CN115385954A - Unsaturated phosphate ester containing catechol group and polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Unsaturated phosphate ester containing catechol group and polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
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- CN115385954A CN115385954A CN202211171102.0A CN202211171102A CN115385954A CN 115385954 A CN115385954 A CN 115385954A CN 202211171102 A CN202211171102 A CN 202211171102A CN 115385954 A CN115385954 A CN 115385954A
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- Prior art keywords
- unsaturated
- acid
- reducing agent
- catechol group
- unsaturated phosphate
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 37
- 239000002253 acid Substances 0.000 title claims abstract description 26
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims description 28
- -1 Unsaturated phosphate ester Chemical class 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 22
- 239000008030 superplasticizer Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002211 L-ascorbic acid Substances 0.000 claims description 8
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 229960003371 protocatechualdehyde Drugs 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- QCKLYDQORUPOIR-UHFFFAOYSA-N ethyl dimethyl phosphite Chemical compound CCOP(OC)OC QCKLYDQORUPOIR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- 229920000151 polyglycol Polymers 0.000 claims 2
- 239000010695 polyglycol Substances 0.000 claims 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims 1
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 31
- 230000000740 bleeding effect Effects 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 58
- 239000007787 solid Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000004576 sand Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 239000004568 cement Substances 0.000 description 12
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XSHISXQEKIKSGC-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate;hydron;chloride Chemical compound Cl.CC(=C)C(=O)OCCN XSHISXQEKIKSGC-UHFFFAOYSA-N 0.000 description 2
- DXLZNKULUVFFFY-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate;hydrochloride Chemical compound Cl.NCCOC(=O)C=C DXLZNKULUVFFFY-UHFFFAOYSA-N 0.000 description 2
- 101000908015 Homo sapiens Putative inactive carboxylesterase 4 Proteins 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 102100023322 Putative inactive carboxylesterase 4 Human genes 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 description 1
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
-
- 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
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of concrete, and particularly relates to o-catechol group-containing unsaturated phosphate and a polycarboxylic acid water reducing agent and a preparation method thereof, wherein the o-catechol group-containing unsaturated phosphate has the following structural formula:
wherein R is 1 Is hydrogen or methyl, R 2 The concrete is methyl or ethyl, so as to solve the problems of sensitivity, quick loss, large hysteresis return and bleeding of concrete under different environmental temperatures, different aggregate mud contents and different admixture mixing amounts.
Description
Technical Field
The invention belongs to the technical field of concrete, and particularly relates to an unsaturated phosphate ester and polycarboxylic acid water reducing agent containing catechol groups and a preparation method thereof.
Background
With the rapid development of domestic economy, the construction industry has also been unprecedented. The concrete is used as a building material with the largest modern use amount and the most extensive application, and the preparation technology of the concrete is continuously developed. Concrete admixture, especially water reducing agent, is a key raw material for the development of high performance of concrete, can enable the concrete to achieve better fluidity under lower mixing amount, improve the workability of the concrete and improve the strength of the concrete, and is widely applied to heavy projects such as highways, bridges, tunnels, dams and the like. The polycarboxylate superplasticizer is a third-generation high-performance water reducing agent developed after a common water reducing agent represented by lignosulfonate and a high-efficiency water reducing agent represented by naphthalene and sulfamate systems, has the advantages of high water reducing rate, low mixing amount, diversified structure and function and the like, can reduce the cost, but has the defect of high sensitivity to concrete materials, easily causes the problems of over-fast concrete loss, segregation, bleeding and the like, and increases the difficulty in concrete production control.
In recent years, with the increasing expansion of construction scale, the demand of sandstone in concrete raw materials is also increasing, high-quality natural sand resources in China are increasingly exhausted, and meanwhile, in order to protect the ecological environment and guarantee the use safety of shipping and bridges, the exploitation of natural sand is also strictly limited, and the yield is increasingly tense. At present, machine-made sand aggregate gradually replaces natural sand to become a main source of building sand. However, due to the fact that the machine-made sand is too fast in application process, the machine-made sand is not sufficiently known, and factors such as production process and production management are insufficient, the machine-made sand and natural sand produced at present have large difference in performance (rough particle surface, more edges and corners, poor gradation and the like), and meanwhile, the parent rock source is unstable, the rock powder content fluctuation is large, and the quality levels are not uniform. The problems of poor wrapping property, poor fluidity, large loss, easy segregation, bleeding and the like of the concrete mixture are often caused, and the hidden danger of the engineering quality is easily caused.
