CN114181355A - Ester-ether mixed viscosity-reducing polycarboxylate superplasticizer and preparation method thereof - Google Patents
Ester-ether mixed viscosity-reducing polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN114181355A CN114181355A CN202111415887.7A CN202111415887A CN114181355A CN 114181355 A CN114181355 A CN 114181355A CN 202111415887 A CN202111415887 A CN 202111415887A CN 114181355 A CN114181355 A CN 114181355A
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- polycarboxylate superplasticizer
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 30
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 238000005886 esterification reaction Methods 0.000 claims abstract description 62
- 239000002253 acid Substances 0.000 claims abstract description 46
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229940074391 gallic acid Drugs 0.000 claims abstract description 40
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 40
- 230000032050 esterification Effects 0.000 claims abstract description 36
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 29
- 150000002148 esters Chemical class 0.000 claims abstract description 21
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002202 Polyethylene glycol Substances 0.000 claims description 26
- 229920001223 polyethylene glycol Polymers 0.000 claims description 26
- 238000007334 copolymerization reaction Methods 0.000 claims description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 22
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 22
- 239000011976 maleic acid Substances 0.000 claims description 22
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 22
- 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 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 20
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 18
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 12
- -1 3-methallyl alcohol Chemical compound 0.000 claims description 12
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 12
- 229930016911 cinnamic acid Natural products 0.000 claims description 12
- 235000013985 cinnamic acid Nutrition 0.000 claims description 12
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002211 L-ascorbic acid Substances 0.000 claims description 10
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 9
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 8
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 8
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 5
- CTDRAOLVEHKAAZ-UHFFFAOYSA-N 4-prop-2-enoxybutan-1-ol Chemical compound OCCCCOCC=C CTDRAOLVEHKAAZ-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000012966 redox initiator Substances 0.000 claims description 5
- BBEUBSMPIQDNHL-UHFFFAOYSA-N (2-ethenylcyclopropyl)methanol Chemical compound OCC1CC1C=C BBEUBSMPIQDNHL-UHFFFAOYSA-N 0.000 claims description 4
- NEJDKFPXHQRVMV-UHFFFAOYSA-N (E)-2-Methyl-2-buten-1-ol Natural products CC=C(C)CO NEJDKFPXHQRVMV-UHFFFAOYSA-N 0.000 claims description 4
- ZSLKGUQYEQVKQE-UHFFFAOYSA-N 1-prop-2-enylcyclohexan-1-ol Chemical compound C=CCC1(O)CCCCC1 ZSLKGUQYEQVKQE-UHFFFAOYSA-N 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 4
- NEJDKFPXHQRVMV-HWKANZROSA-N 2-Methyl-2-buten-1-ol Chemical compound C\C=C(/C)CO NEJDKFPXHQRVMV-HWKANZROSA-N 0.000 claims description 4
- MDFFZNIQPLKQSG-UHFFFAOYSA-N 2-bromoprop-2-en-1-ol Chemical compound OCC(Br)=C MDFFZNIQPLKQSG-UHFFFAOYSA-N 0.000 claims description 4
- OSCXYTRISGREIM-UHFFFAOYSA-N 2-chloroprop-2-en-1-ol Chemical compound OCC(Cl)=C OSCXYTRISGREIM-UHFFFAOYSA-N 0.000 claims description 4
- XEIHLEMBJXRLEI-UHFFFAOYSA-N 2-fluoroprop-2-en-1-ol Chemical compound OCC(F)=C XEIHLEMBJXRLEI-UHFFFAOYSA-N 0.000 claims description 4
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 4
- HJGHXDNIPAWLLE-UHFFFAOYSA-N 3-chloroprop-2-en-1-ol Chemical compound OCC=CCl HJGHXDNIPAWLLE-UHFFFAOYSA-N 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- 229950000688 phenothiazine Drugs 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 230000033116 oxidation-reduction process Effects 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 2
- FETFXNFGOYOOSP-UHFFFAOYSA-N 1-sulfanylpropan-2-ol Chemical compound CC(O)CS FETFXNFGOYOOSP-UHFFFAOYSA-N 0.000 claims description 2
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 61
- 230000000740 bleeding effect Effects 0.000 abstract description 11
- 238000005086 pumping Methods 0.000 abstract description 10
- 239000011372 high-strength concrete Substances 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000011374 ultra-high-performance concrete Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000002156 mixing Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 6
- 239000004568 cement Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 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 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- CYOAEBLVGSUAKP-UHFFFAOYSA-N 2-(4-ethenylphenyl)acetic acid Chemical compound OC(=O)CC1=CC=C(C=C)C=C1 CYOAEBLVGSUAKP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention relates to the technical field of concrete admixtures, in particular to an ester ether mixed viscosity reduction type polycarboxylate superplasticizer and a preparation method thereof. The ester ether mixed viscosity-reduction type polycarboxylate superplasticizer is prepared by copolymerizing an unsaturated polyether monomer, unsaturated acid, a crosslinking monomer and an esterification product; the esterification product is prepared by esterification reaction of gallic acid and allyl alcohol monomer. The ester ether mixed viscosity-reducing polycarboxylate superplasticizer can effectively reduce the viscosity of high-grade concrete, is beneficial to pumping high-strength concrete, ultrahigh-strength concrete, UHPC (ultra high Performance concrete) concrete and the like, realizes pumping construction of the high-strength concrete, and effectively improves the concrete construction efficiency; meanwhile, the workability of the concrete can be improved, and the problems of layering, bleeding and the like of the concrete are avoided; and the slump loss can be reduced by improving the slump retaining performance of the concrete.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to an ester ether mixed viscosity reduction type polycarboxylate superplasticizer and a preparation method thereof.
