CN112608426A - Polycarboxylate superplasticizer and preparation method thereof - Google Patents
Polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN112608426A CN112608426A CN202011348320.8A CN202011348320A CN112608426A CN 112608426 A CN112608426 A CN 112608426A CN 202011348320 A CN202011348320 A CN 202011348320A CN 112608426 A CN112608426 A CN 112608426A
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- unsaturated
- water reducer
- compound
- polycarboxylate
- acid
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 88
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 146
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 82
- 230000002335 preservative effect Effects 0.000 claims abstract description 54
- 239000003755 preservative agent Substances 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 238000005886 esterification reaction Methods 0.000 claims abstract description 26
- 230000032050 esterification Effects 0.000 claims abstract description 25
- 229940126062 Compound A Drugs 0.000 claims abstract description 22
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 17
- 150000001408 amides Chemical class 0.000 claims abstract description 17
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 22
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 21
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- 150000003254 radicals Chemical class 0.000 claims description 13
- 239000012986 chain transfer agent Substances 0.000 claims description 11
- XOYONZYDWNTDAL-UHFFFAOYSA-N n-butoxyprop-2-enamide Chemical compound CCCCONC(=O)C=C XOYONZYDWNTDAL-UHFFFAOYSA-N 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- -1 hydroxybutyl vinyl Chemical group 0.000 claims description 7
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 7
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 claims description 5
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 4
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 claims description 4
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 claims description 4
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 claims description 4
- ZNSSPLQZSUWFJT-UHFFFAOYSA-N pentyl 4-hydroxybenzoate Chemical compound CCCCCOC(=O)C1=CC=C(O)C=C1 ZNSSPLQZSUWFJT-UHFFFAOYSA-N 0.000 claims description 4
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 claims description 4
- 239000004405 propyl p-hydroxybenzoate Substances 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000003573 thiols Chemical group 0.000 claims description 3
- 229940067596 butylparaben Drugs 0.000 claims description 2
- 229960001617 ethyl hydroxybenzoate Drugs 0.000 claims description 2
- 229960002216 methylparaben Drugs 0.000 claims description 2
- 229960003415 propylparaben Drugs 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000005536 corrosion prevention Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 44
- 239000008367 deionised water Substances 0.000 description 31
- 229910021641 deionized water Inorganic materials 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- ZBUXMZFLCYRTOB-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C.CNC(=O)C=C ZBUXMZFLCYRTOB-UHFFFAOYSA-N 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 5
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 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 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 229940043351 ethyl-p-hydroxybenzoate Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical group 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention provides a polycarboxylate superplasticizer which is characterized by comprising the following components in percentage by mass (10-40): (10-20): (2-8): 200 of compound B, unsaturated acid, unsaturated amide monomer and unsaturated polyether macromonomer, wherein the compound B is an esterification product of a preservative compound A and unsaturated anhydride. According to the polycarboxylate water reducer disclosed by the invention, the polycarboxylate water reducer prepared by matching the components can greatly improve the self-corrosion prevention effect of the polycarboxylate water reducer, so that the quality guarantee period of the polycarboxylate water reducer is prolonged, and the polycarboxylate water reducer has better water reducing performance; in the later-stage polycarboxylate water reducer compounding process, no preservative is required to be added, the compounded polycarboxylate water reducer still has good corrosion resistance, the polycarboxylate water reducer can be kept not to deteriorate for a long time, and the polycarboxylate water reducer still has good water reducing performance.
Description
Technical Field
The invention relates to the technical field of polycarboxylic acid water reducing agents, and particularly relates to a polycarboxylic acid water reducing agent and a preparation method thereof.