Disclosure of Invention
The embodiment of the invention provides an unsaturated phosphate ester containing catechol group and a polycarboxylic acid water reducing agent and a preparation method thereof, which are used for solving the problems of sensitivity, quick loss, large hysteresis and bleeding of concrete at different environmental temperatures, different aggregate mud contents and different admixture mixing amounts.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
the application provides an unsaturated phosphate containing catechol group, which has the following structural formula:
wherein R is 1 Is hydrogen or methyl, R 2 Is methyl or ethyl.
The application also provides a preparation method of the o-catechol group-containing unsaturated phosphate ester, which comprises the following steps:
mixing 2-aminoethyl (methyl) acrylate hydrochloride with protocatechualdehyde and dimethyl (ethyl) phosphite, and reacting under the action of an alkaline catalyst to prepare the unsaturated phosphate containing a catechol group.
In some embodiments, the molar ratio of 2-aminoethyl (meth) acrylate hydrochloride, protocatechualdehyde, dimethyl (ethyl) phosphite to basic catalyst is (1.00-1.05): 1:1:1.16.
in some embodiments, the basic catalyst comprises at least one of trimethylamine, triethylamine, and 4-dimethylaminopyridine.
In some embodiments, the reaction temperature is 60-80 ℃ and the reaction time is 4-5h.
The application also provides a polycarboxylate water reducer which comprises the following components:
polyether macromonomer, unsaturated acid, the above-mentioned ortho-diphenol group-containing unsaturated phosphate ester, unsaturated ester, chain transfer agent, oxidant, reducing agent and alkali liquor.
The molar ratio of the polyether macromonomer, the unsaturated acid, the unsaturated phosphate containing the catechol group, the unsaturated ester, the chain transfer agent, the oxidant, the reducing agent and the alkali liquor is 1: (1.5-2.5): (0.2-0.5): (3.0-4.0): (0.1-0.6): (0.1-0.3): (0.02-0.04): (0.3-0.5).
In some embodiments, the polyether macromonomer has a molecular weight of 2000 to 3000, and the polyether macromonomer comprises at least one of isobutenol polyoxyethylene ether, prenol polyoxyethylene ether, vinyl polyethylene glycol ether, and vinyloxybutyl polyethylene glycol ether.
In some embodiments, the unsaturated acid comprises at least one of acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, and fumaric acid.
The unsaturated ester comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
In some embodiments, the chain transfer agent comprises at least one of mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid, and sodium hypophosphite.
The oxidant comprises at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate.
The reducing agent includes at least one of sodium formaldehyde sulfoxylate and L-ascorbic acid.
The base comprises at least one of sodium hydroxide, potassium hydroxide, triethylamine and triethanolamine.
The application also provides a preparation method of the polycarboxylate superplasticizer, which comprises the following steps:
reacting a polyether macromonomer with an oxidant, unsaturated acid, unsaturated ester, unsaturated phosphate containing catechol group, a chain transfer agent and a reducing agent at the temperature of 10-40 ℃, preserving heat for 0.5-3 h, and adding alkali after preserving heat to obtain the polycarboxylic acid water reducing agent.
The invention has the positive effects that:
1. the o-catechol group is introduced into the unsaturated phosphate containing the o-catechol group, and the o-catechol group is used for synthesizing the polycarboxylic acid water reducing agent, so that the adsorption capacity of cement paste on the surface of low-surface-energy machine-made sand can be improved, and the dispersion capacity of the water reducing agent in concrete and the workability of the concrete can be effectively improved.
2. The unsaturated phosphate containing the catechol group provided by the invention is introduced with phosphate groups in the molecular structure, and is used for synthesizing the polycarboxylate superplasticizer, the molecular structure of the molecular side chain of the polycarboxylate superplasticizer can be changed, so that a large amount of phosphate ions and micromolecular alcohol are generated when molecules of the polycarboxylate superplasticizer are hydrolyzed in cement slurry, and the hydration process of cement can be greatly delayed, thereby overcoming the defects of sensitivity, poor workability and the like of the traditional polycarboxylate superplasticizer to concrete materials, and realizing the dual functions of low sensitivity and high slump loss resistance of the polycarboxylate superplasticizer.
