WO2022142125A1 - 降粘型聚羧酸混凝土减水剂及其制备方法 - Google Patents
降粘型聚羧酸混凝土减水剂及其制备方法 Download PDFInfo
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- WO2022142125A1 WO2022142125A1 PCT/CN2021/097841 CN2021097841W WO2022142125A1 WO 2022142125 A1 WO2022142125 A1 WO 2022142125A1 CN 2021097841 W CN2021097841 W CN 2021097841W WO 2022142125 A1 WO2022142125 A1 WO 2022142125A1
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- Prior art keywords
- reducing agent
- viscosity
- reducing
- water
- concrete
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 60
- 239000004567 concrete Substances 0.000 title claims abstract description 60
- 239000002253 acid Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000009467 reduction Effects 0.000 title abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 21
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 19
- -1 isoamylene alcohol Chemical compound 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 14
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims abstract description 14
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 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 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 229930003268 Vitamin C Natural products 0.000 claims description 5
- 125000004386 diacrylate group Chemical group 0.000 claims description 5
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 235000019154 vitamin C Nutrition 0.000 claims description 5
- 239000011718 vitamin C Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical group OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 3
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- LBVGZFLZUZLTKK-UHFFFAOYSA-N [Na].C(C(=C)C)(=O)O.[Na] Chemical compound [Na].C(C(=C)C)(=O)O.[Na] LBVGZFLZUZLTKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000004576 sand Substances 0.000 abstract description 10
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005086 pumping Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000008030 superplasticizer Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 206010016807 Fluid retention Diseases 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- LHTVMBMETNGEAN-UHFFFAOYSA-N pent-1-en-1-ol Chemical compound CCCC=CO LHTVMBMETNGEAN-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000010998 test method Methods 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
-
- 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
- C04B2103/46—Water-loss or fluid-loss reducers, hygroscopic or hydrophilic agents, water retention agents
- C04B2103/465—Water-sorbing agents, hygroscopic or hydrophilic agents
Definitions
- the invention relates to the field of concrete admixtures in building materials, in particular to a viscosity-reducing polycarboxylate concrete water-reducing agent and a preparation method thereof.
- the methods to solve the above problems are mainly through some conventional methods such as increasing the amount of admixtures, the water consumption of concrete, and increasing the air content of concrete.
- these methods will inevitably introduce some other problems.
- the molecular structure of polycarboxylate concrete admixtures can be designed It has strong properties, and the adaptability of polycarboxylate water reducer to different concretes can be achieved by controlling the degree of polymerization of the main chain, the density of side chains, and the types of functional groups.
- As an important raw material for improving the performance of concrete it often has a significant effect on improving the performance and construction performance of concrete.
- Designing a functional polycarboxylate superplasticizer can effectively reduce the water consumption and cementing material consumption of concrete, and adjust the cohesion and water retention of concrete, which is one of the main ways to improve the workability of concrete.
- the invention patent whose publication number is CN 109651566 A discloses a viscosity-reducing polycarboxylate water-reducing agent and a preparation method thereof; the viscosity-reducing type polycarboxylate water-reducing agent is prepared by polymerizing the raw materials including the following components:
- the block-modified unsaturated polyoxyethylene ether, unsaturated carboxylic acid and functional monomer are prepared through copolymerization reaction and alkali neutralization under the action of initiator and chain transfer agent.
- This scheme uses block-modified unsaturated polyoxyethylene ether as the raw material.
- the side chain of the block polyether contains hydrophobic groups, and the molecular structure stretches better. By adding different functional groups to optimize the structure, we can get excellent performance.
- the viscosity-reducing water-reducing agent synthesized by this method has a high dosage, and has the side effect of consuming the water-reducing water-reducing agent to a certain extent.
- the invention patent with publication number CN 108003301 A provides a preparation method of a viscosity-reducing polycarboxylate water-reducing agent, and the viscosity-reducing type polycarboxylate water-reducing agent is obtained by bulk polymerization, which specifically includes the following steps: (1) Mix the polyoxyethylene polyoxypropylene ether and the polyoxyethylene ether, control the temperature to be 40-60°C, stir evenly, and then add the initiator and the mixture of unsaturated carboxylic acid, unsaturated carboxylic acid hydroxyalkyl ester and chain transfer agent (2) After the step (1) is completed, it is aged for 1 to 1.5 hours, and the temperature is lowered to obtain a viscosity-reducing polycarboxylate water-reducing agent.
