CN116040975A - Mud-resistant polycarboxylate superplasticizer and preparation method thereof - Google Patents
Mud-resistant polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN116040975A CN116040975A CN202310058559.9A CN202310058559A CN116040975A CN 116040975 A CN116040975 A CN 116040975A CN 202310058559 A CN202310058559 A CN 202310058559A CN 116040975 A CN116040975 A CN 116040975A
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- Prior art keywords
- mud
- parts
- water reducer
- polycarboxylate
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 151
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 190
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 135
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 46
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002091 cationic group Chemical group 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 6
- 239000013530 defoamer Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 21
- 238000005886 esterification reaction Methods 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 17
- 230000032050 esterification Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 125000004423 acyloxy group Chemical group 0.000 claims description 15
- LKJLUHOHYDJLFF-UHFFFAOYSA-N ethyl(dimethyl)azanium;propane-1-sulfonate Chemical compound CC[NH+](C)C.CCCS([O-])(=O)=O LKJLUHOHYDJLFF-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 claims description 8
- POLZHVHESHDZRD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(=O)OCCO POLZHVHESHDZRD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 claims description 5
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 230000001603 reducing effect Effects 0.000 abstract description 26
- 229920000056 polyoxyethylene ether Polymers 0.000 abstract description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 239000002253 acid Substances 0.000 description 22
- 239000004927 clay Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- -1 acyloxy ethyl dimethylaminopropane sulfonic acid methacrylate Chemical compound 0.000 description 16
- 239000004568 cement Substances 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 15
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 13
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 10
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 239000004567 concrete Substances 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical group OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- MGNVWUDMMXZUDI-UHFFFAOYSA-N propane-1,3-disulfonic acid Chemical compound OS(=O)(=O)CCCS(O)(=O)=O MGNVWUDMMXZUDI-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- AFNWOEJOULWFIS-BTJKTKAUSA-N (z)-4-hydroxy-4-oxobut-2-enoate;tris(2-hydroxyethyl)azanium Chemical compound OC(=O)\C=C/C(O)=O.OCCN(CCO)CCO AFNWOEJOULWFIS-BTJKTKAUSA-N 0.000 description 1
- HHOAKBXSQQKSMI-UHFFFAOYSA-N 1-azaniumyl-2,2-dimethylpropane-1-sulfonate Chemical compound CC(C(S(=O)(=O)O)N)(C)C HHOAKBXSQQKSMI-UHFFFAOYSA-N 0.000 description 1
- IGWIEYXEWVUGCK-UHFFFAOYSA-N 4-aminobenzenesulfonic acid;sodium Chemical group [Na].NC1=CC=C(S(O)(=O)=O)C=C1 IGWIEYXEWVUGCK-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- 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
Abstract
The application discloses an anti-mud polycarboxylate superplasticizer and a preparation method thereof, wherein the anti-mud polycarboxylate superplasticizer comprises the following components in parts by weight: 62-86 parts of hyperbranched polycarboxylate water reducer, 1-2 parts of mud-resistant auxiliary agent, 0.2-0.4 part of defoamer and 0.1-0.4 part of air entraining agent, wherein the hyperbranched polycarboxylate water reducer is a hyperbranched polycarboxylate water reducer with amphoteric groups introduced, and comprises the following components in parts by weight: 2-3 parts of pentaerythritol triacrylate, 97-98 parts of water, 1-2 parts of isopentenyl alcohol polyoxyethylene ether, 0.5-0.8 part of a polymerization monomer containing a cationic group, 14-16 parts of acrylic acid, 2.4-3 parts of an initiator and 0.1-0.2 part of a chain transfer agent. The mud-resistant polycarboxylate water reducer prepared by the method has stronger mud resistance and better water reducing performance by introducing amphoteric groups in the formation process of the hyperbranched polycarboxylate water reducer.
Description
Technical Field
The application relates to the field of polycarboxylate water reducers, in particular to an anti-mud polycarboxylate water reducer and a preparation method thereof.
Background
The water reducing agent is the most widely used additive in concrete, and the water reducing agent can greatly reduce the water consumption of cement on one hand and can also enable the concrete to have higher flow property and mechanical property on the other hand.
The development of the water reducer goes through three stages from lignin water reducer and water-soluble resin water reducer to the most widely used polycarboxylate water reducer at present, and the third-generation polycarboxylate water reducer has the advantages of low addition, high water reduction rate, slump loss and the like and is widely applied to the field of buildings.
However, in recent years, recycled aggregate is increasingly used in concrete, and the recycled aggregate has high mud content, so that clay minerals of the recycled aggregate can adsorb the polycarboxylate water reducer, and the dispersibility and water reducing performance of the polycarboxylate water reducer are damaged. At present, the common solution is to increase the dosage of the water reducer or wash the recycled aggregate, but these methods all lead to the increase of cost and the decrease of water reducing performance.
Disclosure of Invention
In order to reduce the influence of clay on the performance of the polycarboxylate superplasticizer, the application provides an anti-mud polycarboxylate superplasticizer and a preparation method thereof.
