CN114163464B - Esterification product, low-hydration heat ether polycarboxylate water reducer and preparation method thereof - Google Patents
Esterification product, low-hydration heat ether polycarboxylate water reducer and preparation method thereof Download PDFInfo
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- CN114163464B CN114163464B CN202111537781.4A CN202111537781A CN114163464B CN 114163464 B CN114163464 B CN 114163464B CN 202111537781 A CN202111537781 A CN 202111537781A CN 114163464 B CN114163464 B CN 114163464B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 53
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 43
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 40
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 37
- 230000032050 esterification Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 40
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 40
- 230000036571 hydration Effects 0.000 claims abstract description 33
- 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 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 36
- 239000008030 superplasticizer Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- BICZJRAGTCRORZ-UHFFFAOYSA-N 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(O)C=C1 BICZJRAGTCRORZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-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
- 239000007788 liquid Substances 0.000 claims description 3
- 125000005394 methallyl group Chemical group 0.000 claims description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 25
- 239000004568 cement Substances 0.000 abstract description 14
- 239000006185 dispersion Substances 0.000 abstract description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 4
- 239000011372 high-strength concrete Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000463 material Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 16
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 14
- 238000007334 copolymerization reaction Methods 0.000 description 14
- 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 12
- 230000001603 reducing effect Effects 0.000 description 12
- 239000000600 sorbitol Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 8
- 230000000740 bleeding effect Effects 0.000 description 7
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- OYXJBXRTVVLLSJ-UHFFFAOYSA-N prop-2-enoxyboronic acid Chemical compound OB(O)OCC=C OYXJBXRTVVLLSJ-UHFFFAOYSA-N 0.000 description 7
- 150000001642 boronic acid derivatives Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- JLNSPUHKOIYHEZ-UHFFFAOYSA-L disodium 2-hydroxy-2-oxo-1-sulfinylethanolate Chemical compound C(=O)(C(=S=O)[O-])O.C(=O)(C(=S=O)[O-])O.[Na+].[Na+] JLNSPUHKOIYHEZ-UHFFFAOYSA-L 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- -1 alcohol amine Chemical class 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011376 self-consolidating concrete Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- QHFAXRHEKNHTDH-UHFFFAOYSA-N (2-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1C=C QHFAXRHEKNHTDH-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- KJTCDHVTSYVFSY-UHFFFAOYSA-N OC(C)(C)C(C)(C)O.OC1=CC=C(C=C1)OB(O)O Chemical compound OC(C)(C)C(C)(C)O.OC1=CC=C(C=C1)OB(O)O KJTCDHVTSYVFSY-UHFFFAOYSA-N 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- AJXNWWLXMKDNHF-UHFFFAOYSA-L disodium;2-hydroxy-2-sulfonatoacetate Chemical compound [Na+].[Na+].[O-]C(=O)C(O)S([O-])(=O)=O AJXNWWLXMKDNHF-UHFFFAOYSA-L 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- XZSQWMVRHAYHRX-UHFFFAOYSA-N hydroxy phenyl hydrogen phosphate Chemical compound OOP(O)(=O)OC1=CC=CC=C1 XZSQWMVRHAYHRX-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QGLVEAGMVUQOJP-UHFFFAOYSA-N prop-2-enylboronic acid Chemical group OB(O)CC=C QGLVEAGMVUQOJP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to the field of concrete additives, in particular to an esterified product, low-hydration heat ether polycarboxylate water reducer and a preparation method thereof. Wherein the low hydration heat ether type polycarboxylate water reducer comprises an esterification product, unsaturated polyoxyethylene ether, acrylic acid, an unsaturated ester monomer and a functional monomer B; the functional monomer B is a monomer with double bonds and borate. The low-hydration heat ether polycarboxylate water reducer provided by the invention has better dispersion capability, and adaptability to cement, aggregate impurities and environment, obviously improves the workability of concrete, can further complex calcium ions in the concrete, has strong binding capability, effectively reduces hydration heat of high-strength concrete, and has good application prospect and popularization value.
Description
Technical Field
The invention relates to the field of concrete additives, in particular to an esterified product, low-hydration heat ether polycarboxylate water reducer and a preparation method thereof.