- the bulk polymerization reaction is carried out at relatively low temperature, with strong operability, mild conditions and low energy consumption.
- the polycarboxylate water reducer prepared by the above method can effectively reduce the viscosity of concrete mixture, but the viscosity reduction effect of this solution is not ideal.
- the technical problem to be solved by the present invention is to provide a viscosity-reducing polycarboxylate concrete water-reducing agent and a preparation method thereof, so as to overcome the insufficiency of concrete dispersion, stickiness, wrapping and slump loss of machine-made sand concrete during use major issues.
- a viscosity-reducing polycarboxylate concrete water-reducing agent comprising in parts by weight, 120-240 parts of isobutylene alcohol polyoxyethylene polyoxypropylene block polyether, isobutylene alcohol 150-250 parts of pentenol polyoxyethylene ether, 12-50 parts of unsaturated carboxylic acid, 5-20 parts of functional monomer, 0.5-2.0 parts of chain transfer agent, 1-6.0 parts of oxidant, 0.1-2 parts of reducing agent , 10-40 parts of neutralizer, 220-320 parts of deionized water.
- the present invention also provides a preparation method of a viscosity-reducing polycarboxylate concrete water-reducing agent, comprising the following steps:
- isobutylene alcohol polyoxyethylene polyoxypropylene block polyether of the present invention is propylene oxide and ethylene oxide block polyether with different degrees of polymerization, and the average molecular weight is 500-1200.
- prenyl alcohol polyoxyethylene ether of the present invention is a polyether monomer with a molecular weight of 3000-4000.
- the unsaturated carboxylic acid of the present invention is one or more of acrylic acid, itaconic acid, maleic acid or methacrylic acid.
- the functional monomers described in the present invention are hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, dodecyl methacrylate, polyethylene glycol One or more of acrylate or polyethylene glycol dimethacrylate.
- polyethylene glycol diacrylate of the present invention is an acrylate compound with an ethylene glycol polymerization degree of 200-400.
- mass ratio of isobutenol polyoxyethylene polyoxypropylene block polyether of the present invention isopentenol polyoxyethylene ether: unsaturated carboxylic acid: functional monomer: chain transfer agent is 1: ( 0.75 ⁇ 2.2):(0.07 ⁇ 0.12):(0.015 ⁇ 0.03):(0.003 ⁇ 0.008);
- the mixture of the present invention is added dropwise in the form of A and B, and the dropwise addition is completed at a constant speed within 2 to 4 hours;
- the reaction temperature of the viscosity-reducing polycarboxylate water-reducing agent during the dropping process is: 30 ⁇ 50°C;
- the chain transfer agent of the present invention is one or more of thioglycolic acid, sulfonated mercapto acid, mercaptopropionic acid, sodium hypophosphite or sodium methacrylic acid sodium sulfonate;
- the oxidant is At least one of 30% concentration of hydrogen peroxide, ammonium persulfate, dimethyl azodiisobutyrate or diisopropyl peroxydicarbonate;
- the reducing agent is vitamin C, hypophosphorous acid, phosphorous acid, phosphonium
- the neutralizing agent is one or both of potassium hydroxide and sodium hydroxide solution.
- the present invention adopts the method of compound copolymerization of small molecule isobutenol polyoxyethylene polyoxypropylene block polyether and isoprenol polyoxyethylene ether.
- the polyether is embedded in the polyether structure molecule by adding propylene oxide.
- Hydrophobic groups compared with ordinary polyether molecules, polyethers with amphoteric group structure are more diverse in molecular structure, can better stretch molecular chains in concrete, show good dispersibility, and at the same time molecular
- the introduction of hydrophobic groups into the side chain can reduce the HLB value, reduce the binding of free water and molecules, and show the effect of low viscosity.
- prenol polyoxyethylene ether utilizes its long side chain to exert its water-reducing and slump-reducing effect. The two side chain monomers combine with each other to fully play the role of water-reducing and viscosity-reducing.
- the molecular chain is optimized by adding different functional groups, such as the introduction of dodecyl methacrylate, octadecyl methacrylate, polyethylene glycol diacrylate and other groups, etc.