Background
At present, along with the development of the concrete industry, the polycarboxylate superplasticizer is widely applied to a plurality of projects, and as a high-performance water reducing agent, the polycarboxylate superplasticizer has the advantages of low mixing amount, high water reducing rate, strong dispersing capacity, good concrete workability, good slump retaining performance and the like. However, in the practical application of the polycarboxylate water reducer, as the polycarboxylate water reducer is easily polluted by microorganisms such as mold and bacteria, the polycarboxylate water reducer product is easy to grow mold and deteriorate in the transportation and storage processes, so that the water reducing rate of the polycarboxylate water reducer is further reduced, and even the polycarboxylate water reducer completely loses the water reducing performance.
Disclosure of Invention
Based on the above, a polycarboxylate superplasticizer and a preparation method thereof are needed to be provided, aiming at solving the technical problems that the polycarboxylate superplasticizer in the prior art is easy to grow mildew and deteriorate and the water reducing rate is reduced.
In order to achieve the purpose, the invention provides the following technical scheme:
a polycarboxylate superplasticizer comprises the following components in percentage by mass (10-40): (10-20): (2-8): 200 of a compound B, an unsaturated acid, an unsaturated amide monomer and an unsaturated polyether macromonomer, wherein the compound B is an esterification product of a preservative compound A and unsaturated anhydride, and the preservative compound A has the structural formula:
wherein R is C1-C5 alkyl.
Preferably, the preservative compound a is one or more of methyl paraben, ethyl paraben, propyl paraben, butyl paraben and pentyl paraben.
Preferably, the unsaturated anhydride is one or more of maleic anhydride, itaconic anhydride and succinic anhydride.
Preferably, the unsaturated acid is one or more of acrylic acid and methacrylic acid.
Preferably, the unsaturated amide monomer is one or more of N-butoxyacrylamide, N-dimethyl (meth) acrylamide, N-dimethyl bisacrylamide.
Preferably, the unsaturated polyether macromonomer is one or more of allyl polyoxyethylene ether, isobutenol polyoxyethylene ether, prenol polyoxyethylene ether, vinyl polyoxyethylene ether and hydroxybutyl vinyl polyoxyethylene ether.
The invention also provides a preparation method of the polycarboxylate superplasticizer, which comprises the following steps:
1) dissolving unsaturated polyether macromonomer and a compound B in a water solvent;
2) in the presence of an initiator, dropwise adding a mixed solution of unsaturated acid and unsaturated amide monomers in the step 1) to perform free radical copolymerization reaction to obtain the product;
the mass ratio of the compound B, the unsaturated acid, the unsaturated amide monomer and the unsaturated polyether macromonomer is (10-40): (10-20): (2-8): 200 of a carrier;
the compound B is an esterification product of a preservative compound A and unsaturated acid anhydride, and the structural formula of the preservative compound A is as follows:
wherein R is C1-C5 alkyl.
Preferably, the initiator is a free radical water soluble initiator comprising an oxidizing component, or a combination of an oxidizing component initiator and a reducing component.
Preferably, the preparation method of the polycarboxylic acid water reducing agent further comprises the step of dropwise adding a mixed solution of unsaturated acid and unsaturated amide monomer in the step 1) in the presence of a chain transfer agent to perform free radical copolymerization reaction.
Preferably, the chain transfer agent is a thiol chain transfer agent.
The polycarboxylic acid water reducing agent has the following beneficial effects:
compared with the prior art, the polycarboxylate superplasticizer prepared by matching the components can greatly improve the self-anticorrosion effect of the polycarboxylate superplasticizer, so that the quality guarantee period of the polycarboxylate superplasticizer is prolonged, and the polycarboxylate superplasticizer has better water reducing performance; in the later-stage polycarboxylate water reducer compounding process, no preservative is required to be added, the compounded polycarboxylate water reducer still has good corrosion resistance, the polycarboxylate water reducer can be kept not to deteriorate for a long time, and the polycarboxylate water reducer still has good water reducing performance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
The experimental procedures in the following examples are conventional unless otherwise specified. Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, including a technical scheme, and a technical scheme that a and B meet simultaneously; in addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a polycarboxylate superplasticizer which comprises the following components in percentage by mass (10-40): (10-20): (2-8): 200 of a compound B, an unsaturated acid, an unsaturated amide monomer and an unsaturated polyether macromonomer, wherein the compound B is an esterification product of a preservative compound A and unsaturated anhydride, and the preservative compound A has the structural formula:
wherein R is C1-C5 alkyl.