Background
Along with the rapid development of the domestic building industry, the strength grade of concrete is also continuously improved, and high-strength and ultrahigh-strength concrete is gradually applied to building engineering, but due to the characteristics of the high-cement material and low water-cement ratio of the concrete, the viscosity of the concrete is high, pumping is difficult, and the concrete is difficult to apply to construction bodies such as high-rise buildings, large-volume structures and the like in a large scale, so the demand of the market on the high-strength concrete viscosity reducer is continuously increased.
In recent years, aiming at the problem of high-strength concrete viscosity, the viscosity problem is generally solved by adjusting the mixing proportion of concrete and improving the quality of concrete rubber aggregate in the industry, but the viscosity reduction effect by adopting the method is not ideal, and other performances such as concrete durability and the like can be influenced. The existing polycarboxylic acid water reducing agent is used as an important component of concrete, and the molecular structure can be designed according to different requirements due to large adjustability space of the molecular structure, so that the polycarboxylic acid water reducing agent becomes a preferable scheme for solving the problem of concrete viscosity;
at present, the problem is mainly solved by changing the molecular side chain density or the hydrophobic functional group type of the water reducing agent in the industry of the development of the viscosity reduction product of the polycarboxylic acid water reducing agent, and the development difficulty of the product is high and the performance of the viscosity reduction product is uneven due to the large quantity and the multiple types of organic compounds.
Chinese patent with application number CN201811241729.2 and publication date of 2019, 03 and 15 discloses a high-strength concrete viscosity-reducing polycarboxylate superplasticizer, which is prepared from maleic anhydride, polyethylene glycol or polypropylene glycol, small molecular alcohol or alcohol amine and a phosphorylation reagent to obtain maleic anhydride modified phosphate ester for synthesizing the viscosity-reducing polycarboxylate superplasticizer; the viscosity reduction type polycarboxylate superplasticizer prepared by the method requires esterification condensation of maleic anhydride, polyethylene glycol and the like, has strict esterification process requirements, large esterification rate fluctuation, higher production cost and more complex process, and is not beneficial to industrial production.
The Chinese patent with the application number of CN201811597027.8 and the publication date of 2019, 05 and 07 discloses a double viscosity-reducing functional group carboxylic acid water reducer, wherein the adopted viscosity-reducing functional group is of a straight-chain structure, the water reducing rate is higher, the slump retaining performance is good, the production is facilitated, and the viscosity-reducing effect is obvious.
The Chinese patent application with the application number of CN202110144515.9 and the publication date of 2021, 05 years and 14 days discloses a shrinkage-reducing polycarboxylic acid water reducing agent taking gallic acid as a functional polymeric monomer, wherein the gallic acid is subjected to free radical polymerization in a carboxyl condensation mode, the obtained water reducing agent has obvious shrinkage-reducing effect, but the existing polyhydroxy structure needs hydroxyl protection before polymerization, the reaction steps are increased, the production is complicated, and the viscosity-reducing effect of the product is not obvious.
Disclosure of Invention
In order to solve the problems of high viscosity and difficult pumping of high-strength or ultrahigh-strength concrete in the prior art, the invention provides an ester ether mixed viscosity reduction type polycarboxylate superplasticizer which is prepared by copolymerizing an unsaturated polyether monomer, unsaturated acid, a crosslinking monomer and an esterification product;
the esterification product is prepared by esterification reaction of gallic acid and allyl alcohol monomer.
In one embodiment, the allylic alcohol monomer is one or more combinations of 2-methallyl alcohol, 3-methallyl alcohol, 2-chloro-2-propen-1-ol, 3-chloroallyl alcohol, 2-bromo-2-propen-1-ol, 2-fluoroallyl alcohol, 4- (allyloxy) -1-butanol, 1-allylcyclohexanol, (2-vinylcyclopropyl) methanol, 2-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol.
In one embodiment, the molar ratio of gallic acid to allyl alcohol monomer is 1: (2-4).
In one embodiment, the unsaturated polyether monomer is one or more of allyl polyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene polyoxypropylene ether, and isopentenyl polyoxyethylene polyoxypropylene ether, and the molecular weight of the unsaturated polyether monomer is 200-1000.
In one embodiment, the unsaturated acid includes unsaturated acid a and unsaturated acid B, the unsaturated acid a is cinnamic acid, and the unsaturated acid B is one or more of acrylic acid, methacrylic acid, itaconic acid, and maleic acid.
In one embodiment, the crosslinking monomer is polyethylene glycol maleic acid monoester, wherein the polyethylene glycol is one of PEG-200, PEG-400 and PEG-600.
