CN111116839A - High slump loss resistant mud resistant polycarboxylate superplasticizer mother solution as well as preparation method and application thereof - Google Patents
High slump loss resistant mud resistant polycarboxylate superplasticizer mother solution as well as preparation method and application thereof Download PDFInfo
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- CN111116839A CN111116839A CN201911419158.1A CN201911419158A CN111116839A CN 111116839 A CN111116839 A CN 111116839A CN 201911419158 A CN201911419158 A CN 201911419158A CN 111116839 A CN111116839 A CN 111116839A
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- mud
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- solution
- mother liquor
- high slump
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 39
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010413 mother solution Substances 0.000 title claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000008367 deionised water Substances 0.000 claims abstract description 47
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 47
- 239000012452 mother liquor Substances 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 16
- 150000001408 amides Chemical class 0.000 claims abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical group OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 12
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 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
- 239000011734 sodium Substances 0.000 claims description 9
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 230000001502 supplementing effect Effects 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 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 4
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- ATEAWHILRRXHPW-UHFFFAOYSA-J iron(2+);phosphonato phosphate Chemical compound [Fe+2].[Fe+2].[O-]P([O-])(=O)OP([O-])([O-])=O ATEAWHILRRXHPW-UHFFFAOYSA-J 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- ZKODLPLYXXUCHB-UHFFFAOYSA-M sodium;hydroxymethanesulfinate;hydrate Chemical compound O.[Na+].OCS([O-])=O ZKODLPLYXXUCHB-UHFFFAOYSA-M 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- -1 N-methacrylamide Chemical compound 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 claims description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 3
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 3
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 125000005394 methallyl group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004575 stone Substances 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- 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)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a high slump loss resistant mud-resistant polycarboxylate superplasticizer mother liquor, a preparation method and an application thereof, wherein the high slump loss resistant mud-resistant polycarboxylate superplasticizer mother liquor is prepared from the following materials in percentage by mass: ether macromonomer: 25 to 36 percent; oxidizing agent: 0.15 to 0.3 percent; unsaturated carboxylic acid: 2.2-3.0%; mud resistance monomer: 1 to 5 percent; amide monomers: 0.3 to 3 percent; chain transfer agent: 0.01-2%; reducing agent: 0.03-0.06%; pH regulator: 1.0-1.1%; the balance being deionized water. The high slump-retaining mud-resistant polycarboxylate superplasticizer mother liquor with low mixing amount, long slump-retaining time and strong mud resistance is prepared from the raw materials through a synthesis process.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a high slump loss resistant mud resistant polycarboxylate superplasticizer mother liquor, a preparation method and application thereof.
Background
In recent years, with the rapid increase of the quantity of basic construction projects, the consumption of sandstone is correspondingly increased, high-quality sandstone resources are in short supply, the mud content in most sands is higher, the strength and the durability of concrete are reduced, and the drying shrinkage of the concrete is increased. Among them, the workability of concrete doped with a water reducing agent is greatly influenced, and particularly, the workability of a water reducing agent such as polycarboxylic acid is greatly influenced.
At present, two main schemes for solving the problems at home and abroad are provided: firstly, the sand and stone are cleaned, but the operation of the scheme is very troublesome, and the mechanical, manual and material costs are greatly increased; and secondly, the consumption of the polycarboxylate water reducer is increased, so that the clay minerals can adsorb a part of the polycarboxylate water reducer and leave enough polycarboxylate water reducer for cement particles, but the cost is increased due to the increase of the consumption of the polycarboxylate water reducer.
Disclosure of Invention
In view of the above, the invention aims to provide a high slump-retaining mud-resistant polycarboxylate superplasticizer mother liquor with low mixing amount, long slump-retaining time and strong mud resistance.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the high slump retaining and mud resistant polycarboxylate superplasticizer mother liquor is prepared from the following materials in percentage by mass: ether macromonomer: 25 to 36 percent; oxidizing agent: 0.15 to 0.3 percent; unsaturated carboxylic acid: 2.2-3.0%; mud resistance monomer: 1 to 5 percent; amide monomers: 0.3 to 3 percent; chain transfer agent: 0.01-2%; reducing agent: 0.03-0.06%; pH regulator: 1.0-1.1%; the balance being deionized water.