According to the first aspect, the anti-mud polycarboxylate superplasticizer comprises the following components in parts by weight: 62-86 parts of hyperbranched polycarboxylate water reducer, 1-2 parts of mud-resistant auxiliary agent, 0.2-0.4 part of defoamer and 0.1-0.4 part of air entraining agent;
the hyperbranched polycarboxylate water reducer comprises amphoteric groups, and the raw materials of the hyperbranched polycarboxylate water reducer comprise the following components in parts by weight: 2-3 parts of pentaerythritol triacrylate, 97-98 parts of water, 1-2 parts of isopentenyl alcohol polyether, 0.5-0.8 part of a polymeric monomer containing a cationic group, 14-16 parts of acrylic acid, 2.4-3 parts of an initiator and 0.1-0.2 part of a chain transfer agent.
Typically, but not by way of limitation, isopentenyl alcohol polyethers employ isopentenyl alcohol polyoxyethylene ethers.
By adopting the technical scheme, the copolymer with the star-shaped hyperbranched space structure can be obtained by taking pentaerythritol triacrylate as a main polymerization monomer, and the steric hindrance formed by intramolecular cross-linking can inhibit the branch structure in the polycarboxylate water reducer from being embedded into clay, so that the mud resistance of the polycarboxylate water reducer is increased; the isopentenol polyoxyethylene ether with a longer molecular chain is introduced, so that the branch length in the star-shaped structure is increased, and the effect of the steric hindrance effect is improved, thereby enhancing the water reducing performance and the mud resistance of the water reducer.
The anionic groups in the polycarboxylate water reducer can be combined with calcium ions from concrete or clay to destroy the spatial conformation of the copolymer, so that the water reducing performance is reduced, the cationic group-containing polymerization monomer is introduced to compete with the calcium ions for the anionic groups in the copolymer, the spatial conformation of the copolymer is maintained, and the mud resisting effect and the water reducing performance of the polycarboxylate water reducer are improved. However, the space conformation of the main chain is solidified due to the electrostatic action between the anionic and cationic groups, so that the change of the molecular chain conformation is reduced, the adsorption capacity of the water reducer on the cement surface is reduced, and the water reducing effect of the water reducer is affected; because the space structure of the polymer is star-shaped hyperbranched, anions and cations are uniformly distributed in a plurality of branched chains, the electrostatic effect between anions and cations is reduced, the mud resistance of the polycarboxylate water reducer is improved, and the water reducing effect of the water reducer is further exerted. The mud-resistant auxiliary agent is added, so that the water reducing performance of the polycarboxylate water reducer is further improved, and under the special spatial structure of the hyperbranched polycarboxylic acid, the hyperbranched polycarboxylic acid can more uniformly carry the mud-resistant auxiliary agent, the dispersibility of the mud-resistant auxiliary agent is improved, and the mud resistance of the polycarboxylate water reducer is further improved.
Preferably, the pentaerythritol triacrylate comprises the following components in parts by weight: 9-13 parts of pentaerythritol, 28-36 parts of acrylic acid, 0.2-0.6 part of polymerization inhibitor and 0.2-0.6 part of catalyst.
By adopting the technical scheme, the pentaerythritol and the acrylic acid are subjected to esterification reaction to obtain the raw materials containing the ester monomers, so that the functional polycarboxylic acid obtained by polymerization contains the ester monomers, and along with the prolonging of the mixing time of the water reducer and cement, the ester groups are gradually hydrolyzed into carboxylic acid groups and adsorbed on hydrated cement particles, so that the slump retaining performance of the polycarboxylic acid water reducer is improved, and the water reducing performance of the polycarboxylic acid water reducer is further improved; the ratio of pentaerythritol to acrylic acid raw materials is optimized, pentaerythritol triacrylate is obtained by esterification, the pentaerythritol triacrylate monomer is an ester monomer containing three double bonds, and can be used as a polymerized raw material to obtain a high-crosslinking macromolecular structure.
Preferably, the preparation process of the hyperbranched polycarboxylate water reducer comprises the following steps of:
esterification: mixing pentaerythritol, acrylic acid, a polymerization inhibitor and a catalyst, heating to 40-60 ℃, stirring to obtain a mixture, continuously heating the mixture until the temperature reaches 80-90 ℃, adding a water scavenger, continuously heating, maintaining the temperature at 100-110 ℃ for reaction, and carrying out vacuum filtration to obtain an esterified product pentaerythritol triacrylate;
polymerization: and (3) adding water into pentaerythritol triacrylate obtained in the esterification step, mixing and stirring, adding isopentenol polyether, a polymerization monomer containing a cationic group and acrylic acid, mixing and stirring, heating, adding an initiator and a chain transfer agent for polymerization reaction, and cooling to obtain the hyperbranched polycarboxylate water reducer.
Typically, but not by way of limitation, the polymerization inhibitor is para-tertiary butyl catechol, the catalyst is sulfamic acid, the initiator is ammonium persulfate, and the chain transfer agent is mercaptopropionic acid.
Preferably, the polymeric monomer containing a cationic group is acyloxyethyldimethylaminopropane sulfonic acid methacrylate.