- the molecular structure of carboxylate superplasticizer can adjust the molecular HLB value of superplasticizer, increase the thickness of the adsorption layer of polycarboxylate superplasticizer, reduce the force between concrete particles, prevent the agglomeration of particles, and release free water between particles.
- To lubricate in order to achieve the effect of reducing the viscosity of concrete.
- the beneficial effects of the present invention are that, the defects existing in the background technology are solved, and the molecular structure of the viscosity reducing water reducing agent is optimized by introducing some functional monomers so that it has certain slump retention and water retention, and its resistance to inferior sandstone materials is improved.
- Adaptability significantly improve the ability to resist segregation and bleeding; use small molecular block polyether and isopentenyl polyoxyethylene ether to polymerize with functional monomers to improve the hydrophilic and lipophilic structure of polycarboxylic acid molecules, and add a small amount of The hydrophilic crosslinking agent improves the structure of the molecule, increases its viscosity reduction effect through slow release, and improves its adaptability to inferior sand and gravel materials.
- the time required for concrete to flow out of the inverted slump cylinder under the action of the water reducing agent prepared by the method of the present invention is: Significantly reduced, and also has a relative advantage over the sample PV415 on the market. It shows that the polycarboxylate water reducing agent prepared by the method of the present invention can effectively reduce the viscosity of concrete, improve the flow rate of high-grade machine-made sand concrete, greatly improve the working performance of concrete, and basically have no effect on the strength of concrete.