The ether macromonomer is a polyether macromonomer with the molecular weight of 2000-2400.
The polyether macromonomer is one or more of methyl allyl polyoxyethylene ether, isopentenol polyoxyethylene ether and isobutenol polyoxyethylene ether.
The oxidant is one or more of hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate.
Said unsaturation beingThe carboxylic acid is acrylic acid and/or methacrylic acid; the amide monomer is one or more of acrylamide, N-methacrylamide, N-ethyl acrylamide, N, N-dimethylacrylamide or N-diethyl 2-acrylamide; the anti-mud monomer is DTPMP Na2、DTPMP·Na7、DTPMP·Na5One or more of dimethyldiallylammonium chloride and 2-acrylamide-2-methylpropanesulfonic acid.
The chain transfer agent is one or more of thioglycolic acid, mercaptopropionic acid or mercaptoethanol; the reducing agent is one or more of sodium hydroxymethanesulfinate hydrate, sodium sulfite, sodium metabisulfite, sodium bisulfite, ferrous pyrophosphate, ferrous sulfate, sodium hypophosphite or ascorbic acid.
The pH regulator is sodium hydroxide and/or potassium hydroxide.
The preparation method of the high slump retaining and mud resistant polycarboxylate superplasticizer mother liquor specifically comprises the following steps:
adding deionized water into a reaction vessel, controlling the temperature of the reaction vessel within the range of 15-35 ℃, adding an ether macromonomer, and stirring until the ether macromonomer is completely dissolved;
adding unsaturated carboxylic acid and/or an anti-mud monomer into the reaction container, uniformly mixing, and then adding an oxidant;
dissolving unsaturated carboxylic acid, an anti-mud monomer and an amide monomer in deionized water to obtain a solution A for later use; dissolving a chain transfer agent and a reducing agent in deionized water to obtain a solution B for later use;
respectively dripping the solution A and the solution B into the reaction container, wherein the dripping time of the solution A is 1-2.5 hours, and the dripping time of the solution B is 1-3 hours;
and (3) after the reaction vessel is subjected to heat preservation operation, adding a pH regulator, supplementing deionized water, and uniformly mixing to obtain the high slump loss resistant and mud resistant polycarboxylate superplasticizer mother liquor.
The solution A is prepared by dissolving 2.2-3.0 parts of unsaturated carboxylic acid, 0.3-3 parts of amide monomers and 1-5 parts of mud-resistant monomers in deionized water by mass; the solution B is prepared by dissolving 0.01-2 parts of chain transfer agent and 0.03-0.06 part of reducing agent in deionized water.
The high slump loss resistant mud resistant polycarboxylate superplasticizer mother liquor is applied to concrete.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, by a chemical synthesis method, an amide group functional monomer with slow release performance and an amphoteric functional monomer with mud resistance are introduced to prepare the high slump loss resistant polycarboxylic acid water reducer mother liquor, the high slump loss resistant polycarboxylic acid water reducer mother liquor has the advantages of low mixing amount, long slump loss resistant time and strong mud resistance, the adverse effect of mud-containing aggregate in concrete on the workability of the concrete can be reduced, the raw materials are easy to obtain, the preparation process is simple, and the production cost is favorably reduced.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The high slump retaining and mud resistant polycarboxylate superplasticizer mother liquor is prepared from the following materials in percentage by mass: ether macromonomer: 25 to 36 percent; oxidizing agent: 0.15 to 0.3 percent; unsaturated carboxylic acid: 2.2-3.0%; mud resistance monomer: 1 to 5 percent; amide monomers: 0.3 to 3 percent; chain transfer agent: 0.01-2%; reducing agent: 0.03-0.06%; pH regulator: 1.0-1.1%; the balance being deionized water.
The ether macromonomer is a polyether macromonomer with the molecular weight of 2000-2400.
The polyether macromonomer is one or more of methyl allyl polyoxyethylene ether, isopentenol polyoxyethylene ether and isobutenol polyoxyethylene ether.