The preparation method of the methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid comprises the following steps:
a1, dissolving dimethylaminoethyl methacrylate in acetone to obtain a dimethylaminoethyl methacrylate solution; dissolving 1, 3-propanesulfonic acid in acetone to obtain a1, 3-propanesultone solution;
a2, adding a1, 3-propane sultone solution into the dimethylaminoethyl methacrylate solution, reacting for 40-50h in a dark environment, filtering and drying to obtain the acyloxy ethyl dimethylaminopropane sulfonic acid methacrylate.
By adopting the technical scheme, the polymerization monomer containing the cationic group is selected as the acrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid, the cationic group is introduced and the sulfonic group is introduced, so that after star-shaped branches of the polycarboxylic acid extend to between cement particles, a hydration film is formed on the surfaces of the cement particles, the hydration film can destroy the flocculation structure of the cement particles, and the water reducing performance and the dispersibility of the polycarboxylic acid water reducer are improved; the sulfonic group can complex metal ions in clay, so that the combination of the metal ions in clay and the copolymer is reduced, the adsorption of the clay on the water reducer is further reduced, and the mud resistance and the dispersibility of the water reducer are improved. The nitrogen positive ion group is introduced, so that the adsorption sites of the water reducer and cement can be increased, and the water reducing effect is improved.
Preferably, 10-12 parts of hydroxyethyl methacrylate phosphate is also added in the polymerization step.
By adopting the technical scheme, the phosphate radical is introduced, the electronegativity of the phosphate radical is higher than that of the carboxylate radical, the phosphate radical can be preferentially adsorbed to the surface of the clay, the adsorption of the clay to the carboxylate radical is reduced, and the mud resistance of the polycarboxylate water reducer is improved; the carboxylic acid groups on the chain are dispersed due to the space structure of the hyperbranched polycarboxylic acid, the steric hindrance effect of the polyether macromonomer on the branched chain is achieved, the phosphoric acid groups can improve the anionic charge density on the copolymer chain, the amount of the water reducer adsorbed on the cement surface is improved, the electrostatic effect of the water reducer is improved, and the water reducing effect of the water reducer is further enhanced.
Preferably, the polymerization time in the polymerization step is 6 to 8 hours.
By adopting the technical scheme, as the molecular mass of the polycarboxylate water reducer has great influence on the dispersibility, the water reducing performance and the mud resistance, the polycarboxylate water reducer is easy to gel due to the fact that the molecular mass is too large, the electrostatic repulsive force effect of the anionic groups and the cationic groups of the hyperbranched polycarboxylate water reducer is also enhanced, and the dispersibility and the water reducing performance of the polycarboxylate water reducer are reduced; the molecular weight is too small, the side chains and ionic groups carried on the water reducer are reduced, so that the adsorption point of the water reducer is reduced, the steric hindrance effect is reduced, the performance and mud resistance of the water reducer are both poor, and especially, the hyperbranched polycarboxylate water reducer in the application synthesizes a copolymer with a star-shaped space structure, so that the influence can be amplified. Therefore, the polycarboxylic acid water reducer with moderate molecular weight is obtained by controlling the polymerization reaction time, so that the polycarboxylic acid water reducer has better dispersibility, water reducing performance and mud resistance.
Preferably, 4-8 parts of polycarboxylic group monomer is added in the polymerization step, and then the polymerization reaction is carried out.
Typically, but not by way of limitation, the polycarboxylic group monomer is one or a combination of several of itaconic acid and citric acid.
Through adding the multi-carboxyl group monomer, the density of carboxyl groups in the copolymer is improved, the electrostatic repulsion effect of the carboxylic acid groups in the hyperbranched polycarboxylic acid can be further exerted, the amount of carboxyl groups adsorbed on the surface of cement can be improved, the amount of carboxyl groups on the surface of the cement is improved, the release speed of groups with functional performance can be slowed down, the service life of the water reducer is prolonged, and the mud resistance and water reduction performance of the water reducer are enhanced. Itaconic acid is selected as a polycarboxylic group monomer, and the other carboxyl group of the itaconic acid does not participate in polymerization, so that the chemical activity of the water reducing agent can be enhanced by taking the itaconic acid as a branched active group, and the water reducing performance and mud resistance of the water reducing agent are further improved.
Preferably, the raw materials of the anti-mud type polycarboxylate superplasticizer also comprise water, and the weight ratio of the hyperbranched polycarboxylate superplasticizer to the water is 1 (3-5).
By adopting the technical scheme, the proportion of the water and the hyperbranched polycarboxylate water reducer is further optimized, and the phenomenon that gel and coagulation are generated in concrete due to the fact that the mass fraction of the hyperbranched polycarboxylate water reducer is too high is reduced, so that the dispersibility and the water reducing performance of the polycarboxylate water reducer are affected.
Preferably, the mud-resistant auxiliary agent adopts one or more of tetramethyl ammonium chloride, sodium sulfanilate and polyethylene glycol.
By adopting the technical scheme, compared with the polycarboxylate superplasticizer, tetramethyl ammonium chloride, sodium sulfanilate and polyethylene glycol can be preferentially adsorbed with clay, so that the adsorption of the clay on the polycarboxylate superplasticizer is reduced, and the mud resistance of the mud-resistant polycarboxylate superplasticizer is improved.