Background
Along with the continuous development of the infrastructure, the concrete structure gradually advances towards the directions of complicacy, high strength and high performance, various large spans and novel structural bridges continuously appear, and higher requirements are also put on the performance of the concrete. The high-strength self-compacting concrete has higher strength and excellent working performance, the self-compacting performance can meet the requirements of construction of complex structures such as small operation space, difficult vibration, dense reinforcing steel bars and the like, and the higher strength can effectively resist external damage.
In order to meet the performances of high strength, high fluidity, high filling property and the like, the high-strength self-compacting concrete is generally higher in cementing material consumption than ordinary concrete, the early hydration speed of the concrete is high due to the higher cement consumption, the temperature shrinkage cracking is more likely to occur due to the large hydration heat release amount, and in order to solve the problem, the cement hydration is delayed by adopting a method of compounding a hydration heat inhibitor and a retarder at present, so that the hydration heat is reduced. However, most hydration heat inhibitors have the problems of poor adaptability to water reducing agents and cement, and long-term non-coagulation of concrete caused by a compound retarder, so that the development of the polycarboxylate water reducing agent with good dispersion performance and capability of reducing hydration heat has important significance in ensuring engineering quality.
The patent document with publication number of CN107868187A and publication date of 2018, 04 and 03 discloses a preparation method of a low hydration heat polycarboxylate water reducer, which is mainly prepared by mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, hydroxyphenyl phosphoric acid monomer and polymerization inhibitor, catalyzing and preparing functional monomer under the protection of nitrogen, and carrying out free polymerization reaction with polyether macromonomer, initiator and chain transfer agent to obtain the low hydration heat polycarboxylate water reducer.
Patent document with publication number of CN109880023A and publication date of 2019, 06 and 14 discloses a polycarboxylate water reducer for early-strength anti-cracking machine-made sand and a preparation method thereof, wherein polyamine ether macromonomer, polyalcohol ether macromonomer, amide monomer, unsaturated phenyl monomer and polyhydroxy alkene compound are subjected to free radical polymerization in an initiator and a chain transfer agent, and the workability and anti-cracking capability are improved mainly by introducing rigid phenyl groups, but the effect of reducing hydration heat is not mentioned.
The patent document with publication number of CN105712650A and publication date of 2016-06-29 discloses a preparation method of a high-adaptability polycarboxylate superplasticizer, which comprises the steps of fully mixing a monomer a with a chain transfer agent, an initiator and water, and then adding the mixture into N 2 Reversible addition-fragmentation chain transfer polymerization is carried out under the protection to prepare a polyether macromonomer-RAFT reagent, and then the polyether macromonomer-RAFT reagent is reacted with a monomer b and a monomer c in N 2 The polymerization reaction is carried out under the protection to prepare the highly-adaptive polycarboxylate superplasticizer, but the reaction steps are more complex, and the effect of reducing the hydration heat is not mentioned.
Disclosure of Invention
In order to solve the problems that the hydration heat inhibitor has poor adaptability to water reducer and cement, and the compound retarder is non-coagulated for a long time, the invention provides an esterification product which is mainly prepared by esterification reaction of functional monomer A and unsaturated acid;
the functional monomer A is a monomer with benzene ring, borate and hydroxyl.
In some embodiments, the functional monomer a has the structural formula:
the functional monomer A is 4-hydroxyphenylboronic acid pinacol ester.
In some embodiments, the unsaturated acid is one of acrylic acid, methacrylic acid.
In some embodiments, the esterification reaction process is to add unsaturated acid and functional monomer into a reaction vessel for mixing, add catalyst and polymerization inhibitor under the condition of nitrogen, adjust the temperature to 120-135 ℃ and react for 4-6 h, thus obtaining the esterification product.
In some embodiments, the catalyst is one of cerium sulfate, concentrated sulfuric acid, and p-toluenesulfonic acid
In some embodiments, the polymerization inhibitor comprises at least one of hydroquinone, diphenylamine, methyl hydroquinone.
In some embodiments, the molar ratio of the functional monomer A to the unsaturated acid is 1:1.5-4, the catalyst is used in an amount of 0.8-2.5% of the total mass of the unsaturated acid and the functional monomer A, and the polymerization inhibitor is used in an amount of 0.5-3% of the total mass of the unsaturated acid and the functional monomer A.
The invention also provides a low-hydration heat ether polycarboxylate water reducer adopting the esterification product, which comprises the esterification product, unsaturated polyoxyethylene ether, acrylic acid, unsaturated ester monomer and functional monomer B;
the functional monomer B is a monomer with double bonds and borate.