Compared with the prior art, the polycarboxylate superplasticizer prepared by matching the components can greatly improve the self-anticorrosion effect of the polycarboxylate superplasticizer, so that the quality guarantee period of the polycarboxylate superplasticizer is prolonged, and the polycarboxylate superplasticizer has better water reducing performance; in the later-stage polycarboxylate water reducer compounding process, no preservative is required to be added, the compounded polycarboxylate water reducer still has good corrosion resistance, the polycarboxylate water reducer can be kept not to deteriorate for a long time, and the polycarboxylate water reducer still has good water reducing performance.
In some embodiments, the weight average molecular weight of the polycarboxylate superplasticizer is 30000-80000, so that the polycarboxylate superplasticizer has good dispersing capacity and slump retaining capacity.
In some embodiments, the weight average molecular weight of the polycarboxylate superplasticizer is 30000-50000, so that the prepared polycarboxylate superplasticizer has better dispersing capacity and slump retaining capacity.
In some embodiments, the preservative compound a comprises one or more of methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate and amyl p-hydroxybenzoate, and the preservative compound a can be introduced into the molecular structure of the polycarboxylate water reducer through esterification of any one or more of the preservative compound a and unsaturated anhydride, so that the polycarboxylate water reducer has excellent preservative property.
In some embodiments, the unsaturated anhydride is any one or more of maleic anhydride, itaconic anhydride and succinic anhydride, and the unsaturated anhydride is used for esterification with the preservative compound A to generate an esterification product of the preservative compound A and the unsaturated anhydride, so that the preservative compound A is introduced into the polycarboxylic acid water reducing agent, and the polycarboxylic acid water reducing agent has excellent bactericidal and preservative effects and water reducing performance.
In some embodiments, the unsaturated acid is an unsaturated carboxylic acid monomer, and the carboxylic acid group of the unsaturated carboxylic acid monomer provides an adsorption point and an electrostatic repulsion to facilitate the production of the polycarboxylic acid water reducer.
In some embodiments, the unsaturated acid is any one or more of acrylic acid and methacrylic acid, and the carboxylic acid groups of the acrylic acid and the methacrylic acid provide adsorption points and electrostatic repulsion to facilitate the production of the polycarboxylic acid water reducer.
In some embodiments, the unsaturated amide monomer is any one or more of N-butoxyacrylamide, N-dimethyl (meth) acrylamide, N-dimethyl bisacrylamide to improve the water reducing performance of the polycarboxylate water reducer.
In some embodiments, any one or more of unsaturated polyether macromonomer allyl polyoxyethylene ether, isobutenol polyoxyethylene ether, prenol polyoxyethylene ether, vinyl polyoxyethylene ether, hydroxybutyl vinyl polyoxyethylene ether.
Specifically, the molecular weight of the unsaturated polyether macromonomer is 3000-6000, and the polycarboxylic acid water reducing agent synthesized by the unsaturated polyether macromonomer with the molecular weight of 3000-6000 has excellent water reducing performance.
The invention also provides a preparation method of the polycarboxylate superplasticizer, which comprises the steps of
1) Dissolving unsaturated polyether macromonomer and a compound B in a water solvent;
2) in the presence of an initiator, dropwise adding a mixed solution of unsaturated acid and unsaturated amide monomers in the step 1) to perform free radical copolymerization reaction to obtain the product;
the mass ratio of the compound B, the unsaturated acid, the unsaturated amide monomer and the unsaturated polyether macromonomer is (10-40): (10-20): (2-8): 200 of a carrier;
the compound B is an esterification product of a preservative compound A and unsaturated acid anhydride, and the structural formula of the preservative compound A is as follows:
wherein R is C1-C5 alkyl.