- the water reducing agent produced by the invention has a certain function of water reduction and slump retention, which can obviously reduce the slump loss of concrete.
- the method provided by the invention can produce the corresponding polycarboxylate water reducer according to the needs, so as to solve the problems that the traditional polycarboxylate water reducer is easily adsorbed by clay and stone powder, which leads to the excessive viscosity of the concrete mixture and the poor fluidity of the cement concrete. It is beneficial to the long-distance pumping of concrete and the construction of high-rise projects, and is suitable for large-scale industrial promotion and application.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明涉及一种降粘型聚羧酸混凝土减水剂及其制备方法,包括:将低分子量异丁烯醇聚氧乙烯聚氧丙烯嵌段聚醚、异戊烯醇聚氧乙烯醚与适量水混合,控制温度为40~60℃,搅拌均匀;分别滴加由不饱和羧酸、功能单体、链转移剂的混合物水溶液组成的A料以及由链转移剂、还原剂的混合物水溶液组成的B料,滴加时间控制在2~4小时;滴加结束后,在30~50℃条件下熟化1~1.5h,降温制得固含量为40%的降粘型聚羧酸减水剂。本发明制备的减水剂在常温下为液态,贮存性能稳定,能够有效降低高标号混凝土尤其是机制砂混凝土拌合物粘度,有利于混凝土搅拌、运输和泵送,尤其适用高层、超高层建筑泵送混凝土以及长距离输送混凝土的推广与应用。
Description
本发明涉及建筑材料中混凝土外加剂领域,尤其是一种降粘型聚羧酸混凝土减水剂及其制备方法。
随着国家建筑工业的日益发展,建筑材料中体量最大的原材料混凝土的消耗迅速增长,作为混凝土的原材料河砂的消耗也呈迅速增长趋势,由于砂石资源的逐渐枯竭以及国家对环境保护政策的实施,河沙作为一种重要的资源越来越难以获取,作为河沙的替代原材料机制砂逐渐在建筑工程中得到广泛的应用。由于机制砂具有棱角多、断级配现象较严重以及石粉含量多且不稳定的特点,传统普通聚羧酸减水剂虽然具有较高的减水率,对水泥颗粒能起到一定的分散作用,但其大量的极性吸附基团会造成吸附界面间产生较强的相互作用力,从而使混凝土粘度上升,导致了新拌混凝土尤其是高标号混凝土容易出现发粘、偏硬、包裹性差等现象,严重影响了混凝土的质量与施工。
目前解决以上问题的手段主要是通过提高外加剂掺量、混凝土用水量以及提高混凝土含气量等一些常规手段,但这些方法不可避免地会引入一些其它问题,聚羧酸混凝土外加剂分子结构可设计性强,可通过控制主链聚合度、侧链密度、官能团种类来实现聚羧酸减水剂与不同混凝土的适应性。作为提高混凝土性能的一种重要原材料对改善混凝土性能及施工性能往往会有明显作用。设计一种功能型聚羧酸系减水剂可以有效降低混凝土的用水量和胶凝材料用量,调节混凝土的粘聚性和保水性,是改善混凝土工作性的主要途径之一。
公开号为CN 109651566 A的发明专利公开了一种降粘型聚羧酸减水剂及其制备方法;该降粘型聚羧酸减水剂采用包括如下各组分原料经聚合反应制得:嵌段改性不饱和聚氧乙烯醚、不饱和羧酸、功能性单体通过在引发剂及链转移剂的作用下,通过共聚反应并加碱中和制备而成。该方案采用嵌段改性不饱和聚氧乙烯醚作为原料,该嵌段聚醚侧链含有疏水基团,分子结构舒展度更好,通过加入不同功能基团进行结构优化,可以得到性能优异的降粘减水剂,因此其具有成本低,分散性能好,降粘效果明显,引气量低,地材适应性强等优点。但是,按此种方法合成的降粘性减水剂,掺量高,一定程度上具有消耗减水型减水剂的副作用,性价比不高,且对机制砂材料的选择性不高。