In some embodiments, the functional monomer B is 2-propenylboronic acid.
In some embodiments, the unsaturated polyoxyethylene ether is one of 4-hydroxybutyl vinyl ether polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene polyoxypropylene ether, or allyl alcohol polyoxyethylene ether having a molecular weight of 2000-5000.
In some embodiments, the unsaturated ester monomer is one of methyl methacrylate, hydroxyethyl acrylate, or hydroxypropyl methacrylate.
In some embodiments, the mass ratio of the esterification product, the unsaturated polyoxyethylene ether, the acrylic acid, the unsaturated ester monomer and the functional monomer B is 3-6:100:4-10:2-5:2-4.
In some embodiments, the composition further comprises an emulsifier, wherein the emulsifier is sorbitol polyoxyethylene ether tetraoleate, and the amount of the emulsifier is 0.5-1.5% of the total mass of the unsaturated polyoxyethylene ether. Preferably, the polymerization degree of the sorbitol polyoxyethylene ether tetraoleate is 15.
In some embodiments, a chain transfer agent is also included in the composition, the chain transfer agent being one of thioglycolic acid, n-butyl mercaptan, 3-mercaptopropionic acid, trisodium phosphate. The consumption of the chain transfer agent is 0.5-2.5% of the total mass of the unsaturated polyoxyethylene ether.
In some embodiments, an initiator is also included in the composition, the initiator including an oxidizing agent and a reducing agent.
In some embodiments, the oxidizing agent is one of ammonium persulfate, potassium persulfate, sodium persulfate, and hydrogen peroxide. The consumption of the oxidant is 1.5 to 3.5 percent of the total mass of the unsaturated polyoxyethylene ether.
In some embodiments, the reducing agent is one of sodium hypophosphite, disodium 2-hydroxy-2-sulfinylacetate, ascorbic acid, or disodium 2-hydroxy-2-sulfinylacetate. The consumption of the reducing agent is 0.8-2.5% of the total mass of the unsaturated polyoxyethylene ether.
The invention also provides a preparation method of the low-hydration heat ether polycarboxylate superplasticizer, which comprises the following steps:
adding the esterification product, the unsaturated polyoxyethylene ether and the emulsifier into a reaction container for mixing, respectively dripping a chain transfer agent solution, an initiator solution and a mixed solution of acrylic acid, an unsaturated ester monomer and a functional monomer B, reacting for 1.5-2 h at room temperature, preserving heat for a period of time after the reaction is finished, and adding liquid alkali to adjust the pH value to 6-7 to obtain the low hydration heat ether polycarboxylate water reducer.
Preferably, the liquid base is a 32% strength by mass sodium hydroxide solution.
Based on the above, the invention has the following beneficial effects:
1. the invention utilizes 4-hydroxyphenylboronic acid pinacol ester and unsaturated acid to prepare an esterification product, has the advantages of low cost and simple operation, and the prepared esterification product participates in the next copolymerization reaction to lead the main chain of the polycarboxylate water reducer to be provided with benzene rings, boric acid, hydroxyl groups and other groups, and leads the main chain to be provided with rigid benzene rings, so that the main chain has a rigid and difficult-to-bend structure, and ensures that water reducer molecules are difficult to be buried by stone powder in machine-made sand, thereby improving the workability of concrete; and under the alkaline condition of cement, the ester group of the esterified product is gradually hydrolyzed along with the extension of time to continuously release carboxylic acid groups contributing to the water reducing effect, so that the lost water reducing rate is compensated, and the slump retaining effect is achieved.