Compared with the prior art, the preparation method of the polycarboxylate superplasticizer has the advantages that the polycarboxylate superplasticizer with excellent corrosion resistance and water reducing performance is obtained through the free radical copolymerization reaction of the components, the polycarboxylate superplasticizer does not need to be added with a preservative in the later compounding process, the compounded polycarboxylate superplasticizer still has good corrosion resistance, the polycarboxylate superplasticizer can be kept from going bad for a long time, and the polycarboxylate superplasticizer still has good water reducing performance.
Specifically, the water may be, but is not limited to, deionized water.
Specifically, the preparation method of the esterification product of the preservative compound A and the unsaturated anhydride comprises the following steps: the method comprises the steps of adding unsaturated anhydride, a preservative compound A and a polymerization inhibitor into a reaction container, mixing, adding a catalyst under the protection of protective nitrogen, adjusting the temperature, and cooling to room temperature after the reaction is finished to obtain an esterification product.
Specifically, the mass ratio of the preservative compound A to the unsaturated acid anhydride is (55-76): (78-103).
In some embodiments, unsaturated acid anhydride, preservative compound a and polymerization inhibitor are added into a reaction vessel to be mixed, under the protection of protective nitrogen, catalyst is added, the temperature is adjusted to 80-100 ℃, reaction is carried out for 2-5 hours, and the temperature is reduced to room temperature after the reaction is finished, so that an esterification product of preservative compound a and unsaturated acid anhydride is obtained.
In some embodiments, the catalyst is one or more of benzenesulfonic acid, p-toluenesulfonic acid, ethylsulfonic acid, and 98% concentrated sulfuric acid to accelerate the reaction of preservative compound a with the unsaturated anhydride esterification reaction.
Specifically, the dosage of the catalyst is 0.3-3.0% of the total mass of the unsaturated anhydride and the preservative compound A.
In some embodiments, the polymerization inhibitor is one or more of hydroquinone, phenothiazine, and diphenylamine, which react with free radicals in the polymerization chain to terminate polymerization to promote formation of the esterification product of preservative compound a and the unsaturated anhydride.
Specifically, the dosage of the polymerization inhibitor is 0.1-2.0% of the total mass of the unsaturated anhydride and the preservative compound A.
In some embodiments, the initiator is a free radical water soluble initiator, and the initiator comprises an oxidizing component, or a combination of an oxidizing component initiator and a reducing component, to initiate a free radical polymerization reaction during the preparation of the polycarboxylate water reducer, further resulting in the polycarboxylate water reducer having superior water reducing performance.
Specifically, when the initiator is an oxidizing component, the total amount of the oxidizing component initiator accounts for 0.1-2% of the total mass of the unsaturated polyether macromonomer and the unsaturated acid; when the initiator is selected from an oxidation component initiator and a reduction component initiator, the mass ratio of the oxidation component initiator to the reduction component initiator is (0.4-6): 1, so as to better initiate free radical polymerization reaction in the preparation process of the polycarboxylate superplasticizer.
In some embodiments, the oxidizing component initiator is a peroxide or a water-soluble azo-type compound; the initiator of the reducing component is any one of hydrosulfite, sulfite, thiosulfate, pyrosulfite, sodium formaldehyde sulfoxylate and L-ascorbic acid.
Specifically, the peroxide is hydrogen peroxide and persulfate, and the persulfate comprises ammonium persulfate and potassium persulfate.
Specifically, the water-soluble azo compounds include azobisisobutyramidine hydrochloride and azobisisopropylimidazoline hydrochloride.
In some embodiments, the preparation method of the polycarboxylic acid water reducing agent further comprises the step of dropwise adding a mixed solution of unsaturated acid and unsaturated amide monomer in the step 1) in the presence of a chain transfer agent to perform a free radical copolymerization reaction.
In some embodiments, the chain transfer agent is a thiol chain transfer agent effective to promote the free radical copolymerization reaction.
Preferably, the total amount of the chain transfer agent is 0.1-1% of the total mass of the unsaturated carboxylic acid and the unsaturated polyether macromonomer.