公开号为CN 108003301 A的发明专利提供了一种降粘型聚羧酸减水剂的制备方法,通过本体聚合反应制得降粘型聚羧酸减水剂,具体包括以下步骤:(1)将聚氧乙烯聚氧丙烯醚和聚氧乙烯醚混合,控制温度为40~60℃,搅拌均匀,然后加入引发剂及不饱和羧酸、不饱和羧酸羟烷基酯和链转移剂的混合物;(2)所述步骤(1)完成后熟化1~1.5h,降温制得降粘型聚羧酸减水剂。本体聚合反应在相对低温下进行,可操作性强、条件温和、能耗低。以上述方法制备的聚羧酸减水剂能够有效降低混凝土拌合物粘度,但是该方案的降粘效果不理想。
发明内容
本发明要解决的技术问题是:提供一种降粘型聚羧酸混凝土减水剂及其制备方法,以克服机制砂混凝土在使用过程中的混凝土散、粘、包裹性不足以及坍落度损失大等问题。
本发明解决其技术问题所采用的技术方案是:一种降粘型聚羧酸混凝土减水剂,按重量份数包括,异丁烯醇聚氧乙烯聚氧丙烯嵌段聚醚120-240份,异戊 烯醇聚氧乙烯醚150-250份,不饱和羧酸12-50份,功能性单体5-20份,链转移剂0.5-2.0份,氧化剂1-6.0份,还原剂0.1-2份,中和剂10-40份,去离子水220-320份。
同时,本发明还提供了一种降粘型聚羧酸混凝土减水剂的制备方法,包括以下步骤,
1)将低分子量异丁烯醇聚氧乙烯聚氧丙烯嵌段聚醚、异戊烯醇聚氧乙烯醚与适量水混合,控制温度为40~60℃,搅拌均匀;
2)加入氧化剂,搅拌均匀,然后分别滴加由不饱和羧酸、功能单体、链转移剂的混合物水溶液组成的A料以及由链转移剂、还原剂的混合物水溶液组成的B料,滴加时间控制在2~4小时;
3)滴加结束后,在30~50℃条件下熟化1~1.5h,降温制得固含量为40%的降粘型聚羧酸减水剂。
进一步的说,本发明所述的异丁烯醇聚氧乙烯聚氧丙烯嵌段聚醚为不同聚合度的环氧丙烷、环氧乙烷嵌段聚醚,平均分子量为500-1200。
进一步的说,本发明所述的异戊烯醇聚氧乙烯醚是分子量为3000~4000的聚醚单体。
进一步的说,本发明所述的不饱和羧酸为丙烯酸、衣康酸、马来酸或甲基丙烯酸中的一种或多种。
进一步的说,本发明所述的功能性单体为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸十二烷基酯、聚乙二醇二丙烯酸酯或聚乙二醇二甲基丙烯酸酯中的一种或多种。
进一步的说,本发明所述聚乙二醇二丙烯酸酯是乙二醇聚合度为200~400的丙烯酸酯化合物。
进一步的说,本发明所述的异丁烯醇聚氧乙烯聚氧丙烯嵌段聚醚:异戊烯醇聚氧乙烯醚:不饱和羧酸:功能单体:链转移剂的质量比为1:(0.75~2.2):(0.07~0.12):(0.015~0.03):(0.003~0.008);
进一步的说,本发明所述的混合物以A、B料滴加的形式,在2~4小时内以恒定速度滴加完成;降粘型聚羧酸减水剂在滴加过程中反应温度为30~50℃;
进一步的说,本发明所述的链转移剂为巯基乙酸、磺化巯基酸、巯基丙酸、次亚磷酸钠或甲基丙烯基磺酸钠中的一种或多种;所述的氧化剂为30%浓度的双氧水、过硫酸铵、偶氮二异丁酸二甲酯或过氧化二碳酸二异丙酯中的至少一种;所述的还原剂为维生素C、次磷酸、亚磷酸、吊白粉或亚硫酸氢钠中的一种或多种;所述的中和剂为氢氧化钾、氢氧化钠溶液中的一种或两种。
本发明采用的是小分子异丁烯醇聚氧乙烯聚氧丙烯嵌段聚醚和异戊烯醇聚氧乙烯醚复合共聚的方法,该聚醚通过加成环氧丙烷,在聚醚结构分子上嵌入疏水基团,与普通的聚醚分子相比,带有两性基团结构的聚醚在分子结构上更加多样化,在混凝土中能更好地舒展分子链,表现出良好的分散性,同时分子侧链中引入疏水基团,能降低HLB值,减少自由水与分子结合,表现出低粘度的效果。另外,异戊烯醇聚氧乙烯醚利用其长侧链发挥其减水保坍作用。两种侧链单体互相结合充分发挥减水降粘作用。
本发明中通过加入不同功能基团对分子链进行优化,如引入甲基丙烯酸十二烷基酯、甲基丙烯酸十八烷基酯、聚乙二醇二丙烯酸酯等基团等,可以改善聚羧酸减水剂分子结构,调节减水剂分子HLB值,增加聚羧酸减水剂吸附层厚度,减少了混凝土颗粒间的作用力,防止颗粒的团聚,并释放颗粒间的游离水,起到润滑作用,以达到降低混凝土粘度的效果。