In one embodiment, the mass ratio of the unsaturated polyether monomer, the unsaturated acid, the crosslinking monomer and the esterification product is (50-100): (5-15): (3-5): (5-10).
The invention also provides a preparation method of the ester ether mixed viscosity-reducing polycarboxylate superplasticizer, which comprises the following preparation steps:
s100: performing esterification reaction on gallic acid and allyl alcohol monomers at the temperature of 80-120 ℃ to obtain an esterification product;
s200: and carrying out copolymerization reaction on the unsaturated polyether monomer, the unsaturated acid, the crosslinking monomer and the esterification product under an oxidation-reduction initiation system to obtain a copolymerization product, namely the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer.
In one embodiment, during the esterification reaction of S100, a catalyst and a polymerization inhibitor are also added; during the copolymerization reaction of S200, a chain transfer agent is also added.
In one embodiment, the catalyst is one or more of concentrated sulfuric acid, p-toluenesulfonic acid, stannous oxide and dibutyl tin oxide, and the amount of the catalyst accounts for 1-3% of the total mass of gallic acid and allyl alcohol monomers; the polymerization inhibitor is one or a combination of more of p-hydroxyanisole, hydroquinone and phenothiazine, and the dosage of the polymerization inhibitor accounts for 0.1-2% of the total mass of the gallic acid and the allyl alcohol monomer; the redox initiation system comprises an oxidant and a reducing agent, wherein the oxidant is one of ammonium persulfate and hydrogen peroxide, and the using amount of the oxidant is 1-5% of the total mass of the unsaturated polyether monomer; the reducing agent is one or a combination of more of hypophosphite and L-ascorbic acid, and the using amount of the reducing agent is 0.1-2% of the total mass of the unsaturated polyether monomer; the chain transfer agent is one or a combination of more of thioglycolic acid, mercaptoethanol, 2-hydroxypropanethiol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptosuccinic acid, sodium methallylsulfonate and 2-acrylamide-2-methylpropanesulfonic acid, and the dosage of the chain transfer agent is 1-5% of the total mass of the unsaturated polyether monomer.
The ester-ether mixed viscosity-reduction type polycarboxylate superplasticizer for high-strength concrete provided by the invention can reduce the viscosity of concrete, shorten the concrete lifting time, reduce the adsorption on soil and reduce the slump loss, thereby improving the pumping efficiency of concrete and being beneficial to concrete construction; the ester ether mixed viscosity-reduction type polycarboxylate superplasticizer is prepared by copolymerizing allyl alcohol-gallate with an unsaturated polyether monomer, unsaturated acid and a crosslinking monomer, and takes the allyl alcohol-gallate as a part of side chains to increase the steric hindrance effect, thereby reducing the viscosity of concrete, improving the workability of the concrete, avoiding the problems of layering, bleeding and the like of the concrete, and simultaneously improving the appearance of a concrete structure; and moreover, the introduction of the crosslinking monomer can improve the slump retaining performance of the concrete and reduce the slump loss in the pumping process.
Based on the above, compared with the prior art, the ester ether mixed viscosity reduction type polycarboxylate superplasticizer provided by the invention has the following technical effects: the ester ether mixed viscosity-reducing polycarboxylate superplasticizer provided by the invention is a polycarboxylate superplasticizer capable of reducing the viscosity of high-grade concrete, and is prepared by copolymerizing allyl alcohol-gallate with an unsaturated polyether monomer, unsaturated acid and a crosslinking monomer, and can effectively reduce the viscosity of the high-grade concrete, thereby being beneficial to pumping of high-strength concrete, ultrahigh-strength concrete, UHPC (ultra high Performance concrete) concrete and the like, realizing pumping construction of the high-strength concrete, and effectively improving the construction efficiency of the concrete; meanwhile, the workability of the concrete can be improved, and the problems of layering, bleeding and the like of the concrete are avoided; and the slump loss can be reduced by improving the slump retaining performance of the 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 particularly pointed out in the written description and claims hereof.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following will clearly and completely describe the embodiments of the present invention with reference to the technical solutions thereof, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; the technical features designed in the different embodiments of the present 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be noted that all terms (including technical and scientific terms) used herein 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.
The invention provides a preparation method of an ester ether mixed viscosity-reducing polycarboxylate superplasticizer, which comprises the following steps:
(1) esterification reaction: mixing gallic acid and allyl alcohol monomers according to a certain proportion, adding a catalyst and a polymerization inhibitor, and carrying out esterification reaction for 4-5 h at 80-120 ℃ under the protection of nitrogen to obtain an esterification product;
wherein the molar ratio of the gallic acid to the allyl alcohol monomer is 1: (2-4); the dosage of the catalyst accounts for 1 to 3 percent of the total mass of the gallic acid and the allyl alcohol monomer; the dosage of the polymerization inhibitor accounts for 0.1 to 2 percent of the total mass of the gallic acid and the allyl alcohol monomer;
the allyl alcohol monomer is selected from one or more of 2-methallyl alcohol, 3-methallyl alcohol, 2-chloro-2-propen-1-ol, 3-chloroallyl alcohol, 2-bromo-2-propen-1-ol, 2-fluoroallyl alcohol, 4- (allyloxy) -1-butanol, 1-allylcyclohexanol, (2-vinylcyclopropyl) methanol, 2-methyl-2-buten-1-ol and 3-methyl-3-buten-1-ol; the catalyst is selected from one or more of concentrated sulfuric acid, p-toluenesulfonic acid, stannous oxide and dibutyl tin oxide; the polymerization inhibitor is one or more of p-hydroxyanisole, hydroquinone and phenothiazine.