Specifically, the mercaptan chain transfer agent comprises one or more of mercaptopropionic acid, mercaptopropanol, mercaptoacetic acid and mercaptoethanol.
In some embodiments, in the preparation method of the polycarboxylate superplasticizer, the reaction temperature is 15-55 ℃, and the reaction temperature is mainly related to the decomposition efficiency and half-life period of the used initiator.
In some embodiments, in the preparation method of the polycarboxylate superplasticizer, the dropping time of the mixed solution of the unsaturated acid and the unsaturated amide monomer is controlled to be 0.5-3 h, so that the free radical copolymerization reaction is fully performed.
In some embodiments, in order to improve the yield of the carboxylic acid polymer, in the preparation method of the polycarboxylic acid water reducing agent, the heat preservation is continued after the initiator solution is dripped, and the heat preservation time is 0-2 hours.
In some embodiments, the polycarboxylate water reducer can be further neutralized with an alkaline substance to enhance the storage stability of the polycarboxylate water reducer.
Specifically, the amount of the alkaline substance is used for adjusting the pH value of the polycarboxylate superplasticizer to 6-7.
The following are specific examples, and the starting materials in the examples are all commercially available products unless otherwise specified.
Example 1
(1) Preparation of esterification product: adding 60g of maleic anhydride, 78g of methyl p-hydroxybenzoate and 0.68g of hydroquinone into a reaction vessel, mixing, adding 1.10g of concentrated sulfuric acid under the protection of protective nitrogen, adjusting the temperature to 90 ℃ for reaction for 4 hours, and cooling to room temperature after the reaction is finished to obtain an esterification product;
(2) and (3) copolymerization reaction: adding 40g of the esterification product prepared in the step (1), 100g of allyl polyoxyethylene ether with the molecular weight of 4000, 100g of 4000-isobutenol polyoxyethylene ether and 150g of deionized water into a reaction vessel for mixing, then dissolving 15g of acrylic acid and 3g N-butoxyacrylamide into 15g of deionized water to obtain a mixed solution of acrylic acid and N-butoxyacrylamide, dropwise adding the mixed solution of acrylic acid and N-butoxyacrylamide into the reaction vessel, wherein the dropwise adding time of the mixed solution of acrylic acid and N-butoxyacrylamide is 3 hours, and simultaneously dropwise adding a hydrogen peroxide aqueous solution (3.0 g of hydrogen peroxide and 30.0g of deionized water), an ascorbic acid aqueous solution (0.60 g of ascorbic acid and 30.0g of deionized water) and a mercaptopropionic acid aqueous solution (1.8 g of thioglycolic acid and 30.0g of deionized water) into the reaction vessel for reaction respectively, and (3) keeping the reaction temperature at 25 ℃, keeping the temperature for 1h after the dropwise addition is finished, cooling to room temperature after the heat preservation is finished, adjusting the pH to 6-7 by using a sodium hydroxide solution, and adjusting the mass concentration of the polymer to 50% by using deionized water to obtain the polycarboxylic acid water reducer.