In a second aspect, a method for preparing an anti-mud polycarboxylate superplasticizer comprises the following steps: adding the mud-resistant auxiliary agent, the defoaming agent and the air entraining agent into the hyperbranched polycarboxylate water reducer, and uniformly stirring to obtain the mud-resistant polycarboxylate water reducer; or adding the mud-resistant auxiliary agent, the defoaming agent, the air entraining agent and water into the hyperbranched polycarboxylate water reducer, and uniformly stirring to obtain the mud-resistant polycarboxylate water reducer.
Through adopting above-mentioned technical scheme, mix before using for hyperbranched polycarboxylate water reducing agent more even carries anti mud auxiliary agent, improves anti mud effect of anti mud formula polycarboxylate water reducing agent.
In summary, the application has the following beneficial effects:
1. the copolymer with star-shaped hyperbranched space structure is obtained by taking pentaerythritol triacrylate as a main polymerization monomer, and the polymerization problem and the performance problem of the pentaerythritol triacrylate as the main polymerization monomer are improved by introducing isopentenol polyoxyethylene ether with longer molecular chain and methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid. Conversely, after the polycarboxylate water reducer is introduced with the amphoteric group, the water reducing performance and the dispersibility are reduced due to the action of electrostatic repulsion on the chain, and the influence of the electrostatic repulsion can be reduced by adopting the hyperbranched polycarboxylate copolymer with a star-shaped space structure.
2. The polycarboxylic acid monomer is added, so that the density of carboxyl groups and phosphoric acid groups in the copolymer is improved, and the dispersibility, mud resistance and water reducing performance of the polycarboxylic acid water reducer are improved by introducing phosphoric acid groups which can be preferentially combined with clay.
3. The mud-resistant polycarboxylate superplasticizer with better dispersibility, mud resistance and water reducing performance is obtained by compounding the hyperbranched polycarboxylate superplasticizer with the mud-resistant auxiliary agent, the defoaming agent and the initiator.
Detailed Description
The starting materials used in the examples and preparations can be described in detail commercially, and the present application will be described in further detail with reference to examples.
Preparation example
Preparation example of hyperbranched polycarboxylate superplasticizer
Preparation example 1-1, a hyperbranched polycarboxylate water reducer, is prepared by the following steps:
esterification: 11g of pentaerythritol, 32g of acrylic acid, 0.4g of para-tertiary butyl catechol and 0.4g of sulfamic acid are blended, the temperature is regulated to 50 ℃, the mixture is uniformly stirred to obtain a mixture, 3g of benzene is added into the mixture after the temperature is increased to 85 ℃, the esterification reaction is carried out for 8 hours after the temperature is increased to 100 ℃, and then vacuum suction filtration is carried out to obtain an esterification product pentaerythritol triacrylate;
polymerization: taking 2.5g of pentaerythritol triacrylate, which is an esterification product obtained in the esterification step, adding 97.5g of water, mixing and stirring, then adding 1.5g of isopentenyl alcohol polyoxyethylene ether, 0.65g of methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid, 15g of acrylic acid, 2.7g of ammonium persulfate, 6g of itaconic acid, 11g of hydroxyethyl methacrylate phosphate and 0.15g of mercaptopropionic acid, heating to 70 ℃ for carrying out free radical copolymerization reaction for 6h, cooling to room temperature, and regulating pH to 5 by using 1mol/L of sodium hydroxide solution to obtain the hyperbranched polycarboxylate water reducer.
Wherein, the methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid is prepared by the following steps:
a1, 1mol of dimethylaminoethyl methacrylate is dissolved in 500mL of acetone to obtain a dimethylaminoethyl methacrylate solution; 1mol of 1, 3-propanesulfonic acid was dissolved in 500mL of acetone to give a1, 3-propanesultone solution;
a2, adding 1, 3-propane sultone solution into the dimethylaminoethyl methacrylate solution at the speed of 8mL/s, reacting for 40h in a dark environment, filtering and drying to obtain the acyloxyethyl dimethylaminopropane sulfonic acid methacrylate.
Preparation examples 1-2, a hyperbranched polycarboxylate water reducer, is prepared by the following steps:
esterification: 13g of pentaerythritol, 36g of acrylic acid, 0.6g of para-tertiary butyl catechol and 0.6g of sulfamic acid are blended, the temperature is regulated to 60 ℃, the mixture is uniformly stirred to obtain a mixture, 3g of benzene is added into the mixture after the temperature is continuously increased to 80 ℃, the temperature is continuously increased to 105 ℃, the reaction is carried out for 9 hours, and vacuum suction filtration is carried out to obtain an esterified product pentaerythritol triacrylate;
polymerization: taking 3g of the esterified product pentaerythritol triacrylate obtained in the esterification step, adding 97g of water, mixing and stirring, then adding 2g of isopentenyl alcohol polyoxyethylene ether, 0.8g of methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid, 16g of acrylic acid, 2.4g of ammonium persulfate, 4g of itaconic acid, 12g of hydroxyethyl methacrylate phosphate and 0.1g of mercaptopropionic acid, heating to 75 ℃ for free radical copolymerization reaction for 8h, cooling to room temperature, and using 1mol/L of sodium hydroxide solution to adjust pH to 5.5 to obtain the hyperbranched polycarboxylate water reducer.
