CN112794956A - Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof - Google Patents
Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN112794956A CN112794956A CN202011616823.9A CN202011616823A CN112794956A CN 112794956 A CN112794956 A CN 112794956A CN 202011616823 A CN202011616823 A CN 202011616823A CN 112794956 A CN112794956 A CN 112794956A
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 28
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 30
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 30
- 239000011734 sodium Substances 0.000 claims abstract description 29
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 27
- UFDFFEMHDKXMBG-UHFFFAOYSA-N 2-acetamidoprop-2-enoic acid Chemical compound CC(=O)NC(=C)C(O)=O UFDFFEMHDKXMBG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 17
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 abstract description 15
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 15
- -1 alkenyl sulfonate Chemical compound 0.000 claims description 13
- 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 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 239000002585 base Substances 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical group CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 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
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- QYFZAEGNOFAHAD-UHFFFAOYSA-N C(=CC)S(=O)(=O)OC.[Na] Chemical compound C(=CC)S(=O)(=O)OC.[Na] QYFZAEGNOFAHAD-UHFFFAOYSA-N 0.000 claims 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000004568 cement Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 150000003871 sulfonates Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical group CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical group CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 2
- MVHWMCQWFWUXEE-UHFFFAOYSA-M sodium;hexadec-1-ene-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCC=CS([O-])(=O)=O MVHWMCQWFWUXEE-UHFFFAOYSA-M 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PDAVKVAAXOOLCM-UHFFFAOYSA-M sodium;dodec-1-ene-1-sulfonate Chemical compound [Na+].CCCCCCCCCCC=CS([O-])(=O)=O PDAVKVAAXOOLCM-UHFFFAOYSA-M 0.000 description 1
- RUTSRVMUIGMTHJ-UHFFFAOYSA-M sodium;tetradec-1-ene-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCC=CS([O-])(=O)=O RUTSRVMUIGMTHJ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 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
- 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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a viscosity-reducing polycarboxylate superplasticizer and a preparation method thereof, belonging to the technical field of building material additives. The water reducing agent is prepared from the following raw materials in parts by weight: 400 parts of unsaturated polyoxyethylene ether, 35-40 parts of 2-acetaminoacrylic acid, 7-14 parts of alpha-alkenyl sodium sulfonate, 3-5 parts of vinyl phosphoric acid, 2.5-2.8 parts of chain transfer agent, 4-6 parts of oxidant, 1-1.5 parts of reducing agent, 2-8 parts of NaOH solution and 400 parts of deionized water. The water reducing agent disclosed by the invention effectively reduces the viscosity of concrete and improves the workability of the concrete at the doping amount level of 0.05%, has excellent comprehensive performance, is used as a water solvent, is convenient to store and transport, has stable performance, simple preparation process and low cost, is suitable for practical popularization and application, and has wide economic and social benefits.
Description
Technical Field
The invention belongs to the technical field of building material additives, and particularly relates to a viscosity-reducing polycarboxylic acid water reducer and a preparation method thereof.
Background
The polycarboxylic acid water reducing agent becomes a common additive for high-performance concrete, and has the main advantages of low mixing amount, high water reducing rate and good dispersion retention. However, in reality, due to the influence of a plurality of factors such as large mud content of concrete aggregate and use of machine-made sand with large powder content, the viscosity of concrete is high, the workability is poor, and the existing polycarboxylic acid water reducing agent has certain problems and defects in viscosity reduction and also has the problem of further improvement. After the using amount of the cementing material is increased, the viscosity of concrete is increased, the fluidity is poor, the water reducing rate is insufficient, and the existing polycarboxylic acid water reducing agent is not suitable for the concrete of the type.
Therefore, how to improve the viscosity reduction performance of the polycarboxylate superplasticizer, improve the applicability of the polycarboxylate superplasticizer and enhance the use effect of the polycarboxylate superplasticizer becomes the key point of the current research. The currently adopted method is to add external additives, such as an air entraining agent, to form a large amount of micro bubbles, reduce friction between aggregates and increase the dispersion effect, but the viscosity reduction effect of the air entraining agent is gradually reduced or lost along with the prolonging of time. CN105601826A discloses a preparation method of a viscosity reduction type water reducer, which comprises the steps of firstly preparing an unsaturated carboxylic acid monomer, polymerizing the unsaturated carboxylic acid monomer with an unsaturated phosphoric acid monomer to obtain an active macromolecule, and then carrying out graft copolymerization on the active macromolecule and an active small monomer, namely acrylic acid, acrylamide and the like to obtain the water reducer. These methods can achieve the object, but the effects are not significant enough, resulting in an increase in cost.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the polycarboxylic acid water reducer which has the advantages of easily available raw materials and convenient operation, greatly improves the high-efficiency water reducing performance of the polycarboxylic acid water reducer and reduces the manufacturing cost.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the viscosity-reducing polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 400 parts of unsaturated polyoxyethylene ether, 35-40 parts of 2-acetaminoacrylic acid, 7-14 parts of alpha-alkenyl sodium sulfonate, 2.5-2.8 parts of vinyl phosphoric acid, 2.5-2.8 parts of chain transfer agent, 4-6 parts of oxidant, 1-1.5 parts of reducing agent, 2-8 parts of NaOH solution and 400 parts of deionized water.