3. Unsaturated ester monomers are introduced into the molecular structure of the polycarboxylate superplasticizer, so that a large amount of carboxylate ions playing a water reducing role can be slowly released under an alkaline condition, and the slump retaining effect of the polycarboxylate superplasticizer is further improved.
4. The preparation reaction process of the o-catechol group-containing unsaturated phosphate ester is simple, easy to operate and free of pollution.
5. The polycarboxylate superplasticizer disclosed by the invention has excellent performance, has the advantages of strong slump retaining capability, good adaptability to cement, insensitivity to mud and powder contents in concrete materials, improvement on concrete workability and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
Preparation of an unsaturated phosphate containing a catechol group: adding 100mL of absolute ethanol into a clean reaction container, then adding 12.2g of 2-aminoethyl acrylate hydrochloride, 13.8g of protocatechualdehyde and 11.7g of triethylamine, opening and stirring, fully dissolving, then dropwise adding 11.0g of dimethyl phosphite into the solution, keeping the temperature at 60 ℃ for 4 hours, filtering to remove white precipitates to obtain light yellow liquid, removing ethanol by rotary evaporation to obtain light yellow solid, and drying in vacuum to obtain light yellow solid powder, namely unsaturated phosphate containing catechol groups (recorded as BQP-1), wherein the structural formula is as follows:
unsaturated phosphate (BQP-1) containing catechol groups participates in polymerization reaction to prepare the polycarboxylic acid water reducing agent, and the preparation process is as follows:
337g of vinyl polyethylene glycol ether (VPEG) with the molecular weight of 3000 and 342g of water are added into a reaction vessel and stirred to be dissolved, and meanwhile, a material A and a material B are prepared and added dropwise, wherein the material A comprises the following components: 17g of acrylic acid, 40g of hydroxyethyl acrylate, 8g of unsaturated phosphate (BQP-1) containing catechol group and 20g of water are mixed uniformly; b, material B: 1.8g mercaptopropionic acid, 0.5g L-ascorbic acid and 60g water were mixed well. Controlling the initial temperature in the reaction container to be 15 ℃, adding 3.0g of 27.5% hydrogen peroxide solution into the reaction solvent at one time, stirring for 5 minutes, then beginning to dropwise add the material A and the material B, dropwise adding the material A for 50 minutes, dropwise adding the material B for 60 minutes, preserving the heat for 60 minutes after dropwise adding the material B, replenishing water to adjust the concentration of the polymer, and adding alkali to adjust the pH value to be 5-6 to obtain the low-sensitive high-slump-retention type polycarboxylate superplasticizer PCE-1 with the solid content of 40%.
Example 2
Preparation of o-catechol group-containing unsaturated phosphate ester: adding 100mL of absolute ethanol into a clean reaction container, then adding 12.2g of 2-aminoethyl acrylate hydrochloride, 13.8g of protocatechualdehyde and 11.7g of triethylamine, opening and stirring, fully dissolving, then dropwise adding 13.8g of diethyl phosphite into the solution, keeping the temperature at 60 ℃ for 4 hours, filtering to remove white precipitates to obtain light yellow liquid, removing ethanol by rotary evaporation to obtain light yellow solid, and drying in vacuum to obtain light yellow solid powder, namely unsaturated phosphate containing catechol groups (recorded as BQP-2), wherein the structural formula is as follows:
unsaturated phosphate (BQP-2) containing catechol groups participates in polymerization reaction to prepare the polycarboxylic acid water reducing agent, and the preparation process is as follows:
337g of vinyl polyethylene glycol ether (VPEG) with a molecular weight of 3000 and 342g of water are added into a reaction vessel and dissolved by stirring, and meanwhile, a material A and a material B are prepared, wherein the weight ratio of the material A: 17g of acrylic acid, 40g of hydroxyethyl acrylate, 8.7g of o-catechol-group unsaturated phosphate ester (BQP-2) and 20g of water are mixed uniformly; b, material B: 1.8g mercaptopropionic acid, 0.5g L-ascorbic acid and 60g water were mixed well. Controlling the initial temperature in the reaction container to be 15 ℃, adding 3.0g of 27.5% hydrogen peroxide solution into the reaction solvent at one time, stirring for 5 minutes, then beginning to dropwise add the material A and the material B, dropwise adding the material A for 50 minutes, dropwise adding the material B for 60 minutes, preserving heat for 60 minutes after dropwise adding the material B, replenishing water to adjust the polymer concentration, adding alkali to adjust the pH value to be 5-6, and obtaining the low-sensitivity high-slump-retention type polycarboxylate superplasticizer PCE-2 with the solid content of 40%.