(2) And (3) copolymerization reaction: adding an unsaturated polyether monomer and water into a reaction kettle, stirring and dispersing uniformly, adding a chain transfer agent, a crosslinking monomer, unsaturated acid and an esterification product under an oxidation-reduction initiation system, and carrying out copolymerization reaction at normal temperature to obtain a copolymerization product;
wherein the mass ratio of the unsaturated polyether monomer, the unsaturated acid, the crosslinking monomer and the esterification product is (50-100): (5-15): (3-5): (5-10); the dosage of the oxidant in the redox initiation system is 1 to 5 percent of the total mass of the unsaturated polyether monomer; the dosage of the reducing agent is 0.1-2% of the total mass of the unsaturated polyether monomer; the dosage of the chain transfer agent is 1 to 5 percent of the total mass of the unsaturated polyether monomer;
wherein the unsaturated polyether monomer is selected from one or more of allyl polyoxyethylene polyoxypropylene ether, methyl allyl polyoxyethylene polyoxypropylene ether and isopentenyl polyoxyethylene polyoxypropylene ether, and the molecular weight of the unsaturated polyether monomer is 200-1000; the unsaturated acid comprises unsaturated acid A and unsaturated acid B, the unsaturated acid A is selected from cinnamic acid, and the unsaturated acid B is selected from one or more of acrylic acid, methacrylic acid, itaconic acid and maleic acid; the crosslinking monomer is polyethylene glycol maleic acid monoester, wherein the polyethylene glycol is one of PEG-200, PEG-400 and PEG-600; the redox initiation system comprises an oxidant and a reducing agent, wherein the oxidant is one of ammonium persulfate and hydrogen peroxide, and the reducing agent is one or a combination of more of hypophosphite and L-ascorbic acid.
(3) And (3) adding an alkaline solution into the product obtained in the step (2) to neutralize the product until the pH value is 6-7, so as to obtain the ester-ether mixed viscosity-reduction type polycarboxylate superplasticizer.
The invention also provides the following examples and comparative examples:
the present invention provides the reaction feed formulations of the examples and comparative examples set forth in table 1 below:
TABLE 1
Specifically, the specific preparation processes of the examples and the comparative examples are as follows:
example 1:
(1) esterification reaction: mixing gallic acid and 2-methallyl alcohol according to a molar ratio of 1: 2, blending, adding p-toluenesulfonic acid accounting for 3 percent of the total mass of the gallic acid and the 4-vinylbenzoic acid and hydroquinone accounting for 0.5 percent of the total mass of the gallic acid and the 4-vinylbenzoic acid, continuously introducing nitrogen, and carrying out esterification reaction for 4 hours at 120 ℃ to obtain an esterification product.
(2) And (3) copolymerization reaction: adding 50 parts by mass of isopentene polyoxyethylene polyoxypropylene ether (molecular weight is 1000) and 25 parts by mass of water into a reaction kettle, stirring and dispersing uniformly, adding 2 parts by mass of hydrogen peroxide at one time, reacting at 25 ℃ for 10min, and then dropwise adding the solution B and the solution C;
wherein the solution B is 10 parts of sodium hypophosphite solution with the mass concentration of 10%; the solution C is a solution consisting of 10 parts of esterification products, 5 parts of polyethylene glycol maleic acid monoester (polyethylene glycol is PEG-400), 6 parts of cinnamic acid, 4 parts of acrylic acid and 1 part of thioglycolic acid;
(3) and after the dropwise addition of the solution B and the solution C is finished, preserving the heat for 30min, and adding 10 parts of 32% liquid caustic soda by mass concentration for neutralization to obtain the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer. Wherein the liquid alkali is sodium hydroxide solution.
Example 2
(1) Esterification reaction: mixing gallic acid and 2-chloro-2-propylene-1-ol according to a molar ratio of 1: 3, blending in proportion, adding concentrated sulfuric acid accounting for 1 percent of the total mass of the gallic acid and the 4-vinyl phenylacetic acid and 0.1 percent of phenothiazine, continuously introducing nitrogen, and carrying out esterification reaction for 4 hours at 110 ℃ to obtain an esterification product.
(2) And (3) copolymerization reaction: adding 80 parts by mass of methyl allyl polyoxyethylene polyoxypropylene ether (molecular weight is 500) and 40 parts by mass of water into a reaction kettle, stirring and dispersing uniformly, adding 1 part of hydrogen peroxide at one time, reacting at 20 ℃, and dripping solution B and solution C after 10 min;
wherein the solution B is 1 part of L-ascorbic acid solution with the mass concentration of 10%; the solution C is a solution consisting of 5 parts of esterification products, 4 parts of polyethylene glycol maleic acid monoester (polyethylene glycol is PEG-600), 5 parts of cinnamic acid, 5 parts of methacrylic acid and 2 parts of mercaptoethanol;
(3) and after the dropwise addition of the solution B and the solution C is finished, preserving the heat for 30min, and adding 10 parts of 32% liquid caustic soda by mass concentration for neutralization to obtain the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer.