The oxidant is one or more of hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate.
The unsaturated carboxylic acid is acrylic acid and/or methacrylic acid; the amide monomer is one or more of acrylamide, N-methacrylamide, N-ethyl acrylamide, N, N-dimethylacrylamide or N-diethyl 2-acrylamide; the anti-mud monomer is DTPMP Na2、DTPMP·Na7、DTPMP·Na5One or more of dimethyldiallylammonium chloride and 2-acrylamide-2-methylpropanesulfonic acid.
The chain transfer agent is one or more of thioglycolic acid, mercaptopropionic acid or mercaptoethanol; the reducing agent is one or more of sodium hydroxymethanesulfinate hydrate, sodium sulfite, sodium metabisulfite, sodium bisulfite, ferrous pyrophosphate, ferrous sulfate, sodium hypophosphite or ascorbic acid.
The pH regulator is sodium hydroxide and/or potassium hydroxide.
The preparation method of the high slump retaining and mud resistant polycarboxylate superplasticizer mother liquor specifically comprises the following steps:
adding deionized water into a reaction vessel, controlling the temperature of the reaction vessel within the range of 15-35 ℃, adding an ether macromonomer, and stirring until the ether macromonomer is completely dissolved;
adding unsaturated carboxylic acid and/or an anti-mud monomer into the reaction container, uniformly mixing, and then adding an oxidant;
dissolving unsaturated carboxylic acid, an anti-mud monomer and an amide monomer in deionized water to obtain a solution A for later use; dissolving a chain transfer agent and a reducing agent in deionized water to obtain a solution B for later use;
respectively dripping the solution A and the solution B into the reaction container, wherein the dripping time of the solution A is 1-2.5 hours, and the dripping time of the solution B is 1-3 hours;
and (3) after the reaction vessel is subjected to heat preservation operation, adding a pH regulator, supplementing deionized water, and uniformly mixing to obtain the high slump loss resistant and mud resistant polycarboxylate superplasticizer mother liquor.
The solution A is prepared by dissolving 2.2-3.0 parts of unsaturated carboxylic acid, 0.3-3 parts of amide monomers and 1-5 parts of mud-resistant monomers in deionized water by mass; the solution B is prepared by dissolving 0.01-2 parts of chain transfer agent and 0.03-0.06 part of reducing agent in deionized water.
The high slump loss resistant mud resistant polycarboxylate superplasticizer mother liquor is applied to concrete.
Example 1
Adding 330.0g of deionized water into the reaction kettle, and controlling the temperature of the reaction kettle within the range of 15-35 ℃ by insulating the outer layer of the reaction kettle; subsequently, 210.0g of methallyl polyoxyethylene ether (molecular weight of 2400) and 140.0g of prenyl polyoxyethylene ether (molecular weight of 2400) were put into the reaction kettle and stirred continuously until no lump or flake material was evident.
Adding 5.0g of acrylic acid and 8.0g of dimethyldiallylammonium chloride into the reaction kettle, and stirring for 5 min; then 2.5g of 30% industrial grade hydrogen peroxide is added, and the mixture is continuously stirred for 10 min.
A solution A was prepared by dissolving 17.0g of acrylic acid, 4.0g of acrylamide, 3.0g of N, N-diethyl 2-acrylamide, and 2.9g of 2-acrylamido-2-methylpropanesulfonic acid in 40.0g of deionized water, and was used.
A solution B was prepared by dissolving 1.0g of thioglycolic acid, 1.0g of mercaptopropionic acid, and 0.6g of ascorbic acid in 100.0g of deionized water.
And respectively dripping the solution A and the solution B into the reaction kettle, wherein the dripping time of the solution A and the dripping time of the solution B are both 1 h.
And (3) keeping the temperature of the reaction kettle for 6 hours without cooling deionized water circulation, adding 5.0g of sodium hydroxide with the mass concentration of 30-33%, supplementing 130.0g of deionized water, and uniformly stirring to obtain the high slump retaining and mud resistant polycarboxylate superplasticizer mother liquor.