2. The self-made esterification product and the 2-propylene boric acid participate in copolymerization reaction, so that the polycarboxylate water reducer has a plurality of borates in molecules, the borates have stronger adsorption capacity than carboxyl, the dispersion capacity of the polycarboxylate water reducer can be greatly improved, and the adaptability to cement, aggregate impurities and environment can be greatly improved, so that the workability of concrete is improved, and meanwhile, the borates can complex calcium ions in a pore solution, have strong binding capacity, and can effectively reduce the hydration heat of high-strength concrete.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure and/or components pointed out in the written description and claims.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in conjunction with the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some, but not all, embodiments of the present invention; the technical features designed in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
A1, preparing an esterification product: adding 98 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 1.59 parts of cerium sulfate and 2.97 parts of hydroquinone under the protection of nitrogen, regulating the reaction temperature to 120 ℃, and reacting for 5 hours to obtain an esterification product;
a2, copolymerization reaction: according to parts by weight, adding 5 parts of the esterification product prepared in the step A1, 100 parts of 4-hydroxybutyl vinyl ether polyoxyethylene ether with the molecular weight of 3000, 0.8 part of sorbitol polyoxyethylene ether tetraoleate and 119 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2 parts of ammonium persulfate and 20 parts of water into a first dripping device; 2 parts of sodium hypophosphite, 1.2 parts of thioglycollic acid and 20 parts of water are uniformly mixed in a second dripping device; mixing 8 parts of acrylic acid, 3 parts of hydroxyethyl acrylate, 3 parts of 2-propenylboric acid and 20 parts of water uniformly in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the low-hydration heat ether polycarboxylate superplasticizer with the mass concentration of 40%.
Example 2
B1, preparation of an esterification product: adding 58.6 parts of methacrylic acid and 100 parts of 4-hydroxyphenylboric acid pinacol ester into a first reaction vessel for mixing, adding 2.38 parts of concentrated sulfuric acid and 0.80 part of diphenylamine under the protection of nitrogen, regulating the reaction temperature to 135 ℃, and reacting for 4 hours to obtain an esterified product;
b2, copolymerization reaction: according to parts by weight, adding 3 parts of the esterified product prepared by the B1, 100 parts of methyl allyl alcohol polyoxyethylene ether with the molecular weight 2400, 1.5 parts of sorbitol polyoxyethylene ether tetraoleate and 113 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 1.5 parts of hydrogen peroxide and 20 parts of water into a first dripping device; mixing 0.8 part of ascorbic acid, 2 parts of n-butyl mercaptan and 20 parts of water uniformly in a second dripping device; uniformly mixing 4 parts of acrylic acid, 5 parts of methyl methacrylate, 4 parts of 2-propenylboric acid and 20 parts of water in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the low-hydration heat ether polycarboxylate superplasticizer with the mass concentration of 40%.
Example 3
C1, preparation of an esterification product: adding 156 parts of methacrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 6.4 parts of p-toluenesulfonic acid and 5.12 parts of methyl hydroquinone under the protection of nitrogen, regulating the reaction temperature to 125 ℃, and reacting for 6 hours to obtain an esterification product;
c2, copolymerization reaction: according to weight parts, adding 6 parts of the esterification product prepared by C1, 100 parts of allyl polyoxyethylene polyoxypropylene ether with molecular weight of 3000, 0.5 part of sorbitol polyoxyethylene ether tetraoleate and 123 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 3 parts of potassium persulfate and 20 parts of water into a first dripping device; 2.5 parts of 2-hydroxy-2-sulfinylacetic acid disodium salt, 0.5 part of 3-mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; uniformly mixing 10 parts of acrylic acid, 2 parts of hydroxypropyl methacrylate, 2 parts of 2-propenylboric acid and 20 parts of water in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 2 hours, and reacting at constant temperature for 0.5 hour;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the low-hydration heat ether polycarboxylate superplasticizer with the mass concentration of 40%.
Example 4
D1, preparation of an esterification product: adding 65.4 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 3.3 parts of cerium sulfate and 4.9 parts of hydroquinone under the protection of nitrogen, regulating the reaction temperature to 130 ℃, and reacting for 5 hours to obtain an esterification product;
d2, copolymerization reaction: according to parts by weight, adding 4 parts of the esterification product prepared by D1, 100 parts of methallyl polyoxyethylene polyoxypropylene ether with a molecular weight of 5000, 0.8 part of sorbitol polyoxyethylene ether tetraoleate and 116 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 3.5 parts of sodium persulfate with 20 parts of water in a first dripping device; 1.5 parts of 2-hydroxy-2-sulfoacetic acid disodium salt, 2.5 parts of trisodium phosphate and 20 parts of water are uniformly mixed in a second dripping device; mixing 6 parts of acrylic acid, 4 parts of hydroxyethyl acrylate, 3 parts of 2-propenylboric acid and 20 parts of water uniformly in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 2 hours, and reacting at constant temperature for 0.5 hour;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the low-hydration heat ether polycarboxylate superplasticizer with the mass concentration of 40%.