Example 3
Preparation of o-catechol group-containing unsaturated phosphate ester: adding 100mL of absolute ethanol into a clean reaction vessel, then adding 13.7g of 2-aminoethyl methacrylate hydrochloride, 13.8g of protocatechuic aldehyde and 11.7g of triethylamine, stirring, fully dissolving, then dropwise adding 11g of dimethyl phosphite into the solution, keeping the temperature at 60 ℃ for 4 hours, filtering to remove white precipitates to obtain light yellow liquid, removing ethanol by rotary evaporation to obtain light yellow solid, and drying in vacuum to obtain light yellow solid powder, namely unsaturated phosphate containing catechol groups (recorded as BQP-3), wherein the structural formula is as follows:
unsaturated phosphate (BQP-3) containing catechol groups participates in polymerization reaction to prepare the polycarboxylic acid water reducing agent, and the preparation process is as follows:
337g of vinyl polyethylene glycol ether (VPEG) with a molecular weight of 3000 and 342g of water are added into a reaction vessel and dissolved by stirring, and meanwhile, a material A and a material B are prepared, wherein the weight ratio of the material A: 17g of acrylic acid, 40g of hydroxyethyl acrylate, 8.4g of o-catechol-group unsaturated phosphate ester (BQP-3) and 20g of water are mixed uniformly; b, material B: 1.8g mercaptopropionic acid, 0.5g L-ascorbic acid and 60g water were mixed well. Controlling the initial temperature in the reaction container to be 15 ℃, adding 3.0g of 27.5% hydrogen peroxide solution into the reaction solvent at one time, stirring for 5 minutes, then beginning to dropwise add the material A and the material B, dropwise adding the material A for 50 minutes, dropwise adding the material B for 60 minutes, preserving heat for 60 minutes after dropwise adding the material B, replenishing water to adjust the polymer concentration, adding alkali to adjust the pH value to be 5-6, and obtaining the low-sensitivity high-slump-retention type polycarboxylate superplasticizer PCE-3 with the solid content of 40%.
Example 4
Preparation of an unsaturated phosphate containing a catechol group: adding 100mL of absolute ethanol into a clean reaction vessel, then adding 13.7g of 2-aminoethyl methacrylate hydrochloride, 13.8g of protocatechuic aldehyde and 11.7g of triethylamine, stirring, fully dissolving, then dropwise adding 13.8g of diethyl phosphite into the solution, keeping the temperature at 60 ℃ for 4 hours, filtering to remove white precipitates to obtain light yellow liquid, removing ethanol by rotary evaporation to obtain light yellow solid, and drying in vacuum to obtain light yellow solid powder, namely unsaturated phosphate containing catechol groups (recorded as BQP-4), wherein the structural formula is as follows:
unsaturated phosphate (BQP-4) of a catechol group participates in a polymerization reaction to prepare the polycarboxylic acid water reducing agent, and the preparation process is as follows:
337g of vinyl polyethylene glycol ether (VPEG) with the molecular weight of 3000 and 342g of water are added into a reaction vessel and stirred to be dissolved, and meanwhile, a material A and a material B are prepared and added dropwise, wherein the material A comprises the following components: 17g of acrylic acid, 40g of hydroxyethyl acrylate, 9g of o-catechol-group unsaturated phosphate ester (BQP-4) and 20g of water are mixed uniformly; b, material B: 1.8g mercaptopropionic acid, 0.5g L-ascorbic acid and 60g water were mixed well. Controlling the initial temperature in the reaction container to be 15 ℃, adding 3.0g of 27.5% hydrogen peroxide solution into the reaction solvent at one time, stirring for 5 minutes, then beginning to dropwise add the material A and the material B, dropwise adding the material A for 50 minutes, dropwise adding the material B for 60 minutes, preserving heat for 60 minutes after dropwise adding the material B, replenishing water to adjust the polymer concentration, adding alkali to adjust the pH value to be 5-6, and obtaining the low-sensitivity high-slump-retention type polycarboxylate superplasticizer PCE-4 with the solid content of 40%.