Example 2
Adding 330.0g of deionized water into the reaction kettle, and controlling the temperature of the reaction kettle within the range of 15-35 ℃ through the operation of water bath heating; subsequently, 350.0g of methylallyl polyoxyethylene ether (molecular weight 2400) was placed in the reaction vessel and stirred continuously until dissolution was complete.
9.0g of acrylic acid and 9.0g of DTPMP Na7Adding into the reaction kettle, and stirring for 10 min; 2.5g of ammonium persulfate was added and stirring was continued for another 10 min.
A solution A was prepared by dissolving 13.4g of methacrylic acid, 7.0g of acrylamide and 1.5g of 2-acrylamido-2-methylpropanesulfonic acid in 40.0g of deionized water.
A solution B was prepared by dissolving 1.0g of thioglycolic acid, 1.0g of mercaptopropionic acid, and 0.6g of sodium sulfite in 120g of deionized water.
And respectively dripping the solution A and the solution B into the reaction kettle, wherein the dripping time of the solution A is 2.5 hours, and the dripping time of the solution B is 3 hours.
And (3) cooling deionized water for circulation, keeping the temperature of the reaction kettle for 10 hours, adding 5.0g of sodium hydroxide with the mass concentration of 30-33%, supplementing 110.0g of deionized water, and uniformly stirring to obtain the high slump retaining and mud resistant polycarboxylate superplasticizer mother liquor.
Example 3
330.0g of deionized water is added into the reaction kettle, the temperature of the reaction kettle is controlled within the range of 15-35 ℃, and then 345.0g of methyl allyl polyoxyethylene ether (molecular weight of 2400) is placed into the reaction kettle and continuously stirred until no obvious blocky or flaky material exists.
Adding 8.0g of acrylic acid and 6.0g of dimethyldiallylammonium chloride into the reaction kettle, and stirring for 5 min; 1.0g of 30% technical grade hydrogen peroxide and 1.2g of ammonium persulfate were added and stirring was continued for 5 min.
15.0g of acrylic acid, 8.3g of acrylamide, 8.0g of DTPMP Na7Dissolving in 40.0g deionized water to obtain solution A.
Dissolving 1.0g of mercaptopropionic acid, 1.0g of mercaptoethanol and 0.5g of sodium metabisulfite in 110.0g of deionized water to obtain solution B for later use.
And respectively dripping the solution A and the solution B into the reaction kettle, wherein the dripping time of the solution A and the dripping time of the solution B are both 2 hours.
And (3) cooling deionized water for circulation without starting, keeping the temperature of the reaction kettle for 7.5 hours, adding 5.0g of potassium hydroxide with the mass concentration of 30-33%, supplementing 120.0g of deionized water, and uniformly stirring to obtain the high slump retaining and mud resistant polycarboxylate superplasticizer mother liquor.
Example 4
330.0g of deionized water is added into a reaction kettle, the temperature of the reaction kettle is controlled within the range of 15-35 ℃ through water bath heating, 350g of prenyl polyoxyethylene ether (molecular weight of 2400) is placed into the reaction kettle and continuously stirred until no obvious blocky or flaky material exists.
Adding 7.0g of acrylic acid and 7.0g of dimethyl diallyl ammonium chloride into the reaction kettle, and stirring for 10 min; 1.0g of ammonium persulfate, 1.0g of potassium persulfate and 0.4g of 30% industrial grade hydrogen peroxide are added, and the mixture is continuously stirred for 10 min.
16.5g of acrylic acid, 8.0g of acrylamide and 1.5g of 2-acrylamide-2-methylpropanesulfonic acid are dissolved in 40.0g of deionized water to prepare a solution A for later use.
2.0g of mercaptopropionic acid, 0.2g of ascorbic acid, 0.2g of ferrous pyrophosphate and 0.2g of ferrous sulfate were dissolved in 120.0g of deionized water to prepare a solution B for later use.
And respectively dripping the solution A and the solution B into the reaction kettle, wherein the dripping time of the solution A is 1.5 hours, and the dripping time of the solution B is 2 hours.