Wherein, the methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid is prepared by the following steps:
a1, 1mol of dimethylaminoethyl methacrylate is dissolved in 500mL of acetone to obtain a dimethylaminoethyl methacrylate solution; 1mol of 1, 3-propanesulfonic acid was dissolved in 500mL of acetone to give a1, 3-propanesultone solution;
a2, adding the 1, 3-propane sultone solution into the dimethylaminoethyl methacrylate solution at the speed of 10mL/s, reacting for 50h in a dark environment, filtering and drying to obtain the acyloxyethyl dimethylaminopropane sulfonic acid methacrylate.
Preparation examples 1-3, a hyperbranched polycarboxylate water reducer, is prepared by the following steps:
esterification: 9g of pentaerythritol, 28g of acrylic acid, 0.2g of para-tertiary butyl catechol and 0.2g of sulfamic acid are blended, the temperature is regulated to 40 ℃, the mixture is uniformly stirred to obtain a mixture, 3g of benzene is added into the mixture after the temperature is continuously increased to 90 ℃, the temperature is continuously increased to 110 ℃, the reaction is carried out for 8.5 hours, and vacuum filtration is carried out to obtain an esterified product pentaerythritol triacrylate;
polymerization: taking 2g of the esterified product pentaerythritol triacrylate obtained in the esterification step, adding 98g of water, mixing and stirring, then adding 1g of isopentenyl alcohol polyoxyethylene ether, 0.5g of methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid, 14g of acrylic acid, 10g of hydroxyethyl methacrylate phosphate, 3g of ammonium persulfate, 8g of itaconic acid and 0.2g of mercaptopropionic acid, heating to 65 ℃ for carrying out free radical copolymerization reaction for 10h, cooling to room temperature, and regulating the pH to 6 by using a 1mol/L sodium hydroxide solution to obtain the hyperbranched polycarboxylate water reducer.
Wherein, the methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid is prepared by the following steps:
a1, 1mol of dimethylaminoethyl methacrylate is dissolved in 500mL of acetone to obtain a dimethylaminoethyl methacrylate solution; 1mol of 1, 3-propanesulfonic acid was dissolved in 500mL of acetone to give a1, 3-propanesultone solution;
a2, adding the 1, 3-propane sultone solution into the dimethylaminoethyl methacrylate solution at the speed of 12mL/s, reacting for 45h in a dark environment, filtering and drying to obtain the acyloxyethyl dimethylaminopropane sulfonic acid methacrylate.
Preparation example 1-4, a hyperbranched polycarboxylate water reducer, is different from preparation example 1-1 in that: the methacryloyloxyethyl dimethyl aminopropanesulfonic acid was replaced with an equivalent amount of methacryloyloxyethyl trimethyl ammonium chloride.
Preparation example 1-5, a hyperbranched polycarboxylate water reducer, is different from preparation example 1-1 in that: the free radical copolymerization time in the polymerization step was 4h.
Preparation examples 1-6, a hyperbranched polycarboxylate water reducer, differ from preparation example 1-1 in that: the free radical copolymerization time in the polymerization step was 10h.
Preparation examples 1-7, a hyperbranched polycarboxylate water reducer, differ from preparation example 1-1 in that: itaconic acid was replaced with an equal amount of acrylic acid in the polymerization step.
Preparation examples 1-8, a hyperbranched polycarboxylate water reducer, differ from preparation example 1-1 in that: in the esterification step, pentaerythritol is replaced with an equal amount of sorbitol.
Preparation examples 1-9, a hyperbranched polycarboxylate water reducer, differ from preparation example 1-1 in that: in the polymerization step, pentaerythritol triacrylate was replaced with an equivalent amount of acrylic acid.
Preparation examples 1-10, a hyperbranched polycarboxylate water reducer, differ from preparation example 1-1 in that the isopentenol polyoxyethylene ether was replaced with an equal amount of acyloxyethyl dimethyl aminopropanesulfonic acid methacrylate.
Preparation examples 1-11, a hyperbranched polycarboxylate water reducer, differ from preparation example 1-1 in that the acyloxy ethyl dimethyl aminopropanesulfonic acid methacrylate was replaced with an equal amount of isopentenol polyoxyethylene ether.
Preparation examples 1-12, a hyperbranched polycarboxylate water reducer, differs from preparation example 1-1 in that the acyloxy ethyl dimethyl aminopropanesulfonic acid methacrylate and the isopentenol polyoxyethylene ether are replaced with equal amounts of pentaerythritol triacrylate.
Preparation examples 1-13, a hyperbranched polycarboxylate water reducer, were different from preparation example 1-1 in that methacrylic acid acyloxyethyldimethylaminopropane sulfonic acid was not added in the polymerization step, and an equal amount of methacrylic acid acyloxyethyldimethylaminopropane sulfonic acid was added in the dilution step.
Preparation examples 1-14, a hyperbranched polycarboxylate water reducer, differ from preparation example 1-1 in that: hydroxyethyl methacrylate phosphate is replaced with an equivalent amount of acrylic acid.