Example 3
(1) Esterification reaction: gallic acid and 4- (allyloxy) -1-butanol are mixed according to a molar ratio of 1: 4, blending in proportion, adding stannous oxide accounting for 2 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid and 1 percent of p-hydroxyanisole, continuously introducing nitrogen, and carrying out esterification reaction for 4 hours at 80 ℃ to obtain an esterification product.
(2) And (3) copolymerization reaction: adding 60 parts by mass of allyl polyoxyethylene polyoxypropylene ether (molecular weight is 200) and 30 parts by mass of water into a reaction kettle, stirring and dispersing uniformly, adding 3 parts by mass of ammonium persulfate at one time, reacting at 30 ℃ for 10min, and then dropwise adding the solution B and the solution C;
wherein the solution B is 6 parts of sodium hypophosphite solution with the mass concentration of 10%; the solution C is a solution consisting of 6 parts of esterification products, 3 parts of polyethylene glycol maleic acid monoester (polyethylene glycol is PEG-400), 3 parts of cinnamic acid, 2 parts of itaconic acid and 3 parts of 3-mercaptopropionic acid;
(3) and after the dropwise addition of the solution B and the solution C is finished, preserving the heat for 30min, and adding 5 parts of 32% liquid caustic soda by mass concentration for neutralization to obtain the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer.
Example 4
(1) Esterification reaction: mixing gallic acid and 3-methyl-3-butylene-1-alcohol according to a molar ratio of 1: 3, blending in proportion, adding dibutyltin oxide accounting for 1 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid and hydroquinone accounting for 2 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid, continuously introducing nitrogen, and carrying out esterification reaction for 4 hours at 90 ℃ to obtain an esterification product.
(2) And (3) copolymerization reaction: adding 100 parts by mass of isopentene polyoxyethylene polyoxypropylene ether (molecular weight is 800) and 50 parts by mass of water into a reaction kettle, stirring and dispersing uniformly, adding 2 parts by mass of ammonium persulfate at one time, reacting at 25 ℃ for 10min, and then dropwise adding the solution B and the solution C;
wherein the solution B is 4 parts of L-ascorbic acid solution with the mass concentration of 10%; the solution C is a solution consisting of 8 parts of esterification products, 5 parts of polyethylene glycol maleic acid monoester (polyethylene glycol is PEG-200), 10 parts of cinnamic acid, 5 parts of maleic acid and 1 part of sodium methallyl sulfonate;
(3) and after the dropwise addition of the solution B and the solution C is finished, preserving the heat for 30min, and adding 15 parts of 32% liquid caustic soda by mass concentration for neutralization to obtain the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer.
Comparative example 1
(1) And (3) copolymerization reaction: adding 100 parts by mass of isopentene polyoxyethylene polyoxypropylene ether (molecular weight is 800) and 50 parts by mass of water into a reaction kettle, stirring and dispersing uniformly, adding 2 parts by mass of ammonium persulfate at one time, reacting at 25 ℃ for 10min, and then dropwise adding the solution B and the solution C;
wherein the solution B is 4 parts of L-ascorbic acid solution with the mass concentration of 10%; the solution C is a solution consisting of 5 parts of polyethylene glycol maleic acid monoester (polyethylene glycol is PEG-200), 10 parts of cinnamic acid, 5 parts of maleic acid and 1 part of sodium methallyl sulfonate;
(2) and after the dropwise addition of the solution B and the solution C is finished, preserving the heat for 30min, and adding 15 parts of 32% liquid caustic soda by mass concentration for neutralization to obtain the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer.
Comparative example 2
(1) Esterification reaction: mixing gallic acid and 3-methyl-3-butylene-1-alcohol according to a molar ratio of 1: 3, blending in proportion, adding dibutyltin oxide accounting for 1 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid and hydroquinone accounting for 2 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid, continuously introducing nitrogen, and carrying out esterification reaction for 4 hours at 90 ℃ to obtain an esterification product.
(2) And (3) copolymerization reaction: adding 100 parts by mass of isopentene polyoxyethylene polyoxypropylene ether (molecular weight is 800) and 50 parts by mass of water into a reaction kettle, stirring and dispersing uniformly, adding 2 parts by mass of ammonium persulfate at one time, reacting at 25 ℃ for 10min, and then dropwise adding the solution B and the solution C;
wherein the solution B is 4 parts of L-ascorbic acid solution with the mass concentration of 10%; the solution C is a solution consisting of 8 parts of esterification products, 10 parts of cinnamic acid, 5 parts of maleic acid and 1 part of sodium methallyl sulfonate;
(3) and after the dropwise addition of the solution B and the solution C is finished, preserving the heat for 30min, and adding 15 parts of 32% liquid caustic soda by mass concentration for neutralization to obtain the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer.