Comparative example 1: conventional slump-retaining polycarboxylic acid water reducing agent
337g of vinyl polyethylene glycol ether (VPEG) with a molecular weight of 3000 and 342g of water are added into a reaction vessel and dissolved by stirring, and meanwhile, a material A and a material B are prepared, wherein the weight ratio of the material A: 17g of acrylic acid, 42.7g of hydroxyethyl acrylate and 20g of water are mixed uniformly; b, material B: 1.8g mercaptopropionic acid, 0.5g L-ascorbic acid and 60g water were mixed well. Controlling the initial temperature in the reaction container to be 15 ℃, adding 3.0g of 27.5% hydrogen peroxide solution into the reaction solvent at one time, stirring for 5 minutes, then beginning to dropwise add the material A and the material B, dropwise adding the material A for 50 minutes, dropwise adding the material B for 60 minutes, preserving the temperature for 60 minutes after dropwise adding the material B, supplementing water to adjust the concentration of the polymer, and adding alkali to adjust the pH value to be 5-6, thus obtaining the polycarboxylic acid water reducer D1 with the solid content of 40%.
Comparative example 2: conventional phosphate slump-retaining polycarboxylate superplasticizer
337g of vinyl polyethylene glycol ether (VPEG) with the molecular weight of 3000 and 342g of water are added into a reaction vessel and stirred to be dissolved, and meanwhile, a material A and a material B are prepared and added dropwise, wherein the material A comprises the following components: 17g acrylic acid, 40g hydroxyethyl acrylate, 5.3g commercially available 2-hydroxyethyl methacrylate phosphate and 20g water, mixed well; b, material B: 1.8g mercaptopropionic acid, 0.5g L-ascorbic acid and 60g water were mixed well. Controlling the initial temperature in the reaction container to be 15 ℃, adding 3.0g of 27.5% hydrogen peroxide solution into the reaction solvent at one time, stirring for 5 minutes, then beginning to dropwise add the material A and the material B, dropwise adding the material A for 50 minutes, dropwise adding the material B for 60 minutes, preserving the heat for 60 minutes after dropwise adding the material B, supplementing water to adjust the concentration of the polymer, and adding alkali to adjust the pH value to be 5-6, thus obtaining the polycarboxylic acid water reducer D2 with the solid content of 40%.
The low-sensitivity high-slump-retaining type polycarboxylate water reducers (PCE-1, PCE-2, PCE-3 and PCE-4) synthesized in the examples 1 to 4 and the high-slump-retaining type polycarboxylate water reducers (D1 and D2) synthesized in the comparative examples 1 to 2 are subjected to an effect test respectively. Namely, the product of the invention is compared with the comparative high slump loss resistant polycarboxylate superplasticizer net slurry experiment.
The method is carried out according to GB/T8022-2012 "concrete admixture homogeneity test method". The cement is NZ P.O42.5R cement, the cement dosage is 500g, the water dosage is 145g, and the specific experimental data are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, under the condition of the same net slurry ratio and the same doping amount, the examples 1 to 4 have longer slow release effect and smaller late loss compared with the comparative examples 1 to 2, which shows that the high slump-resistant polycarboxylic acid water reducer has better slump resistance.
Compared with the concrete experiment of the comparative high slump retaining type polycarboxylate superplasticizer, the product provided by the invention is used for comparison.
The method is carried out according to GB 8076-2008 'concrete admixture'. The cement is Emei P.O42.5R cement, secondary fly ash, guanghan product machine-made sand (fineness modulus 3.0, mud content 5%), common macadam grading (5-31.5, mud content 1%), and the mixing amount is 1.8% of the mass of the cementing material (the solid content of the additive is 10% solution, and the ratio of the water reducing mother liquor to the slump retaining mother liquor is 6.5. The concrete mixing proportion is as follows: 165kg of water, 280kg of cement, 70kg of coal ash, 900kg of machine-made sand and 1000kg of broken stone. Specific experimental data are shown in table 2.