Preferably, the unsaturated polyoxyethylene ether is isobutylene alcohol polyoxyethylene ether or isoamylene alcohol polyoxyethylene ether, and the average molecular weight is 2200-.
Preferably, the sodium alpha-alkenyl sulfonate is R1-CH ═ CH- (CH)2)n-SO3Na, where R1 ═ C9-13 and n is 1, 2, 3.
Preferably, the alpha-sodium alkenyl sulfonate is one or more of sodium dodecenyl sulfonate, sodium tetradecenyl sulfonate and sodium hexadecenyl sulfonate.
Preferably, the chain transfer agent is one or more of mercaptopropionic acid, thioglycolic acid, mercaptoethanol and sodium hypophosphite.
Preferably, the oxidant is one or more of hydrogen peroxide, ammonium persulfate and potassium persulfate.
Preferably, the reducing agent is one or more of sodium formaldehyde sulfoxylate, sodium hypophosphite, ascorbic acid and sodium bisulfite.
Preferably, the mass concentration of the NaOH solution is 32%.
A preparation method of a viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
1) weighing the components according to the proportion, dissolving the weighed unsaturated polyoxyethylene ether in 300 parts of water containing 200-15 parts of 2-acetamino acrylic acid and adding an oxidant to obtain a substrate;
2) dissolving alpha-sodium alkenyl sulfonate, the rest 2-acetamido acrylic acid, vinyl phosphoric acid, a chain transfer agent and a reducing agent into 70-80 parts of water to be used as dropwise adding solution;
3) heating the base solution to 20 +/-2 ℃, starting dropwise adding the solution, controlling the reaction temperature not to exceed 40 +/-2 ℃, keeping the temperature and continuing to react for 1-2 hours after the addition is finished, and adding 2-8 parts of liquid alkali to adjust the pH value to 6-7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
Preferably, the dropping time of the dropping solution in the step (3) is controlled to be 1.5-3 hours.
Each of the raw materials of the present invention is commercially available.
The folding-fixing mixing amount of the water reducing agent is 0.05-0.1%.
The existing polycarboxylic acid water reducing agent basically belongs to the mature industrial technology, and the performance tends to be stable. The performance of the existing polycarboxylic acid water reducing agent is greatly improved, the cost is reduced, and the performance is greatly improved by modifying the structure of the water reducing agent only from the essence. In the prior art, the performance of the polycarboxylic acid water reducing agent is improved by means of adding carboxylate radicals, sulfonate radicals, phosphate radicals and the like. However, the preparation process is complex, the raw materials are various, the cost is greatly increased, and in practical application, the comprehensive performance of the prepared water reducing agent is not outstanding, so that the water reducing agent is difficult to be practically applied.
Aiming at the problems in the prior art, the inventor selects the best backing material and the best modifier, only grafts the sulfonic side chain, and matches with the 2-acetaminoacrylic acid for synergistic interaction, thereby realizing the effect of multiple purposes, effectively reducing the viscosity of the concrete under the doping level of 0.05 percent, improving the workability of the concrete, having excellent comprehensive performance, being used as a water solvent, being convenient to store and transport, having stable performance, simple preparation process and low cost, being suitable for practical popularization and application, and having wide economic benefit and social benefit.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
Example 1
The viscosity-reducing polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 300 parts of unsaturated polyoxyethylene ether, 35 parts of 2-acetamido acrylic acid, 7 parts of alpha-alkenyl sodium sulfonate, 3 parts of vinyl phosphoric acid, 2.5 parts of chain transfer agent, 4 parts of oxidant, 1 part of reducing agent, 2 parts of NaOH solution and 300 parts of deionized water.
The unsaturated polyoxyethylene ether is the isobutenol polyoxyethylene ether, and the average molecular weight is 2200-2400.
The alpha-alkenyl sodium sulfonate is dodecenyl sodium sulfonate
The chain transfer agent is mercaptopropionic acid.
The oxidant is hydrogen peroxide.
The reducing agent is sodium formaldehyde sulfoxylate.
The mass concentration of the NaOH solution is 32%.
A preparation method of a viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
1) weighing the components according to the proportion, dissolving the weighed unsaturated polyoxyethylene ether in 220 parts of water, and adding an oxidant and 10 parts of 2-acetamino acrylic acid to obtain a base material;
2) dissolving alpha-sodium alkenyl sulfonate, the rest 2-acetamido acrylic acid, vinyl phosphoric acid, a chain transfer agent and a reducing agent into 80 parts of water to be used as a dropwise adding solution;
3) heating the base solution to 20 +/-2 ℃, starting dropwise adding the solution, controlling the reaction temperature not to exceed 40 +/-2 ℃, keeping the temperature for continuously reacting for 1 hour after the addition is finished, and adding 2 parts of liquid caustic soda to adjust the pH value to 6-7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
The dropping time of the dropping solution in the step (3) is controlled to be 1.5 hours.