Comparative example 3
(1) Esterification reaction: mixing gallic acid and acryloyl chloride according to a molar ratio of 1: 3, blending in proportion, adding dibutyltin oxide accounting for 1 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid and hydroquinone accounting for 2 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid, continuously introducing nitrogen, and carrying out esterification reaction for 4 hours at 90 ℃ to obtain an esterification product.
(2) And (3) copolymerization reaction: adding 100 parts by mass of isopentene polyoxyethylene polyoxypropylene ether (molecular weight is 800) and 50 parts by mass of water into a reaction kettle, stirring and dispersing uniformly, adding 2 parts by mass of ammonium persulfate at one time, reacting at 25 ℃ for 10min, and then dropwise adding the solution B and the solution C;
wherein the solution B is 4 parts of L-ascorbic acid solution with the mass concentration of 10%; the solution C is a solution consisting of 8 parts of esterification products, 5 parts of polyethylene glycol maleic acid monoester (polyethylene glycol is PEG-200), 10 parts of cinnamic acid, 5 parts of maleic acid and 1 part of sodium methallyl sulfonate;
(3) and after the dropwise addition of the solution B and the solution C is finished, preserving the heat for 30min, and adding 15 parts of 32% liquid caustic soda by mass concentration for neutralization to obtain the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer.
Comparative example 4
(1) Esterification reaction: mixing gallic acid and 3-methyl-3-butylene-1-alcohol according to a molar ratio of 1: 3, blending in proportion, adding dibutyltin oxide accounting for 1 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid and hydroquinone accounting for 2 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid, continuously introducing nitrogen, and carrying out esterification reaction for 4 hours at 90 ℃ to obtain an esterification product.
(2) And (3) copolymerization reaction: adding 100 parts by mass of isopentene polyoxyethylene polyoxypropylene ether (molecular weight is 800) and 50 parts by mass of water into a reaction kettle, stirring and dispersing uniformly, adding 2 parts by mass of ammonium persulfate at one time, reacting at 25 ℃ for 10min, and then dropwise adding the solution B and the solution C;
wherein the solution B is 4 parts of L-ascorbic acid solution with the mass concentration of 10%; the solution C is a solution consisting of 8 parts of esterification products, 5 parts of polyethylene glycol maleic acid monoester (polyethylene glycol is PEG-200), 15 parts of maleic acid and 1 part of sodium methallyl sulfonate;
(3) and after the dropwise addition of the solution B and the solution C is finished, preserving the heat for 30min, and adding 15 parts of 32% liquid caustic soda by mass concentration for neutralization to obtain the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer.
Comparative example 5
(1) Esterification reaction: mixing gallic acid and 3-methyl-3-butylene-1-alcohol according to a molar ratio of 1: 3, blending in proportion, adding dibutyltin oxide accounting for 1 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid and hydroquinone accounting for 2 percent of the total mass of the gallic acid and the 4-vinyl benzoic acid, continuously introducing nitrogen, and carrying out esterification reaction for 4 hours at 90 ℃ to obtain an esterification product.
(2) And (3) copolymerization reaction: adding 100 parts by mass of isopentenyl polyoxyethylene ether (molecular weight is 800) and 50 parts by mass of water into a reaction kettle, stirring and dispersing uniformly, adding 2 parts of ammonium persulfate at one time, reacting at 25 ℃ for 10min, and then dropwise adding a solution B and a solution C;
wherein the solution B is 4 parts of L-ascorbic acid solution with the mass concentration of 10%; the solution C is a solution consisting of 8 parts of esterification products, 5 parts of polyethylene glycol maleic acid monoester (polyethylene glycol is PEG-200), 10 parts of cinnamic acid, 5 parts of maleic acid and 1 part of sodium methallyl sulfonate;
(3) and after the dropwise addition of the solution B and the solution C is finished, preserving the heat for 30min, and adding 15 parts of 32% liquid caustic soda by mass concentration for neutralization to obtain the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer.
The samples synthesized in examples 1-4 and comparative examples 1-5 were tested for initial slump and expansion, and slump and expansion over time, emptying time of the slump bucket and emptying time of the slump bucket, bleeding rate and concrete state according to GB 8076-. The concrete mixing proportion is as follows: cement 360kg/m390kg/m of fly ash (II level)390kg/m of mineral powder (S95)3700kg/m of sand3368kg/m stone (5-10mm)3682kg/m of stone (10-20mm)3The spreading degree was controlled at 650. + -.10 mm, and the results are shown in Table 2.
