.5 part of 2-hydroxy-2-sulfonic acid disodium salt, 1.2 parts of dodecyl mercaptan, 18 parts of 32wt% sodium hydroxide aqueous solution, 5 parts of trisodium phosphate and the balance of water, and the solid content is adjusted to 50%.
(2) Dissolving methacrylic acid and acrylamide in 15 parts by weight of deionized water to obtain a first solution; dissolving 2-hydroxy-2-sulfonic acid disodium acetate in 30 parts by weight of deionized water to obtain a second solution; dissolving dodecyl mercaptan in 30 parts by weight of deionized water to obtain a third solution;
(3) adding methyl allyl polyoxyethylene polyether, unsaturated alcohol amine ester small monomer, dimethylaminoethyl methacrylate, triallylamine, hydrogen peroxide and the rest deionized water into a four-neck flask, and stirring at room temperature until the methyl allyl polyoxyethylene polyether, the unsaturated alcohol amine ester small monomer, the dimethylaminoethyl methacrylate, the triallylamine, the hydrogen peroxide and the rest deionized water are dissolved;
(4) simultaneously dropwise adding the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the dropwise adding of the first solution is completed within 5 hours, the dropwise adding time of the first solution is 280min, the dropwise adding time of the second solution is 300min, the dropwise adding time of the third solution is 300min, and after the dropwise adding is completed, the heat preservation reaction is carried out for 3 hours;
(5) and after the heat preservation is finished, adding trisodium phosphate, and then adjusting the pH value to 6.0 by using a 32wt% sodium hydroxide aqueous solution to obtain the rapid hardening and super early strength polycarboxylate superplasticizer PCE-4.
Comparison of Performance
The rapid hardening and super early strength polycarboxylate superplasticizer provided in embodiments 1 to 4 of the invention is subjected to a net slurry fluidity test according to relevant standards specified in GB/T8077-2012 "concrete admixture homogeneity test method", wherein the cement is conch cement 52.5, the comparison sample is a product of a certain famous foreign company, the code is PCE-0, and the detection results are shown in the following table:
TABLE 1 clean pulp test results
| Classes of water reducing agents | Solid content/%) | Anchoring proportion/% of | Neat paste fluidity/mm |
| PCE-0 | 45 | 0.13 | 220 |
| PCE-1 | 50 | 0.13 | 255 |
| PCE-2 | 50 | 0.13 | 256 |
| PCE-3 | 50 | 0.13 | 264 |
| PCE-4 | 50 | 0.13 | 253 |
The concrete is prepared from cement, flyash, mineral powder, sand, stone and water in a mixing ratio of 315: 58: 41: 669: 1189: 138. Wherein: the cement is conch P.O 52.5.5, the fly ash is II-grade ash, the sand is medium sand with fineness modulus of 2.7, and the stones are continuous graded broken stones with particle size of 5-31.5, and the mixture ratio is weight parts; the slump of the discharged machine is 70 +/-20 mm, and the design strength is C50; the fluidity and the setting time of the concrete are tested according to relevant regulations of GB8076-2008 'concrete admixture'. The finishing time is the time period from adding water to the surface of the concrete test block with no gloss and dark and hard, namely the concrete finishing time, and the test results are shown in the following table:
TABLE 2 concrete test results
As can be seen from the clear slurry experiment in Table 1, the water reducing rates of the quick-hardening and super-early-strength polycarboxylate superplasticizers PCE-1 to PCE-4 prepared in the examples 1 to 4 are all higher than that of the comparative sample PCE-0. From the concrete experimental results shown in Table 2, it can be seen that the rapid-hardening and super-early-strength polycarboxylate superplasticizers PCE-1 to PCE-4 prepared in examples 1 to 4 have the same initial slump as PCE-0, lower mixing amount, higher water reducing rate, obviously shorter plastering time and setting time than PCE-0, and obviously higher early compressive strength values of 1d, 3d and 7d than PCE-0, so that the polycarboxylate superplasticizer prepared by the invention has an outstanding function of promoting cement hydration reaction, can obviously shorten the setting time of concrete and greatly improve the early strength of concrete.