本发明的有益效果是,解决了背景技术中存在的缺陷,通过引入一些功能单体优化降粘性减水剂的分子结构使其具有一定的保坍和保水性,提高其对劣质砂石材料的适应性,明显改善抵抗离析、泌水的能力;利用小分子嵌段聚醚和异戊烯基聚氧乙烯醚与功能单体聚合,改善聚羧酸分子的亲水亲油结构,并添加少量亲水性交联剂改善分子的结构,通过缓慢释放提高其降粘效果并改善其对劣质砂石材料的适应性。
现在结合实施例对本发明作进一步详细的说明。
实施例1
1、在四口烧瓶内,加入异丁烯基聚氧乙烯聚氧丙烯醚(平均分子量600)120g,再加入150g异戊烯基聚氧乙烯醚(平均分子量3000),升温到45℃,搅拌溶解。
2、控温在45℃,往釜内加入双氧水(30%)4g,搅拌10min,然后内以恒定速度,滴加由30g丙烯酸、5g丙烯酸羟乙酯和1.5g磺化巯基酸的混合溶液组成的A料和0.5g维C水溶液的B料,滴加时间分别为3h、3.5h。
3、滴加结束后,继续熟化1h,然后降温至30℃。
4、向合成好的降粘型聚羧酸减水剂中加入氢氧化钠溶液中和,调节pH为6,补水至有效浓度40%,即得降粘型聚羧酸减水剂。
实施例2
1、在四口烧瓶内,加入异丁烯基聚氧乙烯聚氧丙烯醚(平均分子量600)120g,再加入150g异戊烯基聚氧乙烯醚(平均分子量3000),升温到45℃,搅拌溶解。
2、控温在45℃,往釜内加入双氧水(30%)4g,搅拌10min,然后内以恒定速度,滴加由25g丙烯酸、10g甲基丙酸甲酯和1.5g磺化巯基酸的混合溶液 组成的A料和0.5g维C水溶液的B料,滴加时间分别为3h、3.5h。
3、滴加结束后,继续熟化1h,然后降温至30℃。
4、向合成好的降粘型聚羧酸减水剂中加入氢氧化钠溶液中和,调节pH为6,补水至有效浓度40%,即得降粘型聚羧酸减水剂。
实施例3
1、在四口烧瓶内,加入异丁烯基聚氧乙烯聚氧丙烯醚(平均分子量1200)240g,再加入180g异戊烯基聚氧乙烯醚(平均分子量3000),升温到45℃,搅拌溶解。
2、控温在45℃,往釜内加入双氧水(30%)4g,搅拌10min,然后内以恒定速度,滴加由30g丙烯酸、5g丙烯酸羟乙酯和1.5g磺化巯基酸的混合溶液组成的A料和0.5g维C水溶液的B料,滴加时间分别为3h、3.5h。
3、滴加结束后,继续熟化1h,然后降温至30℃。
4、向合成好的降粘型聚羧酸减水剂中加入氢氧化钠溶液中和,调节pH为6,补水至有效浓度40%,即得降粘型聚羧酸减水剂。
实施例4
1、在四口烧瓶内,加入异丁烯基聚氧乙烯聚氧丙烯醚(平均分子量1200)120g,再加入180g异戊烯基聚氧乙烯醚(平均分子量3000),升温到45℃,搅拌溶解。
2、控温在45℃,往釜内加入双氧水(30%)4g,搅拌10min,然后内以恒定速度,滴加由30g丙烯酸、5g丙烯酸羟乙酯、0.2g聚乙二醇二丙烯酸酯和1g磺化巯基酸的混合溶液组成的A料和0.5g维C水溶液的B料,滴加时间分别为3h、3.5h。
3、滴加结束后,继续熟化1h,然后降温至30℃。
4、向合成好的降粘型聚羧酸减水剂中加入氢氧化钠溶液中和,调节pH为6,补水至有效浓度40%,即得降粘型聚羧酸减水剂。
实施例5
1、在四口烧瓶内,加入异丁烯基聚氧乙烯聚氧丙烯醚(平均分子量600)120g,再加入250g异戊烯基聚氧乙烯醚(平均分子量4000),升温到45℃,搅拌溶解。
2、控温在45℃,往釜内加入双氧水(30%)4g,搅拌10min,然后内以恒定速度,滴加由30g丙烯酸、5g丙烯酸羟乙酯和1g磺化巯基酸的混合溶液组成的A料和0.5g维C水溶液的B料,滴加时间分别为3h、3.5h。
3、滴加结束后,继续熟化1h,然后降温至30℃。
4、向合成好的降粘型聚羧酸减水剂中加入氢氧化钠溶液中和,调节pH为6,补水至有效浓度40%,即得降粘型聚羧酸减水剂。
实验结果:
按照表1所示的C60混凝土配合比制备高强混凝土,在相同水灰比条件下通过调整减水剂的用量控制混凝土的初始扩展度控制在500~550mm,检测初始、1h后混凝土坍落度、扩展度,含气量控制在2.0~3.0%,参照《普通混凝土拌合物性能试验方法标准》(GB/T 50080-2016),以倒置坍落度筒法流动时间试验来测试混凝土的粘度,混凝土流出倒置坍落度筒的用时越小,表示混凝土的粘度越小。并且以市售的减水型减水剂和型号为PV415的降粘型减水剂作为对比,检测掺有实施例1~5中合成的降粘型聚羧酸减水剂的降粘效果。