TABLE 2 concrete Performance test results
As can be seen from the test results in table 2:
the ester ether mixed viscosity-reducing polycarboxylate superplasticizer provided by the embodiments 1-4 is applied to concrete, and the test result shows that: the concrete in the embodiments 1-4 has small loss of the concrete with time, the loss of the concrete with time of the expansion degree 2h is only 10mm-20mm, the polycarboxylate superplasticizer can improve the slump retaining performance of the concrete, reduce the slump loss in the pumping process, has the excellent effects of short emptying time, low bleeding rate, good workability, low viscosity, high flow rate and the like, can reduce the viscosity of the concrete, shorten the lifting time of the concrete, reduce the adsorption on soil, reduce the slump loss, thereby improving the pumping efficiency of the concrete and being beneficial to the construction of high-grade concrete; meanwhile, the workability of the concrete can be improved, and the problems of layering, bleeding and the like of the concrete are avoided;
the copolymerization product provided in comparative example 1 was applied to concrete, and the test results showed that: compared with the examples 1-4, the expansion degree is increased with time, the emptying time is long, the bleeding rate is up to 30 percent, the workability of the concrete is general, the viscosity is high, and the flow rate is slow;
the copolymerization product provided in comparative example 2 was applied to concrete, and the test results showed that: compared with the examples 1-4, the expansion degree is increased with time, the emptying time is long, the bleeding rate is as high as 22%, the workability of concrete is good, but the loss is fast and the flow rate is slow;
the copolymerization product provided in comparative example 3 was applied to concrete, and the test results showed that: compared with the examples 1-4, the expansion degree is increased with time, the emptying time is long, the bleeding rate is up to 27%, the workability of the concrete is good, but the viscosity is high, and the flow rate is slow;
the copolymerization product provided in comparative example 4 was applied to concrete, and the test results showed that: compared with the examples 1-4, the expansion degree is increased with time, the emptying time is long, the bleeding rate is up to 18 percent, the workability of the concrete is good, but the viscosity is high, and the flow rate is slow;
the copolymerization product provided in comparative example 5 was applied to concrete, and the test results showed that: compared with the examples 1-4, the expansion degree is increased with time, the emptying time is long, the bleeding rate is up to 23%, and the workability of the concrete is general, the viscosity is high, and the flow rate is slow.
It should be noted that:
in addition to the practical options presented in the above specific examples, it is preferred that the molar ratio of gallic acid to allyl alcohol monomer in the esterification reaction is in the range of 1: (2-4), including but not limited to the practical choices embodied in the above embodiments;
in addition to the practical choices embodied in the above specific examples, preferably the allylic alcohol monomer may be selected from one or more combinations of 2-methallyl alcohol, 3-methallyl alcohol, 2-chloro-2-propen-1-ol, 3-chloroallyl alcohol, 2-bromo-2-propen-1-ol, 2-fluoroallyl alcohol, 4- (allyloxy) -1-butanol, 1-allylcyclohexanol, (2-vinylcyclopropyl) methanol, 2-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, including but not limited to the practical choices embodied in the above examples;
in addition to the practical choices embodied in the above specific embodiments, preferably in the copolymerization reaction, the mass ratio of the unsaturated polyether monomer, the unsaturated acid, the crosslinking monomer and the esterification product is (50-100): (5-15): (3-5): (5-10), including but not limited to the practical choices embodied in the above embodiments;
in addition to the practical choices embodied in the above specific examples, the unsaturated polyether monomer may be preferably selected from one or more combinations of allyl polyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene polyoxypropylene ether, and isopentenyl polyoxyethylene polyoxypropylene ether, and the molecular weight thereof is within the range of 200-1000, including but not limited to the practical choices embodied in the above examples;
in addition to the practical choices embodied in the above specific examples, preferably the unsaturated acid comprises unsaturated acid a selected from cinnamic acid and unsaturated acid B selected from one or more combinations of acrylic acid, methacrylic acid, itaconic acid, maleic acid, including but not limited to the practical choices embodied in the above examples;
in addition to the practical choices embodied in the above specific embodiments, preferably the crosslinking monomer may be selected from polyethylene glycol maleic acid monoester, wherein the polyethylene glycol may be selected from one of PEG-200, PEG-400, PEG-600, including but not limited to the practical choices embodied in the above embodiments;
besides the actual choices embodied in the above specific examples, the catalyst, the polymerization inhibitor, the oxidant and the reductant in the redox initiation system, the chain transfer agent, etc. are all common reagents used in esterification and copolymerization reactions, and the selection of the type and the selection of the proportion can be adjusted adaptively within the concept and the protection scope of the invention, including but not limited to the actual choices embodied in the above examples;
in summary, the specific parameters or some common reagents in the above-mentioned embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
In addition, the raw materials used may be those commercially available or prepared by methods conventional in the art, unless otherwise specified.
In addition, it will be appreciated by those skilled in the art that, although there may be many problems with the prior art, each embodiment or aspect of the present invention may be improved only in one or several respects, without necessarily simultaneously solving all the technical problems listed in the prior art or in the background. It will be understood by those skilled in the art that nothing in a claim should be taken as a limitation on that claim.
Although terms such as unsaturated polyether monomers, unsaturated acids, crosslinking monomers, etc. are used more often herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention; the terms "first," "second," and the like in the description and in the claims, if any, of the embodiments of the invention 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 used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An ester ether mixed viscosity reduction type polycarboxylate superplasticizer is characterized in that: is prepared by copolymerizing unsaturated polyether monomer, unsaturated acid, crosslinking monomer and esterification product;
the esterification product is prepared by esterification reaction of gallic acid and allyl alcohol monomer.