Example 2
(1) Preparation of esterification product: adding 76g of itaconic anhydride, 101g of ethyl p-hydroxybenzoate and 0.92g of phenothiazine into a reaction vessel, mixing, adding 1.34g of benzenesulfonic acid under the protection of protective nitrogen, adjusting the temperature to 95 ℃, reacting for 3 hours, and cooling to room temperature after the reaction is finished to obtain an esterification product;
(2) and (3) copolymerization reaction: adding 10g of the esterification product prepared in the step (1), 200g of prenyl polyoxyethylene ether with the molecular weight of 6000 and 120g of deionized water into a reaction container, mixing, then dissolving 12g of methacrylic acid and 4g N, N-dimethyl (methyl) acrylamide into 15g of deionized water to obtain a mixed solution of the methacrylic acid and the N, N-dimethyl (methyl) acrylamide, dropwise adding the mixed solution of the methacrylic acid and the N, N-dimethyl (methyl) acrylamide into the reaction container, wherein the dropwise adding time of the mixed solution of the methacrylic acid and the N, N-dimethyl (methyl) acrylamide is 2 hours, simultaneously, adding an ammonium persulfate solution (wherein 3.0g of ammonium persulfate, 30.0g of deionized water), a sodium hypophosphite aqueous solution (wherein 4.0g of sodium hypophosphite, 30.0g of deionized water) and a mercaptoethanol aqueous solution (wherein 1.1g of mercaptoethanol, 30.0g of deionized water) are respectively dripped into the reaction containers for reaction, the reaction temperature is 40 ℃, heat preservation is carried out for 0.5h after dripping is finished, the temperature is reduced to room temperature after heat preservation is finished, the pH value is adjusted to 6-7 by sodium hydroxide solution, and the mass concentration of the polymer is adjusted to 50% by deionized water, so that the polycarboxylic acid water reducer is obtained.
Example 3
(1) Preparation of esterification product: adding 55g of succinic anhydride, 89g of propyl p-hydroxybenzoate and 0.83g of diphenylamine into a reaction vessel, mixing, adding 1.20g of ethylsulfonic acid under the protection of protective nitrogen, adjusting the temperature to 100 ℃ for reaction for 2 hours, and cooling to room temperature after the reaction is finished to obtain an esterified product;
(2) and (3) copolymerization reaction: adding 20g of the esterification product prepared in the step (1), 200g of vinyl polyoxyethylene ether with the molecular weight of 3000 and 120g of deionized water into a reaction container for mixing, then dissolving 20g of acrylic acid and 5g N, N-dimethyl bisacrylamide into 15g of deionized water to obtain a mixed solution of acrylic acid and N, N-dimethyl bisacrylamide, dropwise adding the mixed solution of acrylic acid and N, N-dimethyl bisacrylamide into the reaction container, dropwise adding the mixed solution of acrylic acid and N, N-dimethyl bisacrylamide for 0.5h, and simultaneously dropwise adding a hydrogen peroxide aqueous solution (wherein 2.5g of hydrogen peroxide and 30.0g of deionized water), a formaldehyde sodium sulfoxylate aqueous solution (wherein 1.2g of formaldehyde sodium sulfoxylate and 30.0g of deionized water) and a thioglycollic acid aqueous solution (wherein 1.2g of thioglycollic acid and 30.0g of deionized water) into the reaction container for reaction respectively, and (3) keeping the reaction temperature at 15 ℃, keeping the temperature for 2h after the dropwise addition is finished, cooling to room temperature after the heat preservation is finished, adjusting the pH to 6-7 by using a sodium hydroxide solution, and adjusting the mass concentration of the polymer to 50% by using deionized water to obtain the polycarboxylic acid water reducer.
Example 4
(1) Preparation of esterification product: adding 70g of maleic anhydride, 70g of methyl p-hydroxybenzoate, 33g of amyl p-hydroxybenzoate and 0.93g of hydroquinone into a reaction vessel, mixing, adding 1.66g of ethylsulfonic acid under the protection of protective nitrogen, adjusting the temperature to 80 ℃ for reaction for 5 hours, and cooling to room temperature after the reaction is finished to obtain an esterification product;
(2) and (3) copolymerization reaction: adding 30g of the esterification product prepared in the step (1), 200g of methacryloxypolyoxyethylene ether with the molecular weight of 4000 and 130g of deionized water into a reaction vessel for mixing, then dissolving 16g of acrylic acid and 6g N, N-dimethyl bisacrylamide into 15g of deionized water to obtain a mixed solution of acrylic acid and N, N-dimethyl bisacrylamide, dropwise adding the mixed solution of acrylic acid and N, N-dimethyl bisacrylamide into the reaction vessel, dropwise adding the mixed solution of acrylic acid and N, N-dimethyl bisacrylamide for 1h, and simultaneously dropwise adding a potassium persulfate aqueous solution (3.2 g of potassium persulfate and 30.0g of deionized water), a sodium bisulfite aqueous solution (3.6 g of sodium bisulfite and 30.0g of deionized water) and a mercaptoethanol aqueous solution (1.3 g of mercaptoethanol and 30.0g of deionized water) into the reaction vessel for reaction respectively, and (3) keeping the reaction temperature at 55 ℃, keeping the temperature for 2h after the dropwise addition is finished, cooling to room temperature after the heat preservation is finished, adjusting the pH to 6-7 by using a sodium hydroxide solution, and adjusting the mass concentration of the polymer to 50% by using deionized water to obtain the polycarboxylic acid water reducer.