It will be appreciated by those skilled in the art that the components and technical parameters of the present invention may be varied within the following ranges while achieving the same or similar technical effects as the above embodiments:
a quick-hardening super-early-strength polycarboxylate superplasticizer is prepared from the following raw materials in parts by weight: 180-230 parts of polyether monomer with the molecular weight of 5000-6000, 15-19 parts of unsaturated monocarboxylic acid or derivative thereof, 5-12 parts of unsaturated alcohol amine ester small monomer, 2-5 parts of dimethylaminoethyl methacrylate, 2-5 parts of triallylamine, 0.7-2.0 parts of oxidant, 0.2-0.6 part of reducing agent, 0.6-1.2 parts of chain transfer agent, 14-18 parts of 32wt% sodium hydroxide aqueous solution, 1-5 parts of trisodium phosphate and a proper amount of deionized water, wherein the amount of the deionized water enables the solid content of the rapid-hardening super-early-strength polycarboxylic acid water reducer to reach 45-55%; the unsaturated alcohol amine ester small monomer is prepared by carrying out esterification reaction on acrylic acid and N, N-diethylethanolamine at a molar ratio of 2: 1-1.5 under the catalysis of phosphorous acid at 105-115 ℃, the polyether monomer is at least one of allyl polyoxyethylene polyether, methallyl polyoxyethylene polyether and isopentenol polyoxyethylene ether, the unsaturated monocarboxylic acid or derivative is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, acrylamide and methacrylamide, and the polyether monomer is used as a monomer.
2. The rapid hardening super early strength polycarboxylate superplasticizer according to claim 1, characterized in that: the preparation method of the unsaturated alcohol amine ester small monomer comprises the following steps:
(1) adding acrylic acid and N, N-diethylethanolamine into a reaction vessel provided with a condensing device;
(2) injecting nitrogen while stirring, heating to 55-60 ℃, adding p-phenylenediamine, and stirring for 20-30 min, wherein the p-phenylenediamine accounts for 1.0-1.5% of the total mass of the acrylic acid and the N, N-diethylethanolamine;
(3) continuously heating to 105-115 ℃, adding phosphorous acid, and reacting for 3-5 h at constant temperature, wherein the phosphorous acid accounts for 1.0-1.2% of the total amount of acrylic acid and N, N-diethylethanolamine;
(4) and after the reaction is stopped, carrying out reduced pressure distillation to obtain unreacted acrylic acid, thus obtaining the unsaturated alcohol amine ester small monomer.
The oxidant is at least one of ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide. The chain transfer agent is at least one of thioglycolic acid, mercaptoethanol, 3-mercaptopropionic acid, thioglycerol, isooctyl 3-mercaptopropionate, trisodium phosphate, dodecyl mercaptan and thiomalic acid. The reducing agent is at least one of 2-hydroxy-2-sulfinato acetic acid, 2-hydroxy-2-sulfinato acetic acid disodium salt, 2-hydroxy-2-sulfonato acetic acid and 2-hydroxy-2-sulfonato acetic acid disodium salt.
The preparation method of the rapid hardening and super early strength polycarboxylate superplasticizer comprises the following steps:
(1) weighing the raw material components in parts by weight;
(2) dissolving unsaturated monocarboxylic acid or a derivative thereof in 10-15 parts by weight of deionized water to obtain a first solution; dissolving a reducing agent in 25-30 parts by weight of deionized water to obtain a second solution; dissolving a chain transfer agent in 25-30 parts by weight of deionized water to obtain a third solution;
(3) adding a polyether monomer, an unsaturated alcohol amine ester small monomer, dimethylaminoethyl methacrylate, triallylamine, an oxidant and the rest deionized water into a reaction vessel, and stirring at room temperature until the polyether monomer, the unsaturated alcohol amine ester small monomer, the dimethylaminoethyl methacrylate, the triallylamine, the oxidant and the rest deionized water are dissolved;
(4) simultaneously dropwise adding the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the dropwise adding is finished within 2-5 h, the dropwise adding of the second solution is delayed by 10-20 min compared with that of the first solution, the dropwise adding of the third solution is delayed by 10-30 min compared with that of the first solution, and after the dropwise adding is finished, the heat preservation reaction is carried out for 1-3 h;
(5) and (3) adding 1-5 parts by weight of trisodium phosphate into the material obtained in the step (4), and adjusting the pH value to 6.0-6.5 by using a proper amount of 32wt% sodium hydroxide aqueous solution to obtain the rapid hardening and super early strength polycarboxylate superplasticizer.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
1. A rapid hardening super early strength polycarboxylate superplasticizer is characterized in that: the feed is prepared from the following raw materials in parts by weight: 180-230 parts of polyether monomer with the molecular weight of 5000-6000, 15-19 parts of unsaturated monocarboxylic acid or derivative thereof, 5-12 parts of unsaturated alcohol amine ester small monomer, 2-5 parts of dimethylaminoethyl methacrylate, 2-5 parts of triallylamine, 0.7-2.0 parts of oxidant, 0.2-0.6 part of reducing agent, 0.6-1.2 parts of chain transfer agent, 14-18 parts of 32wt% sodium hydroxide aqueous solution, 1-5 parts of trisodium phosphate and a proper amount of deionized water, wherein the amount of the deionized water enables the solid content of the rapid-hardening and ultra-early-strength polycarboxylic acid water reducer to reach 45-55%; the unsaturated alcohol amine ester small monomer is prepared by carrying out esterification reaction on acrylic acid and N, N-diethylethanolamine at a molar ratio of 2: 1-1.5 under the catalysis of phosphorous acid at 105-115 ℃, the polyether monomer is at least one of allyl polyoxyethylene polyether, methallyl polyoxyethylene polyether and isopentenol polyoxyethylene ether, and the unsaturated monocarboxylic acid or derivative is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, acrylamide and methacrylamide.