2. The ester ether mixed viscosity-reducing polycarboxylate superplasticizer according to claim 1, characterized in that: the allyl alcohol monomer is one or more of 2-methallyl alcohol, 3-methallyl alcohol, 2-chloro-2-propen-1-ol, 3-chloroallyl alcohol, 2-bromo-2-propen-1-ol, 2-fluoroallyl alcohol, 4- (allyloxy) -1-butanol, 1-allylcyclohexanol, (2-vinylcyclopropyl) methanol, 2-methyl-2-buten-1-ol and 3-methyl-3-buten-1-ol.
3. The ester ether mixed viscosity-reducing polycarboxylate superplasticizer according to claim 1, characterized in that: the molar ratio of the gallic acid to the allyl alcohol monomer is 1: (2-4).
4. The ester ether mixed viscosity-reducing polycarboxylate superplasticizer according to claim 1, characterized in that: the unsaturated polyether monomer is one or a combination of more of allyl polyoxyethylene polyoxypropylene ether, methyl allyl polyoxyethylene polyoxypropylene ether and isopentenyl polyoxyethylene polyoxypropylene ether, and the molecular weight of the unsaturated polyether monomer is 200-1000.
5. The ester ether mixed viscosity-reducing polycarboxylate superplasticizer according to claim 1, characterized in that: the unsaturated acid comprises an unsaturated acid A and an unsaturated acid B, wherein the unsaturated acid A is cinnamic acid, and the unsaturated acid B is one or more of acrylic acid, methacrylic acid, itaconic acid and maleic acid.
6. The ester ether mixed viscosity-reducing polycarboxylate superplasticizer according to claim 1, characterized in that: the crosslinking monomer is polyethylene glycol maleic acid monoester, wherein the polyethylene glycol is one of PEG-200, PEG-400 and PEG-600.
7. The ester ether mixed viscosity-reducing polycarboxylate superplasticizer according to claim 1, characterized in that: the mass ratio of the unsaturated polyether monomer, the unsaturated acid, the crosslinking monomer and the esterification product is (50-100): (5-15): (3-5): (5-10).
8. The preparation method of the ester ether mixed viscosity-reducing polycarboxylate superplasticizer according to any one of claims 1 to 7, characterized by comprising the following steps: the preparation method comprises the following preparation steps:
s100: performing esterification reaction on gallic acid and allyl alcohol monomers at the temperature of 80-120 ℃ to obtain an esterification product;
s200: and carrying out copolymerization reaction on the unsaturated polyether monomer, the unsaturated acid, the crosslinking monomer and the esterification product under an oxidation-reduction initiation system to obtain a copolymerization product, namely the ester-ether mixed viscosity-reduction polycarboxylic acid water reducer.
9. The preparation method of the ester ether mixed viscosity-reducing polycarboxylate superplasticizer according to claim 8, characterized by comprising the following steps: in the esterification reaction process of S100, catalyst and polymerization inhibitor are also added; during the copolymerization reaction of S200, a chain transfer agent is also added.
10. The preparation method of the ester ether mixed viscosity-reducing polycarboxylate superplasticizer according to claim 9, characterized by comprising the following steps: the catalyst is one or a combination of more of concentrated sulfuric acid, p-toluenesulfonic acid, stannous oxide and dibutyl tin oxide, and the amount of the catalyst accounts for 1-3% of the total mass of gallic acid and allyl alcohol monomers; the polymerization inhibitor is one or a combination of more of p-hydroxyanisole, hydroquinone and phenothiazine, and the dosage of the polymerization inhibitor accounts for 0.1-2% of the total mass of the gallic acid and the allyl alcohol monomer;
the redox initiation system comprises an oxidant and a reducing agent, wherein the oxidant is one of ammonium persulfate and hydrogen peroxide, and the using amount of the oxidant is 1-5% of the total mass of the unsaturated polyether monomer; the reducing agent is one or a combination of more of hypophosphite and L-ascorbic acid, and the using amount of the reducing agent is 0.1-2% of the total mass of the unsaturated polyether monomer;
the chain transfer agent is one or a combination of more of thioglycolic acid, mercaptoethanol, 2-hydroxypropanethiol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptosuccinic acid, sodium methallylsulfonate and 2-acrylamide-2-methylpropanesulfonic acid, and the dosage of the chain transfer agent is 1-5% of the total mass of the unsaturated polyether monomer.
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Citations (3)
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|---|---|---|---|---|
| CN103145928A (en) * | 2012-08-29 | 2013-06-12 | 成都理工大学 | Low-cost polyester polycarboxylic acid water reducer |
| CN103804609A (en) * | 2014-01-21 | 2014-05-21 | 北京奥润开元环保科技研究院有限公司 | Polycarboxylic acid water reducer with reticular structure and preparation method thereof |
| CN109970922A (en) * | 2019-01-29 | 2019-07-05 | 武汉苏博新型建材有限公司 | A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145928A (en) * | 2012-08-29 | 2013-06-12 | 成都理工大学 | Low-cost polyester polycarboxylic acid water reducer |
| CN103804609A (en) * | 2014-01-21 | 2014-05-21 | 北京奥润开元环保科技研究院有限公司 | Polycarboxylic acid water reducer with reticular structure and preparation method thereof |
| CN109970922A (en) * | 2019-01-29 | 2019-07-05 | 武汉苏博新型建材有限公司 | A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process |
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