Comparative example 1
And (3) copolymerization reaction: adding 100g of allyl polyoxyethylene ether with the molecular weight of 4000, 100g of 4000-isobutenol polyoxyethylene ether and 100g of deionized water into a reaction vessel for mixing, then dissolving 15g of acrylic acid and 3g N-butoxyacrylamide into 15g of deionized water to obtain a mixed solution of acrylic acid and N-butoxyacrylamide, dropwise adding the mixed solution of acrylic acid and N-butoxyacrylamide into the reaction vessel, dropwise adding the mixed solution of acrylic acid and N-butoxyacrylamide for 3 hours, and simultaneously dropwise adding a hydrogen peroxide aqueous solution (3.0 g of hydrogen peroxide and 30.0g of deionized water), an ascorbic acid aqueous solution (0.60 g of ascorbic acid and 30.0g of deionized water) and a mercaptopropionic acid aqueous solution (1.8 g of thioglycolic acid and 30.0g of deionized water) into the reaction vessel for reaction at the reaction temperature of 25 ℃, and (3) preserving heat for 1h after the dropwise addition is finished, cooling to room temperature after the heat preservation is finished, adjusting the pH to 6-7 by using a sodium hydroxide solution, and adjusting the mass concentration of the polymer to 50% by using deionized water to obtain the polycarboxylic acid water reducer.
Performance evaluation
The performance of the polycarboxylic acid water reducing agent of the present invention was evaluated by combining examples 1 to 4, comparative example 1, a commercially available polycarboxylic acid water reducing agent product without adding a preservative, and a polycarboxylic acid water reducing agent obtained by adding a paraben preservative to a commercially available polycarboxylic acid water reducing agent product.
1. Change in appearance
TABLE 1 polycarboxylate superplasticizer appearance variation
As can be seen from Table 1, compared with the commercial polycarboxylate water reducer products without the preservative in the comparative example 1 and the commercial polycarboxylate water reducer products with no preservative added and the paraben preservative added in the commercial polycarboxylate water reducer products, the polycarboxylate water reducer in the example has no peculiar smell or mold in 12 months, but in the commercial polycarboxylate water reducer products in the comparative example 1 and the commercial polycarboxylate water reducer products without preservative added, the polycarboxylate water reducer begins to generate peculiar smell or mold in 1 month; when a nipagin ester preservative is added into a commercial polycarboxylate water reducer product, the polycarboxylate water reducer can be kept free from generating peculiar smell and mould in the first three months, but the peculiar smell and the mould begin to generate in 6 months; the shelf life of the commercial polycarboxylate water reducer added with the nipagin ester preservative is still far shorter than that of the polycarboxylate water reducer in the invention, so that the polycarboxylate water reducer in the invention can have a superior preservative effect for a long time. In addition, the polycarboxylate superplasticizer does not need to be additionally added with a preservative in the later compounding process, and the compounded polycarboxylate superplasticizer still has good corrosion resistance.
2. Water reducing agent evaluation
The water reducing rates of the polycarboxylic acid water reducing agents of examples 1 to 4 and comparative example 1, which were commercially available without adding a preservative, and the polycarboxylic acid water reducing agents to which a paraben preservative was added in the commercially available polycarboxylic acid water reducing agent product of the present invention were tested by using reference cement according to the test requirements in "concrete admixture" (GB 8076-2008).