Examples
Example 1, an anti-mud polycarboxylate water reducer is prepared by the following steps:
1.5g of sodium sulfanilate, 0.3g of defoamer, 0.25g of air entraining agent and 296g of water are added into 74g of hyperbranched polycarboxylate water reducer and uniformly stirred, so that the anti-mud polycarboxylate water reducer is obtained.
Wherein the hyperbranched polycarboxylate water reducer is prepared from preparation example 1-1.
Example 2, an anti-mud polycarboxylate water reducer, was prepared by the following steps:
1g of tetramethyl ammonium chloride, 0.2g of defoamer, 0.1g of air entraining agent and 430g of water are added into 86g of hyperbranched polycarboxylate water reducer and stirred uniformly, so that the anti-mud polycarboxylate water reducer is obtained.
Wherein the hyperbranched polycarboxylate water reducer is prepared from preparation examples 1-2.
Example 3, an anti-mud polycarboxylate water reducer, was prepared by the following steps:
2g of sodium sulfanilate, 0.4g of defoamer, 0.4g of air entraining agent and 186g of water are added into 62g of hyperbranched polycarboxylate water reducer and stirred uniformly, thus obtaining the anti-mud polycarboxylate water reducer.
Wherein the hyperbranched polycarboxylate water reducer is prepared from preparation examples 1-3.
Example 4, an anti-mud polycarboxylate superplasticizer, was different from example 1 in that: hyperbranched polycarboxylate water reducers were derived from preparation examples 1-4.
Example 5, an anti-mud polycarboxylate superplasticizer, is different from example 1 in that: hyperbranched polycarboxylate water reducers were obtained from preparation examples 1 to 5.
Example 6, an anti-mud polycarboxylate superplasticizer, is different from example 1 in that: hyperbranched polycarboxylate water reducers were obtained from preparation examples 1 to 6.
Example 7, an anti-mud polycarboxylate superplasticizer, was different from example 1 in that: hyperbranched polycarboxylate water reducers were derived from preparation examples 1-7.
Example 8, an anti-mud polycarboxylate superplasticizer, is different from example 1 in that: the water is replaced by an equivalent amount of hyperbranched polycarboxylate water reducer.
Example 9, an anti-mud polycarboxylate superplasticizer, is different from example 1 in that: hyperbranched polycarboxylate water reducers were derived from preparation examples 1-8.
Example 10, an anti-mud polycarboxylate superplasticizer, was different from example 1 in that: hyperbranched polycarboxylate water reducers were derived from preparation examples 1-14.
Comparative example
Comparative example 1, an anti-mud polycarboxylate superplasticizer, differs from example 1 in that the hyperbranched polycarboxylate superplasticizer was derived from preparation examples 1-9.
Comparative example 2, an anti-mud polycarboxylate superplasticizer, differs from example 1 in that the hyperbranched polycarboxylate superplasticizer was derived from preparation examples 1-10.
Comparative example 3, an anti-mud polycarboxylate superplasticizer, differs from example 1 in that the hyperbranched polycarboxylate superplasticizer was derived from preparation examples 1-11.
Comparative example 4, an anti-mud polycarboxylate superplasticizer, differs from example 1 in that the hyperbranched polycarboxylate superplasticizer was derived from preparation examples 1-12.
Comparative example 5, an anti-mud polycarboxylate superplasticizer, differs from example 1 in that the hyperbranched polycarboxylate superplasticizer was derived from preparation examples 1-13.
Comparative example 6, an anti-mud polycarboxylate superplasticizer, differs from example 1 in that sodium sulfanilic acid was replaced with an equivalent amount of hyperbranched polycarboxylate superplasticizer.
Comparative example 7, an anti-mud polycarboxylate superplasticizer, was prepared by the following steps:
(1) Grinding 3.1g of maleic anhydride, adding into 5.5g of dry powder glucose, dissolving 1g of concentrated sulfuric acid, 0.1g of polymerization inhibitor and 1.2g of deionized water into a solution, adding the solution into a mixture of maleic anhydride and glucose under stirring, aging for 15 minutes, placing into an oven, reacting for 2 hours at 120 ℃ to fully volatilize and dry water, and obtaining a mixture I. The mixture I is ground, then 2.57g of 50% phosphoric acid aqueous solution is added, fully stirred and uniformly mixed, aged for 15 minutes, and then placed into an oven to be heated and reacted for 1.5 hours at 120 ℃ to obtain a mixture II.
(2) Mixing 6.5g maleic anhydride, 4.5g triethanolamine, 0.2g polymerization inhibitor and 9g polyethylene glycol monomethyl ether uniformly, reacting for 1 hour under the catalysis of 0.2g p-toluenesulfonic acid at 120 ℃, and cooling to room temperature to obtain a solid mixture III composed of triethanolamine maleate and polyethylene glycol monomethyl ether maleate.
(3) 2g of acrylic acid, 1g of acrylamide and 0.45g of initiating aid L-ascorbic acid are dissolved in deionized water to prepare a dropwise solution A material for standby, and 2.5g of initiating agent hydrogen peroxide is dissolved in deionized water to prepare a dropwise solution B material for standby.