And (3) cooling deionized water for circulation, keeping the temperature of the reaction kettle for 8 hours, adding 5.0g of sodium hydroxide with the mass concentration of 30-33%, supplementing 110g of deionized water, and uniformly stirring to obtain the high slump retaining and mud resistant polycarboxylate superplasticizer mother liquor.
Example 5
330.0g of deionized water is added into the reaction kettle, the temperature of the reaction kettle is controlled within the range of 15-35 ℃, 345.0g of isobutylene alcohol polyoxyethylene ether (molecular weight 2000) is placed into the reaction kettle and stirred continuously until no obvious blocky or flaky material exists, namely the dissolution is complete.
Adding 7.0g of acrylic acid and 6.0g of dimethyldiallylammonium chloride into the reaction kettle, and stirring until the mixture is uniformly mixed; 1.5g of 30% technical grade hydrogen peroxide and 1.0g of ammonium persulfate are added and stirring is continued until uniform mixing occurs.
16.4g of acrylic acid, 8.0g of acrylamide, 1.5g of 2-acrylamido-2-methylpropanesulfonic acid and 6.0g of DTPMP Na5Dissolving in 40.0g deionized water to obtain solution A.
1.0g of thioglycolic acid, 1.0g of mercaptopropionic acid, 0.4g of sodium hypophosphite and 0.2g of sodium hydroxymethanesulfinate hydrate (also called sodium formaldehyde sulfoxylate) were dissolved in 120g of deionized water to prepare solution B for later use.
And respectively dripping the solution A and the solution B into the reaction kettle, wherein the dripping time of the solution A is 2 hours, and the dripping time of the solution B is 1 hour.
And (3) cooling deionized water for circulation without starting, keeping the temperature of the reaction kettle for 5.5 hours, adding 5.0g of potassium hydroxide with the mass concentration of 30-33%, supplementing 110.0g of deionized water, and uniformly stirring to obtain the high slump retaining and mud resistant polycarboxylate superplasticizer mother liquor.
The high slump loss resistant mud resistant polycarboxylate superplasticizer mother liquor obtained in examples 1-5 is subjected to a net slurry fluidity test by referring to GB8077-2012 'concrete admixture homogeneity test method'. Wherein, the test conditions are that the water-to-gel ratio W/C is 0.29, the folding and fixing doping amount of the admixture is 0.16, and the dosage of the sodium montmorillonite is 6.0g, and the following table is obtained.
Table 1: data sheet for net paste fluidity of examples 1-5
From the above table, it can be seen that, compared with the samples without adding the polycarboxylic acid water reducer, the common slump-retaining polycarboxylic acid water reducer and the common mud-resistant polycarboxylic acid water reducer, the samples added with the high slump-retaining mud-resistant polycarboxylic acid water reducer mother liquor obtained in the examples 1 to 5 have obvious changes in net slurry fluidity, specifically, the net slurry fluidity value is greatly improved within 0 to 1h, which indicates that the mud-resistant slump-retaining polycarboxylic acid water reducer has obvious effect on mud resistance; within 2h, the net slurry flow value is only slightly reduced, and almost no loss is caused, namely the slump retaining effect is high. And further, the high slump loss resistant and mud resistant polycarboxylate superplasticizer mother liquor can be obtained, and the effects of high slump loss resistance and high mud resistance are achieved by introducing the slow release and mud resistant functional monomer. In addition, because the raw materials are easy to obtain and the preparation method is simple, the cost of the high slump loss resistant mud-resistant polycarboxylate superplasticizer mother liquor is lower than that of a commercially available concentrated slump loss resistant polycarboxylate superplasticizer, and the high slump loss resistant mud-resistant polycarboxylate superplasticizer mother liquor has certain economic benefit.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by those skilled in the art from the description of the invention are covered by the claims of the invention.