Comparative example 1
And (3) selecting commercial Poi nt-TS8 polycarboxylate superplasticizer mother liquor and boric acid, and compounding the commercial Poi nt-TS8 polycarboxylate superplasticizer mother liquor and the boric acid with the dosage of 0.15% and 0.2% of that of the cementing material respectively for concrete verification.
Comparative example 2
E1, preparation of esterification products: adding 98 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 1.59 parts of cerium sulfate and 2.97 parts of hydroquinone under the protection of nitrogen, regulating the reaction temperature to 120 ℃, and reacting for 5 hours to obtain an esterification product;
e2, copolymerization reaction: according to weight parts, adding 5 parts of the esterified product prepared by E1, 100 parts of 4-hydroxybutyl vinyl ether polyoxyethylene ether with molecular weight of 3000, 0.8 part of sorbitol polyoxyethylene ether tetraoleate and 119 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2 parts of ammonium persulfate and 20 parts of water in a first dripping device; 2 parts of sodium hypophosphite, 1.2 parts of thioglycollic acid and 20 parts of water are uniformly mixed in a second dripping device; mixing 8 parts of acrylic acid, 3 parts of hydroxyethyl acrylate, 3 parts of 2-propenylboric acid and 20 parts of water uniformly in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the low-hydration heat ether polycarboxylate superplasticizer with the mass concentration of 40%.
Comparative example 3
F1, copolymerization reaction: according to weight parts, firstly adding 100 parts of 4-hydroxybutyl vinyl ether polyoxyethylene ether with molecular weight of 3000, 0.8 part of sorbitol polyoxyethylene ether tetraoleate and 112 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2 parts of ammonium persulfate and 20 parts of water into a first dripping device; 2 parts of sodium hypophosphite, 1.2 parts of thioglycollic acid and 20 parts of water are uniformly mixed in a second dripping device; mixing 8 parts of acrylic acid, 3 parts of hydroxyethyl acrylate, 3 parts of 2-propenylboric acid and 20 parts of water uniformly in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the low-hydration heat ether polycarboxylate superplasticizer with the mass concentration of 40%.
Comparative example 4
G1, preparation of esterification products: adding 98 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 1.59 parts of cerium sulfate and 2.97 parts of hydroquinone under the protection of nitrogen, regulating the reaction temperature to 120 ℃, and reacting for 5 hours to obtain an esterification product;
g2, copolymerization reaction: according to weight parts, adding 5 parts of the esterification product prepared by G1, 100 parts of 4-hydroxybutyl vinyl ether polyoxyethylene ether with molecular weight of 3000, 0.8 part of sorbitol polyoxyethylene ether tetraoleate and 115 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2 parts of ammonium persulfate and 20 parts of water in a first dripping device; 2 parts of sodium hypophosphite, 1.2 parts of thioglycollic acid and 20 parts of water are uniformly mixed in a second dripping device; mixing 8 parts of acrylic acid, 3 parts of hydroxyethyl acrylate and 20 parts of water uniformly in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the low-hydration heat ether polycarboxylate superplasticizer with the mass concentration of 40%.
Comparative example 5
H1, preparation of esterification products: adding 98 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 1.59 parts of cerium sulfate and 2.97 parts of hydroquinone under the protection of nitrogen, regulating the reaction temperature to 120 ℃, and reacting for 5 hours to obtain an esterification product;
h2, copolymerization: according to weight parts, adding 5 parts of an esterification product prepared by H1, 100 parts of 4-hydroxybutyl vinyl ether polyoxyethylene ether with a molecular weight of 3000, 0.8 part of sorbitol polyoxyethylene ether tetraoleate and 119 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2 parts of ammonium persulfate and 20 parts of water in a first dropwise adding device; 2 parts of sodium hypophosphite, 1.2 parts of thioglycollic acid and 20 parts of water are uniformly mixed in a second dripping device; 8 parts of acrylic acid, 3 parts of hydroxyethyl acrylate, 3 parts of vinylphenylboronic acid and 20 parts of water are uniformly mixed in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the low-hydration heat ether polycarboxylate superplasticizer with the mass concentration of 40%.