(4) Adding the mixture II, the mixture III, 58g of isopentenyl polyoxyethylene ether macromonomer and 70g of deionized water prepared in the steps 2 and 3 into a container, stirring and dissolving the mixture, adding 1.5g of thioglycollic acid, stirring for 10 minutes, reacting at room temperature, and simultaneously dropwise adding the material A and the material B into a base solution at uniform speed; and (3) dropwise adding the material A for 2 hours at 50 ℃, dropwise adding the material B for 3 hours, preserving heat for 1 hour, and adjusting the pH value of the reaction solution to 6-7 by using a sodium hydroxide solution after the temperature is cooled to room temperature, thus obtaining the anti-mud type polycarboxylate superplasticizer.
Performance test
The mud-resistant polycarboxylate water reducers of examples 1 to 10 and comparative examples 1 to 7 and the preparation method thereof were subjected to performance test, and each test was tested in parallel for 6 times to obtain an average value.
Test 1: the cement paste fluidity test was carried out according to GB/T8077-2012 "concrete admixture homogeneity test method", wherein the clay content in cement was 5%, the fold-fixing blending amount of the anti-mud type polycarboxylate superplasticizer was 0.18%, and the results are shown in Table 1.
Table 1: cement paste flow performance results
As can be seen from the combination of the examples 1-4 and the table 1, the prepared anti-mud polycarboxylic acid water reducer is better in paste fluidity by adding the methacrylic acid acyloxy ethyl dimethyl amino propane sulfonic acid as a monomer containing a cationic group, and the sulfonic acid group is capable of complexing metal ions in clay, so that the combination of the metal ions in clay and a copolymer is reduced, the adsorption effect of the clay on the water reducer is further reduced, and the mud resistance and the dispersibility of the water reducer are improved. The methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid is selected and used, and has the advantages that the methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid belongs to a cationic monomer without chloride ions, so that the chloride ion corrosion possibly caused when the concrete is used for concrete later is reduced, and the application range of the anti-mud type polycarboxylate water reducer is increased.
It can be seen from the combination of examples 1 to 3 and examples 5 to 6 and the combination of Table 1 that the better anti-mud type polycarboxylate superplasticizer can be obtained by controlling the polymerization time between 6 and 8 hours, because the gel or agglomeration phenomenon can be caused by the too large molecular weight of the polycarboxylate copolymer; too small molecular weight results in poor steric hindrance effect and electrostatic repulsion effect, so that the polycarboxylic acid copolymer is easier to embed into gaps of clay, and further the mud resistance of the water reducer is reduced. Thus too large and too small a molecular weight of the polycarboxylic acid copolymer affects the mud resistance of the polycarboxylic acid.
As can be seen from the combination of examples 1 to 3, example 7 and example 10 and the combination of table 1, the mud-resistant polycarboxylate water reducer prepared by incorporating itaconic acid and hydroxyethyl methacrylate phosphate during polymerization has better performance due to the following: the itaconic acid contains two carboxyl groups, so that the density of unit carboxyl groups formed by the copolymer is increased, the adsorption sites of the composite polycarboxylic acid on the surfaces of clay and cement are improved, and the mud resistance of the composite polycarboxylic acid is enhanced.
It can be seen from the combination of examples 1-3 and 8 and the combination of table 1 that the sludge-resistant polycarboxylate water reducer adopts undiluted hyperbranched polycarboxylate water reducer mother liquor, and the water reducing performance of the sludge-resistant polycarboxylate water reducer is reduced, because the mass fraction of the hyperbranched polycarboxylate water reducer is too high, the content of active groups such as anionic and cationic groups, carboxyl groups, sulfonic groups and the like in unit volume is too high, the gel and coagulation phenomena are easily generated in concrete, and the dispersibility and the water reducing performance of the polycarboxylate water reducer are affected.
As can be seen by combining examples 1-3 and example 9 and combining Table 1, the performance of the anti-mud type polycarboxylate superplasticizer is reduced by adopting sorbitol instead of pentaerythritol in the esterification process, because the performance of the polycarboxylate superplasticizer is greatly affected by the conditions in the polymerization process, including raw materials, and the alcohol substances in the esterification process are preferred, so that the prepared anti-mud type polycarboxylate superplasticizer has better performance.