TABLE 2
As can be seen from the data in Table 2, examples 1-4 of the present invention are superior to the concrete mixtures of comparative examples 1-2 in terms of state, slump retention, and 28d compressive strength when used in machine-made sand concrete. The o-catechol group is introduced into the polymeric side chain of the polycarboxylate superplasticizer under the condition of introducing the o-catechol group-containing unsaturated phosphate ester, so that the adhesive capacity of polycarboxylate superplasticizer molecules on the surface of low-surface-energy machine-made sand can be effectively enhanced, and the purposes of reducing bleeding and slurry bleeding are achieved, thereby improving the workability and the homogeneity of concrete mixtures; meanwhile, the molecules of the polycarboxylic acid water reducing agent can be hydrolyzed in the cement paste to continuously release a large amount of phosphate ions and micromolecular alcohol, so that the hydration process of cement can be greatly delayed, and the slump retaining effect is achieved. The workability and the homogeneity of the concrete mixture are jointly improved by the synergistic effect of the catechol group and the phosphate group, so that the durability and the compressive strength of the concrete are improved.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. An unsaturated phosphate containing catechol group is characterized in that the structural formula is as follows:
wherein R is 1 Is hydrogen or methyl, R 2 Is methyl or ethyl.
2. A process for producing the catechol group-containing unsaturated phosphoric acid ester according to claim 1, which comprises the steps of:
mixing 2-aminoethyl (methyl) acrylate hydrochloride with protocatechualdehyde and dimethyl (ethyl) phosphite, and reacting under the action of an alkaline catalyst to prepare the unsaturated phosphate containing catechol groups.
3. The production method according to claim 2, wherein the molar ratio of the 2-aminoethyl (meth) acrylate hydrochloride, protocatechualdehyde, dimethyl (ethyl) phosphite to the basic catalyst is (1.00 to 1.05): 1:1:1.16.
4. the method according to claim 3, wherein the basic catalyst comprises at least one of trimethylamine, triethylamine and 4-dimethylaminopyridine.
5. The method according to claim 2, wherein the reaction temperature is 60-80 ℃ and the reaction time is 4-5 hours.
6. The polycarboxylate superplasticizer is characterized by comprising the following components:
polyether macromonomer, unsaturated acid, catechol group-containing unsaturated phosphate ester according to claim 1, unsaturated ester, chain transfer agent, oxidizing agent, reducing agent and alkali solution;
the molar ratio of the polyether macromonomer, the unsaturated acid, the unsaturated phosphate containing the catechol group, the unsaturated ester, the chain transfer agent, the oxidant, the reducing agent and the alkali liquor is 1: (1.5-2.5): (0.2-0.5): (3.0-4.0): (0.1-0.6): (0.1-0.3): (0.02 to 0.04): (0.3-0.5).
7. The water reducing agent according to claim 6, wherein the molecular weight of the polyether macromonomer is 2000-3000, and the polyether macromonomer comprises at least one of isobutylene polyoxyethylene ether, isopentenyl polyoxyethylene ether, vinyl polyglycol ether and vinyloxybutyl polyglycol ether.
8. The polycarboxylate water reducer according to claim 6, characterized in that the unsaturated acid comprises at least one of acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and fumaric acid;
the unsaturated ester comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
9. The polycarboxylate water reducer according to claim 6, wherein the chain transfer agent comprises at least one of mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid and sodium hypophosphite;
the oxidant comprises at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate;
the reducing agent comprises at least one of sodium formaldehyde sulfoxylate and L-ascorbic acid;
the base comprises at least one of sodium hydroxide, potassium hydroxide, triethylamine and triethanolamine.
10. A method for preparing a polycarboxylic acid water reducer according to any one of claims 6 to 9, characterized by comprising the steps of:
reacting a polyether macromonomer with an oxidant, unsaturated acid, unsaturated ester, unsaturated phosphate containing catechol group, a chain transfer agent and a reducing agent at the temperature of 10-40 ℃, preserving heat for 0.5-3 h, and adding alkali after preserving heat to obtain the polycarboxylic acid water reducing agent.
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| CN116023062B (en) * | 2022-12-28 | 2024-05-03 | 四川金江建材科技有限公司 | Water-based synergist for concrete and preparation method thereof |
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