Comparative example 6
I1, preparation of an esterification product: adding 98 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 1.59 parts of cerium sulfate and 2.97 parts of hydroquinone under the protection of nitrogen, regulating the reaction temperature to 120 ℃, and reacting for 5 hours to obtain an esterification product;
and I2, copolymerization reaction: according to weight parts, adding 5 parts of the esterified product prepared by I1, 100 parts of 4-hydroxybutyl vinyl ether polyoxyethylene ether with molecular weight of 3000, 0.8 part of sorbitol polyoxyethylene ether tetraoleate and 119 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2 parts of ammonium persulfate and 20 parts of water in a first dripping device; 2 parts of sodium hypophosphite, 1.2 parts of thioglycollic acid and 20 parts of water are uniformly mixed in a second dripping device; 8 parts of acrylic acid, 3 parts of hydroxyethyl acrylate, 3 parts of 2-acrylamide phenylboronic acid and 20 parts of water are uniformly mixed in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the low-hydration heat ether polycarboxylate superplasticizer with the mass concentration of 40%.
Comparative example 7
J1, copolymerization reaction: according to the weight parts, firstly adding 5 parts of 2-acrylamide phenylboronic acid, 100 parts of 4-hydroxybutyl vinyl ether polyoxyethylene ether with the molecular weight of 3000, 0.8 part of sorbitol polyoxyethylene ether tetraoleate and 119 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2 parts of ammonium persulfate and 20 parts of water in a first dripping device; 2 parts of sodium hypophosphite, 1.2 parts of thioglycollic acid and 20 parts of water are uniformly mixed in a second dripping device; mixing 8 parts of acrylic acid, 3 parts of hydroxyethyl acrylate, 3 parts of 2-propenylboric acid and 20 parts of water uniformly in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the low-hydration heat ether polycarboxylate superplasticizer with the mass concentration of 40%.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limited thereto; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.
In addition, unless otherwise specified, the starting materials employed may also be commercially available products conventionally used in the art or may be prepared by methods conventionally used in the art.
The low hydration heat ether type polycarboxylate water reducer synthesized in examples 1-4 is compared with the machine-made sand concrete used in comparative examples 1-7, conch PO52.5R cement is adopted, the mixing amount of the water reducer in examples 1-4 is 0.15 percent (folded solid content) of the cementing material, the mixing amount of the water reducer in comparative examples 2-7 is 0.15 percent (folded solid content) of the cementing material, and the mixing amount of the additive in comparative example 1 refers to a specific compound formula. According to GB 8076-2008 concrete admixture, the bleeding rate, the expansion degree and the like of the concrete admixture are measured, and the concrete mixing ratio is as follows: 430kg/m cement 3 30kg/m of fly ash 3 90kg/m of mineral powder 3 700kg/m machine-made sand 3 682kg/m of large stone 3 368kg/m of small stone 3 The concrete test results are shown in Table 1, and the samples of the examples and comparative examples were subjected to a cement hydration heat test in accordance with the above admixture amounts, and the 3d hydration heat values are shown in Table 2.
Table 1 concrete performance test data
Table 2 comparison of the heat of hydration and the heat of hydration reduction of the cements of examples and comparative examples
Sample of | 3d hydration Heat value (J/g) | Reduction rate/% |
Example 1 | 214.7 | 33.00% |
Example 2 | 213.5 | 33.4% |
Example 3 | 219.4 | 31.5% |
Example 4 | 215.3 | 32.8% |
Comparative example 1 | 320.5 | - |
Comparative example 2 | 280.3 | 12.5% |
Comparative example 3 | 270.4 | 15.6% |
Comparative example 4 | 276.1 | 13.9% |
Comparative example 5 | 262.5 | 18.1% |
Comparative example 6 | 260.4 | 18.8% |
Comparative example 7 | 272.2 | 15.1% |
As can be seen from the test results of tables 1 and 2, the performances of the examples are superior to those of the comparative examples, and the results of the examples 1-4 and the comparative example 1 show that compared with the mode of adopting the existing water reducing agent to compound retarder, the low-hydration heat ether polycarboxylate water reducing agent provided by the invention has better water reducing and slump retaining performances, lower bleeding rate ratio and good workability, and greatly reduces the hydration heat of cement 3 d;
as can be seen from example 1 and comparative example 2, the effect of the polycarboxylate water reducer prepared by directly participating in copolymerization after esterification reaction of the functional monomer A selected by the invention is better than that of the polycarboxylate water reducer prepared by participating in copolymerization after 4-hydroxyphenyl phosphorylation in terms of water reducing performance, hydration heat reducing performance, bleeding rate ratio and workability;