As can be seen from the combination of examples 1 to 3 and comparative examples 1 to 5 and the combination of table 1, the types of monomers contained pentaerythritol triacrylate, isopentenol polyoxyethylene ether and methacrylic acid acyloxyethyl dimethyl aminopropanesulfonic acid, and the prepared mud-resistant polycarboxylate water reducer had better mud resistance because: the star-shaped hyperbranched polycarboxylate water reducer obtained by polymerizing pentaerythritol triacrylate has better water reducing performance, and the special space structure of the star-shaped hyperbranched polycarboxylate water reducer is not easy to embed into clay, so that the mud resistance of the water reducer is improved; the amphoteric group is introduced, the anion and the cation group can be combined with clay firstly, the adsorption of the clay to the carboxyl group is reduced, the cation and the anion can maintain the stability of the space conformation of the polycarboxylic acid copolymer, and the change of the space conformation formed after the anion group is adsorbed by the clay is reduced, so that the mud resistance of the water reducer is improved. When pentaerythritol triacrylate, isopentenyl alcohol polyoxyethylene ether and methacrylic acid acyloxy ethyl dimethyl aminopropane sulfonic acid are used as polymerized monomers, the compatibility effect of mud resistance exists, and after star-shaped hyperbranched structures formed by the polymerization of pentaerythritol triacrylate, the anionic groups and cationic groups introduced by the isopentenyl alcohol polyoxyethylene ether and the methacrylic acid acyloxy ethyl dimethyl aminopropane sulfonic acid can increase the chain length of a branched chain, further improve the steric hindrance effect and enhance the mud resistance; the hyperbranched structure can also reduce the electrostatic effect between anions and cations and improve the water reducing performance and mud resistance of the water reducer. When the cation concentration is too large, the adsorption of cement to the water reducer can be influenced, so that the effect of the water reducer is influenced, and too small cation concentration can cause too much anions to be adsorbed by clay, so that the effect of the water reducer is weakened.
The compound polycarboxylic acid of the application optimizes the proportion of each raw material by combining examples 1-3 and comparative examples 6-7 and combining table 1, and has better mud resistance and water reducing performance compared with the conventional polycarboxylic acid water reducer.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The anti-mud polycarboxylate superplasticizer is characterized by comprising the following components in parts by weight: 62-86 parts of hyperbranched polycarboxylate water reducer, 1-2 parts of mud-resistant auxiliary agent, 0.2-0.4 part of defoamer and 0.1-0.4 part of air entraining agent;
the hyperbranched polycarboxylate water reducer comprises amphoteric groups, and the raw materials of the hyperbranched polycarboxylate water reducer comprise the following components in parts by weight: 2-3 parts of pentaerythritol triacrylate, 97-98 parts of water, 1-2 parts of isopentenyl alcohol polyether, 0.5-0.8 part of a polymeric monomer containing a cationic group, 14-16 parts of acrylic acid, 2.4-3 parts of an initiator and 0.1-0.2 part of a chain transfer agent.
2. The anti-mud polycarboxylate superplasticizer as claimed in claim 1, wherein the pentaerythritol triacrylate comprises the following components in parts by weight: 9-13 parts of pentaerythritol, 28-36 parts of acrylic acid, 0.2-0.6 part of polymerization inhibitor and 0.2-0.6 part of catalyst.
3. The mud-resistant polycarboxylate superplasticizer as set forth in claim 2, wherein the preparation process of the hyperbranched polycarboxylate superplasticizer comprises the following steps:
esterification: mixing pentaerythritol, acrylic acid, a polymerization inhibitor and a catalyst, heating to 40-60 ℃, stirring to obtain a mixture, continuously heating the mixture until the temperature reaches 80-90 ℃, adding a water scavenger, continuously heating, maintaining the temperature at 100-110 ℃ for reaction, and carrying out vacuum filtration to obtain an esterified product pentaerythritol triacrylate;
polymerization: and (3) adding water into pentaerythritol triacrylate obtained in the esterification step, mixing and stirring, adding isopentenol polyether, a polymerization monomer containing a cationic group and acrylic acid, mixing and stirring, heating, adding an initiator and a chain transfer agent for polymerization reaction, and cooling to obtain the hyperbranched polycarboxylate water reducer.
4. The anti-mud polycarboxylate superplasticizer as set forth in claim 1, wherein: the polymerization monomer containing the cationic group is methacrylic acid acyloxy ethyl dimethyl ammonia propane sulfonic acid.
5. The mud-resistant polycarboxylate superplasticizer as set forth in claim 3, wherein 10-12 parts of hydroxyethyl methacrylate phosphate is further added in the polymerization step.
6. A mud-resistant polycarboxylate superplasticizer as defined in claim 3, wherein: the polymerization reaction time in the polymerization step is 6-8h.
7. A mud-resistant polycarboxylate superplasticizer as defined in claim 3, wherein: and 4-8 parts of polycarboxylic group monomer is added in the polymerization step, and then polymerization reaction is carried out.
8. The anti-mud polycarboxylate superplasticizer as set forth in claim 1, wherein: the raw materials of the anti-mud type polycarboxylate superplasticizer also comprise water, and the weight ratio of the hyperbranched polycarboxylate superplasticizer to the water is 1 (3-5).
9. The mud-resistant polycarboxylate superplasticizer as set forth in claim 1, wherein said mud-resistant adjuvant is a combination of one or more of tetramethyl ammonium chloride, sodium sulfanilate and polyethylene glycol.
10. The method for preparing the anti-mud type polycarboxylate superplasticizer according to any one of claims 1-9, comprising the following steps: adding the mud-resistant auxiliary agent, the defoaming agent and the air entraining agent into the hyperbranched polycarboxylate water reducer, and uniformly stirring to obtain the mud-resistant polycarboxylate water reducer; or adding the mud-resistant auxiliary agent, the defoaming agent, the air entraining agent and water into the hyperbranched polycarboxylate water reducer, and uniformly stirring to obtain the mud-resistant polycarboxylate water reducer.
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