The results are as follows:
TABLE 2 Water reduction Rate testing
As can be seen from Table 2, the water reducing performance of the polycarboxylic acid water reducer of the present invention is more than 30% and most of the water reducing performance can reach 33% to 34% within 12 months, compared with the commercial polycarboxylic acid water reducer product of comparative example 1 without adding the preservative and the commercial polycarboxylic acid water reducer product with adding the paraben preservative, in the commercial polycarboxylic acid water reducer product of comparative example 1 without adding the preservative, the water reducing rate is decreased within 0 to 12 months, and is decreased to 27% within 12 months, and when the commercial polycarboxylic acid water reducer product is added with the paraben preservative, the water reducing rate of the polycarboxylic acid water reducer is decreased to a degree which is moderate, but within 0 to 12 months, the water reducing rate is still decreased within 0 to 12 months, and is decreased to 28.5% within 12 months, although the water reducing rate of the commercial polycarboxylate water reducer with the nipagin ester preservative at 12 months is higher than that of the commercial polycarboxylate water reducer with the comparative example 1 and the commercial polycarboxylate water reducer without the preservative, the water reducing rate is still far lower than that of the polycarboxylate water reducer in the embodiments 1-4 of the invention, so that the water reducer in the invention can still have excellent water reducing performance for 12 months.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. The polycarboxylate superplasticizer is characterized by comprising the following components in percentage by mass (10-40): (10-20): (2-8): 200 of a compound B, an unsaturated acid, an unsaturated amide monomer and an unsaturated polyether macromonomer, wherein the compound B is an esterification product of a preservative compound A and unsaturated anhydride, and the preservative compound A has a structural formula as follows:
wherein R is C1-C5 alkyl.
2. The polycarboxylate water reducer according to claim 1, wherein said preservative compound A is one or more of methyl paraben, ethyl paraben, propyl paraben, butyl paraben and pentyl paraben.
3. The polycarboxylate water reducer according to claim 1, characterized in that the unsaturated anhydride is one or more of maleic anhydride, itaconic anhydride and succinic anhydride.
4. The polycarboxylate water reducer according to claim 1, characterized in that the unsaturated acid is one or more of acrylic acid and methacrylic acid.
5. The polycarboxylate water reducer according to claim 1, characterized in that the unsaturated amide monomer is one or more of N-butoxyacrylamide, N-dimethyl (meth) acrylamide, N-dimethyl bisacrylamide.
6. The polycarboxylate water reducer according to claim 1, wherein the unsaturated polyether macromonomer is one or more selected from allyl polyoxyethylene ether, isobutenol polyoxyethylene ether, prenol polyoxyethylene ether, vinyl polyoxyethylene ether and hydroxybutyl vinyl polyoxyethylene ether.
7. A preparation method of a polycarboxylate superplasticizer is characterized by comprising the following steps:
1) dissolving unsaturated polyether macromonomer and a compound B in a water solvent;
2) in the presence of an initiator, dropwise adding a mixed solution of unsaturated acid and unsaturated amide monomers in the step 1) to perform free radical copolymerization reaction to obtain the product;
the mass ratio of the compound B to the unsaturated acid to the unsaturated amide monomer to the unsaturated polyether macromonomer is (10-40): (10-20): (2-8): 200 of a carrier;
the compound B is an esterification product of a preservative compound A and unsaturated acid anhydride, and the preservative compound A has a structural formula as follows:
wherein R is C1-C5 alkyl.
8. The method of claim 7, wherein the initiator is a free radical water soluble initiator comprising an oxidizing component, or a combination of an oxidizing component initiator and a reducing component.
9. The preparation method of claim 7, further comprising the step of dropwise adding a mixed solution of the unsaturated acid and the unsaturated amide monomer in the step 1) in the presence of a chain transfer agent to perform a radical copolymerization reaction.
10. The method according to claim 9, wherein the chain transfer agent is a thiol chain transfer agent.
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