2. The rapid hardening super early strength polycarboxylate superplasticizer according to claim 1, characterized in that: the preparation method of the unsaturated alcohol amine ester small monomer comprises the following steps:
(1) adding acrylic acid and N, N-diethylethanolamine into a reaction vessel provided with a condensing device;
(2) injecting nitrogen while stirring, heating to 55-60 ℃, adding p-phenylenediamine, and stirring for 20-30 min, wherein the p-phenylenediamine accounts for 1.0-1.5% of the total mass of the acrylic acid and the N, N-diethylethanolamine;
(3) continuously heating to 105-115 ℃, adding phosphorous acid, and reacting for 3-5 h at constant temperature, wherein the phosphorous acid accounts for 1.0-1.2% of the total amount of acrylic acid and N, N-diethylethanolamine;
(4) and after the reaction is stopped, carrying out reduced pressure distillation to obtain unreacted acrylic acid, thus obtaining the unsaturated alcohol amine ester small monomer.
3. The rapid hardening super early strength polycarboxylate superplasticizer according to claim 1, characterized in that: the oxidant is at least one of ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide.
4. The rapid hardening super early strength polycarboxylate superplasticizer according to claim 1, characterized in that: the chain transfer agent is at least one of thioglycolic acid, mercaptoethanol, 3-mercaptopropionic acid, thioglycerol, isooctyl 3-mercaptopropionate, trisodium phosphate, dodecyl mercaptan and thiomalic acid.
5. The rapid hardening super early strength polycarboxylate superplasticizer according to claim 1, characterized in that: the reducing agent is at least one of 2-hydroxy-2-sulfinato acetic acid, 2-hydroxy-2-sulfinato acetic acid disodium salt, 2-hydroxy-2-sulfonato acetic acid and 2-hydroxy-2-sulfonato acetic acid disodium salt.
6. The method for preparing the rapid hardening ultra-early strength polycarboxylate superplasticizer according to any one of claims 1 to 5, characterized by comprising the following steps: the method comprises the following steps:
(1) weighing the raw material components in parts by weight;
(2) dissolving unsaturated monocarboxylic acid or a derivative thereof in 10-15 parts by weight of deionized water to obtain a first solution; dissolving a reducing agent in 25-30 parts by weight of deionized water to obtain a second solution; dissolving a chain transfer agent in 25-30 parts by weight of deionized water to obtain a third solution;
(3) adding a polyether monomer, an unsaturated alcohol amine ester small monomer, dimethylaminoethyl methacrylate, triallylamine, an oxidant and the rest of deionized water into a reaction container, and stirring at room temperature until the polyether monomer, the unsaturated alcohol amine ester small monomer, the dimethylaminoethyl methacrylate, the triallylamine, the oxidant and the rest of the deionized water are dissolved;
(4) simultaneously dropwise adding the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the dropwise adding is finished within 2-5 h, the dropwise adding of the second solution is delayed by 10-20 min compared with that of the first solution, the dropwise adding of the third solution is delayed by 10-30 min compared with that of the first solution, and after the dropwise adding is finished, the heat preservation reaction is carried out for 1-3 h;
(5) and (3) adding 1-5 parts by weight of trisodium phosphate into the material obtained in the step (4), and adjusting the pH value to 6.0-6.5 by using a proper amount of 32wt% sodium hydroxide aqueous solution to obtain the rapid hardening and super early strength polycarboxylate superplasticizer.
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| CN103936934A (en) * | 2014-05-06 | 2014-07-23 | 武汉理工大学 | Preparation method of triisopropanolamine modified early strength polycarboxylate superplasticizer |
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