Claims (10)
1. The high slump retaining and mud resisting type polycarboxylate superplasticizer mother liquor is characterized by being prepared from the following materials in percentage by mass:
ether macromonomer: 25 to 36 percent;
oxidizing agent: 0.15 to 0.3 percent;
unsaturated carboxylic acid: 2.2-3.0%;
mud resistance monomer: 1 to 5 percent;
amide monomers: 0.3 to 3 percent;
chain transfer agent: 0.01-2%;
reducing agent: 0.03-0.06%;
pH regulator: 1.0-1.1%;
the balance being deionized water.
2. The mother liquor as claimed in claim 1, wherein the ether macromonomer is polyether macromonomer with molecular weight of 2000-2400.
3. The mother liquor of a high slump loss and mud resistance type polycarboxylate superplasticizer according to claim 2, wherein the polyether macromonomer is one or more of methallyl polyoxyethylene ether, isopentenol polyoxyethylene ether and isobutenol polyoxyethylene ether.
4. The high slump loss resistant and mud resistant polycarboxylate water reducer mother liquor as claimed in claim 1, wherein the oxidant is one or more of hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate.
5. The high slump loss and mud resistance type polycarboxylate superplasticizer mother liquor as claimed in claim 1, wherein the unsaturated carboxylic acid is acrylic acid and/or methacrylic acid;
the amide monomer is one or more of acrylamide, N-methacrylamide, N-ethyl acrylamide, N, N-dimethylacrylamide or N-diethyl 2-acrylamide;
the anti-mud monomer is DTPMP Na2、DTPMP·Na7、DTPMP·Na5One or more of dimethyldiallylammonium chloride and 2-acrylamide-2-methylpropanesulfonic acid.
6. The high slump loss and mud resistance type polycarboxylate superplasticizer mother liquor as claimed in claim 1, wherein the chain transfer agent is one or more of thioglycolic acid, mercaptopropionic acid or mercaptoethanol;
the reducing agent is one or more of sodium hydroxymethanesulfinate hydrate, sodium sulfite, sodium metabisulfite, sodium bisulfite, ferrous pyrophosphate, ferrous sulfate, sodium hypophosphite or ascorbic acid.
7. The high slump loss resistant and mud resistant polycarboxylate water reducer mother liquor as claimed in claim 1, wherein the pH regulator is sodium hydroxide and/or potassium hydroxide.
8. A preparation method of a high slump retaining and mud resistant polycarboxylate superplasticizer mother solution is characterized in that,
the method specifically comprises the following steps:
adding deionized water into a reaction vessel, controlling the temperature of the reaction vessel within the range of 15-35 ℃, adding an ether macromonomer, and stirring until the ether macromonomer is completely dissolved;
adding unsaturated carboxylic acid and/or an anti-mud monomer into the reaction container, uniformly mixing, and then adding an oxidant;
dissolving unsaturated carboxylic acid, an anti-mud monomer and an amide monomer in deionized water to obtain a solution A for later use; dissolving a chain transfer agent and a reducing agent in deionized water to obtain a solution B for later use;
respectively dripping the solution A and the solution B into the reaction container, wherein the dripping time of the solution A is 1-2.5 hours, and the dripping time of the solution B is 1-3 hours;
and (3) after the reaction vessel is subjected to heat preservation operation, adding a pH regulator, supplementing deionized water, and uniformly mixing to obtain the high slump loss resistant and mud resistant polycarboxylate superplasticizer mother liquor.
9. The preparation method of the high slump loss resistant and mud resistant polycarboxylate superplasticizer mother liquor as claimed in claim 8, wherein the solution A is prepared by dissolving 2.2-3.0 parts by mass of unsaturated carboxylic acid, 0.3-3 parts by mass of amide monomers and 1-5 parts by mass of mud resistant monomers in deionized water; the solution B is prepared by dissolving 0.01-2 parts of chain transfer agent and 0.03-0.06 part of reducing agent in deionized water.