from the embodiment 1 and the proportion 3-4, the addition of the esterified product and the functional monomer B effectively enhances the water-reducing and slump-retaining properties of the finally prepared polycarboxylate water reducer, so that the concrete added with the polycarboxylate water reducer has lower bleeding rate and good workability, and has obvious effect of reducing hydration heat;
meanwhile, by combining the comparative example 5 and the comparative example 6, compared with other types of boric acid monomers in the prior art, the functional monomer B adopted by the invention has better water reducing performance and hydration heat reducing effect, and the workability improving effect and bleeding rate reducing effect are more obvious;
compared with the water reducer prepared by directly copolymerizing unsaturated phenylboronic acid monomers containing double bonds, the water reducer prepared by the method has the advantages that the functional monomers A are esterified to prepare the esterified product containing benzene rings, borate and hydroxyl groups, and then the esterified product is copolymerized, so that the polycarboxylic acid water reducer has a plurality of borate groups in molecules, the borate groups have stronger adsorption capacity compared with carboxyl groups, the dispersion capacity of the polycarboxylic acid water reducer can be greatly improved, and the adaptability to cement, aggregate impurities and environment can be greatly improved, so that the bleeding rate ratio of concrete is reduced, the workability of the concrete is improved, and meanwhile, the borate groups can complex calcium ions in the concrete, the binding capacity is strong, and the hydration heat of the high-strength concrete can be effectively reduced.
In conclusion, compared with the prior art, the low-hydration heat ether polycarboxylate water reducer provided by the invention has better dispersion capability, and adaptability to cement, aggregate impurities and environment, obviously reduces the bleeding rate ratio of concrete, improves the workability of concrete, can further complex calcium ions in the concrete, has strong binding capability, effectively reduces the hydration heat of high-strength concrete, and has good application prospect and popularization value.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present invention may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Although terms such as an esterification product, an unsaturated polyoxyethylene ether, an acrylic acid, an unsaturated ester monomer, a functional monomer B, and the like are more used herein, the possibility of using other terms is not excluded. These terms are used merely for convenience in describing and explaining the nature of the invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention; the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (5)
1. A low hydration heat ether polycarboxylate water reducer is characterized in that: is prepared from an esterification product, unsaturated polyoxyethylene ether, acrylic acid, an unsaturated ester monomer and a functional monomer B;
the functional monomer B is a monomer with double bonds and borate;
the esterification product is obtained by esterification reaction of a functional monomer A and unsaturated acid;
the functional monomer A is a monomer with benzene ring, borate and hydroxyl at the same time;
the functional monomer A is 4-hydroxyphenylboronic acid pinacol ester; the structural formula of the functional monomer A is as follows:
the unsaturated acid is one of acrylic acid and methacrylic acid;
the mass ratio of the esterified product to the unsaturated polyoxyethylene ether to the acrylic acid to the unsaturated ester monomer to the functional monomer B is 3-4: 100:4 to 6:4 to 5:2 or 3 to 4:100:4 to 6:4 to 5:4.
2. the low hydration heat ether type polycarboxylate superplasticizer as defined in claim 1, wherein: the unsaturated polyoxyethylene ether is one of 4-hydroxybutyl vinyl ether polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene polyoxypropylene ether or allyl alcohol polyoxyethylene ether with the molecular weight of 2000-5000.
3. The low hydration heat ether type polycarboxylate superplasticizer as defined in claim 1, wherein: the unsaturated ester monomer is one of methyl methacrylate, hydroxyethyl acrylate or hydroxypropyl methacrylate.
4. The low hydration heat ether type polycarboxylate superplasticizer as defined in claim 1, wherein: the functional monomer B is 2-propylene boric acid.
5. A method for preparing the low hydration heat ether type polycarboxylate superplasticizer according to any one of claims 1-4, characterized in that: the method comprises the following steps:
adding the esterification product, the unsaturated polyoxyethylene ether and the emulsifier into a reaction container for mixing, respectively dripping a chain transfer agent solution, an initiator solution and a mixed solution of acrylic acid, an unsaturated ester monomer and a functional monomer B, reacting at room temperature, preserving heat after the reaction is finished, and adding liquid alkali to adjust the pH value to obtain the low-hydration heat ether polycarboxylate water reducer.
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