表1 C60机制砂混凝土配合比
表2降粘型减水剂混凝土性能对比表
由上表可看出,在控制混凝土初始工作性能一定范围条件下,对比空白条件下(不加降粘型),按本发明方法制备的减水剂作用下混凝土流出倒坍落度筒的用时显著减小,并且对比市场上的样品PV415也有相对优势。说明按本发明方法制备的聚羧酸减水剂能够有效降低混凝土的粘度,改善高标号机制砂混凝土的流速,混凝土工作性能得到很大改善,对混凝土强度基本无影响。另外通过本发明生产的减水剂具有一定的减水保坍功能,可明显减小混凝土的坍落度损失。通过本发明提供的方法可以根据需要生产对应的聚羧酸减水剂解决传统聚羧酸减水剂易被粘土、石粉吸附导致混凝土拌合物粘度过大,水泥混凝土的流动性差的问题,有利于混凝土的远距离泵送和高层工程施工,适于大规模的工业推广和应用。
以上说明书中描述的只是本发明的具体实施方式,各种举例说明不对本发 明的实质内容构成限制,所属技术领域的普通技术人员在阅读了说明书后可以对以前所述的具体实施方式做修改或变形,而不背离发明的实质和范围。
Claims (10)
- 一种降粘型聚羧酸混凝土减水剂,其特征在于:按重量份数包括,异丁烯醇聚氧乙烯聚氧丙烯嵌段聚醚120-240份,异戊烯醇聚氧乙烯醚150-250份,不饱和羧酸12-50份,功能性单体5-20份,链转移剂0.5-2.0份,氧化剂1-6.0份,还原剂0.1-2份,中和剂10-40份,去离子水220-320份。
- 一种如权利要求1所述的降粘型聚羧酸混凝土减水剂的制备方法,其特征在于:包括以下步骤,1)将低分子量异丁烯醇聚氧乙烯聚氧丙烯嵌段聚醚、异戊烯醇聚氧乙烯醚与适量水混合,控制温度为40~60℃,搅拌均匀;2)加入氧化剂,搅拌均匀,然后分别滴加由不饱和羧酸、功能单体、链转移剂的混合物水溶液组成的A料以及由链转移剂、还原剂的混合物水溶液组成的B料,滴加时间控制在2~4小时;3)滴加结束后,在30~50℃条件下熟化1~1.5h,降温制得固含量为40%的降粘型聚羧酸减水剂。
- 如权利要求1或2所述的降粘型聚羧酸混凝土减水剂,其特征在于:所述的异丁烯醇聚氧乙烯聚氧丙烯嵌段聚醚为不同聚合度的环氧丙烷、环氧乙烷嵌段聚醚,平均分子量为500-1200。
- 如权利要求1或2所述的降粘型聚羧酸混凝土减水剂,其特征在于:所述的异戊烯醇聚氧乙烯醚是分子量为3000~4000的聚醚单体。
- 如权利要求1或2所述的降粘型聚羧酸混凝土减水剂,其特征在于:所述的不饱和羧酸为丙烯酸、衣康酸、马来酸或甲基丙烯酸中的一种或多种。
- 如权利要求1或2所述的降粘型聚羧酸混凝土减水剂,其特征在于:所述的功能性单体为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸十二烷基酯、聚乙二醇二丙烯酸酯或聚乙二醇二甲基丙烯 酸酯中的一种或多种。
- 如权利要求6所述的降粘型聚羧酸混凝土减水剂,其特征在于:所述聚乙二醇二丙烯酸酯是乙二醇聚合度为200~400的丙烯酸酯化合物。
- 如权利要求2所述的降粘型聚羧酸混凝土减水剂的制备方法,其特征在于:所述的异丁烯醇聚氧乙烯聚氧丙烯嵌段聚醚:异戊烯醇聚氧乙烯醚:不饱和羧酸:功能单体:链转移剂的质量比为1:(0.75~2.2):(0.07~0.12):(0.015~0.03):(0.003~0.008);
- 如权利要求2所述的降粘型聚羧酸混凝土减水剂的制备方法,其特征在于:所述的混合物以A、B料滴加的形式,在2~4小时内以恒定速度滴加完成;降粘型聚羧酸减水剂在滴加过程中反应温度为30~50℃;
- 如权利要求1或2中任一项所述的降粘型聚羧酸混凝土减水剂,其特征在于:所述的链转移剂为巯基乙酸、磺化巯基酸、巯基丙酸、次亚磷酸钠或甲基丙烯基磺酸钠中的一种或多种;所述的氧化剂为30%浓度的双氧水、过硫酸铵、偶氮二异丁酸二甲酯或过氧化二碳酸二异丙酯中的至少一种;所述的还原剂为维生素C、次磷酸、亚磷酸、吊白粉或亚硫酸氢钠中的一种或多种;所述的中和剂为氢氧化钾、氢氧化钠溶液中的一种或两种。
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