10. The application of the high slump loss resistant mud resistant polycarboxylate superplasticizer mother liquor as claimed in claim 1 in concrete.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354047A (en) * | 2021-06-17 | 2021-09-07 | 深圳市三绿科技有限公司 | Sandstone flocculating agent inhibition and regulation agent and preparation method thereof |
| CN114213601A (en) * | 2021-12-27 | 2022-03-22 | 中建西部建设新材料科技有限公司 | Hydrolysis regulation slow-release anti-mud polycarboxylate superplasticizer and preparation method thereof |
| CN114621401A (en) * | 2022-04-26 | 2022-06-14 | 洛阳君江建材科技有限公司 | Dispersant for red mud slurrying |
| CN114620960A (en) * | 2022-04-26 | 2022-06-14 | 洛阳君江建材科技有限公司 | Method for preparing building material from red mud |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774293A (en) * | 2014-12-17 | 2015-07-15 | 厦门路桥翔通建材科技有限公司 | Mud-resistant polycarboxylic acid water reducer and preparation method thereof |
| CN105110687A (en) * | 2015-07-30 | 2015-12-02 | 厦门路桥翔通建材科技有限公司 | Mud resisting and slump retaining type polycarboxylic acids water reducer and preparation method thereof |
| CN106749962A (en) * | 2016-11-28 | 2017-05-31 | 浙江建研科之杰新材料有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer high and preparation method thereof |
| CN106977129A (en) * | 2017-04-10 | 2017-07-25 | 河北润砼新材料科技有限公司 | Anti- mud collapse protective poly-carboxylic acid high efficiency water reducing agent and preparation method thereof |
| CN109970927A (en) * | 2019-04-23 | 2019-07-05 | 四川同舟化工科技有限公司 | A kind of high-thin arch dam ultra early-strength polycarboxylate water-reducer and preparation method thereof |
| CN110002784A (en) * | 2019-03-13 | 2019-07-12 | 兰州同邦建材有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer and its preparation method and application |
| CN110003402A (en) * | 2019-04-23 | 2019-07-12 | 四川同舟化工科技有限公司 | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and its low temperature preparation method of lower shrinkage high-adaptability |
-
2019
- 2019-12-31 CN CN201911419158.1A patent/CN111116839A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774293A (en) * | 2014-12-17 | 2015-07-15 | 厦门路桥翔通建材科技有限公司 | Mud-resistant polycarboxylic acid water reducer and preparation method thereof |
| CN105110687A (en) * | 2015-07-30 | 2015-12-02 | 厦门路桥翔通建材科技有限公司 | Mud resisting and slump retaining type polycarboxylic acids water reducer and preparation method thereof |
| CN106749962A (en) * | 2016-11-28 | 2017-05-31 | 浙江建研科之杰新材料有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer high and preparation method thereof |
| CN106977129A (en) * | 2017-04-10 | 2017-07-25 | 河北润砼新材料科技有限公司 | Anti- mud collapse protective poly-carboxylic acid high efficiency water reducing agent and preparation method thereof |
| CN110002784A (en) * | 2019-03-13 | 2019-07-12 | 兰州同邦建材有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer and its preparation method and application |
| CN109970927A (en) * | 2019-04-23 | 2019-07-05 | 四川同舟化工科技有限公司 | A kind of high-thin arch dam ultra early-strength polycarboxylate water-reducer and preparation method thereof |
| CN110003402A (en) * | 2019-04-23 | 2019-07-12 | 四川同舟化工科技有限公司 | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and its low temperature preparation method of lower shrinkage high-adaptability |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354047A (en) * | 2021-06-17 | 2021-09-07 | 深圳市三绿科技有限公司 | Sandstone flocculating agent inhibition and regulation agent and preparation method thereof |
| CN114213601A (en) * | 2021-12-27 | 2022-03-22 | 中建西部建设新材料科技有限公司 | Hydrolysis regulation slow-release anti-mud polycarboxylate superplasticizer and preparation method thereof |
| CN114621401A (en) * | 2022-04-26 | 2022-06-14 | 洛阳君江建材科技有限公司 | Dispersant for red mud slurrying |
| CN114620960A (en) * | 2022-04-26 | 2022-06-14 | 洛阳君江建材科技有限公司 | Method for preparing building material from red mud |
| CN119161121A (en) * | 2024-09-02 | 2024-12-20 | 杭州临安引力外加剂有限公司 | A method for producing composite water reducing agent capable of realizing resource utilization |
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