Each of the raw materials of the present invention is commercially available.
The folding solid content of the water reducing agent is 0.05 percent.
Example 2
The viscosity-reducing polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 350 parts of unsaturated polyoxyethylene ether, 38 parts of 2-acetamido acrylic acid, 10 parts of alpha-alkenyl sodium sulfonate, 3 parts of vinyl phosphoric acid, 2.6 parts of chain transfer agent, 5 parts of oxidant, 1.2 parts of reducing agent, 5 parts of NaOH solution and 350 parts of deionized water.
The unsaturated polyoxyethylene ether is isopentenol polyoxyethylene ether, and the average molecular weight is 2200-2400.
The alpha-sodium alkenyl sulfonate is tetradecene sodium alkenyl sulfonate.
The chain transfer agent is thioglycolic acid.
The oxidant is ammonium persulfate.
The reducing agent is sodium hypophosphite.
The mass concentration of the NaOH solution is 32%.
A preparation method of a viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
1) weighing the components according to the proportion, dissolving the weighed unsaturated polyoxyethylene ether in 280 parts of water, and adding an oxidant and 13 parts of 2-acetamido acrylic acid to obtain a bottom material;
2) dissolving alpha-sodium alkenyl sulfonate, the rest 2-acetamido acrylic acid, vinyl phosphoric acid, a chain transfer agent and a reducing agent in 70 parts of water to be used as a dropwise adding solution;
3) heating the base solution to 20 +/-2 ℃, starting dropwise adding the solution, controlling the reaction temperature not to exceed 40 +/-2 ℃, keeping the temperature and continuing to react for 1.5 hours after the addition is finished, and adding 6 parts of liquid alkali to adjust the pH value to 6-7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
The dropping time of the dropping solution in the step (3) is controlled to be 2 hours.
Each of the raw materials of the present invention is commercially available.
The folding solid content of the water reducing agent is 0.05 percent.
Example 3
The viscosity-reducing polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 400 parts of unsaturated polyoxyethylene ether, 40 parts of 2-acetamido acrylic acid, 14 parts of alpha-alkenyl sodium sulfonate, 4 parts of vinyl phosphoric acid, 2.8 parts of chain transfer agent, 6 parts of oxidant, 1.5 parts of reducing agent, 8 parts of NaOH solution and 400 parts of deionized water.
The unsaturated polyoxyethylene ether is isopentenol polyoxyethylene ether, and the average molecular weight is 2200-2400.
The alpha-sodium alkenyl sulfonate is sodium hexadecenyl sulfonate.
The chain transfer agent is mercaptoethanol.
The oxidant is potassium persulfate.
The reducing agent is ascorbic acid.
The mass concentration of the NaOH solution is 32%.
A preparation method of a viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
1) weighing the components according to the proportion, dissolving the weighed unsaturated polyoxyethylene ether in 320 parts of water, and adding an oxidant and 15 parts of 2-acetamino acrylic acid to obtain a bottom material;
2) dissolving alpha-sodium alkenyl sulfonate, the rest 2-acetamido acrylic acid, vinyl phosphoric acid, a chain transfer agent and a reducing agent into 80 parts of water to be used as a dropwise adding solution;
3) heating the base solution to 20 +/-2 ℃, starting dropwise adding the solution, controlling the reaction temperature not to exceed 40 +/-2 ℃, keeping the temperature for continuously reacting for 2 hours after the addition is finished, and adding 8 parts of liquid alkali to adjust the pH value to 6-7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
The dropping time of the dropping solution in the step (3) is controlled to be 3 hours.
Each of the raw materials of the present invention is commercially available.
The folding solid content of the water reducing agent is 0.05 percent.
Example 4
The viscosity-reducing polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 400 parts of unsaturated polyoxyethylene ether, 40 parts of 2-acetamido acrylic acid, 14 parts of alpha-alkenyl sodium sulfonate, 5 parts of vinyl phosphoric acid, 2.8 parts of chain transfer agent, 6 parts of oxidant, 1.5 parts of reducing agent, 8 parts of NaOH solution and 400 parts of deionized water.
The unsaturated polyoxyethylene ether is the isobutenol polyoxyethylene ether, and the average molecular weight is 2200-2400.
The alpha-alkenyl sodium sulfonate is a mixture of dodecenyl sodium sulfonate, tetradecenyl sodium sulfonate, hexadecenyl sodium sulfonate and the like in mass.
The chain transfer agent is prepared by mixing mercaptopropionic acid, thioglycolic acid, mercaptoethanol, sodium hypophosphite and the like in mass.
The oxidant is a mixture of hydrogen peroxide, ammonium persulfate, potassium persulfate and the like.
The reducing agent is a mixture of sodium formaldehyde sulfoxylate, sodium hypophosphite, ascorbic acid, sodium bisulfite and the like.
The mass concentration of the NaOH solution is 32%.
A preparation method of a viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
1) weighing the components according to the proportion, dissolving the weighed unsaturated polyoxyethylene ether in 330 parts of water, and adding an oxidant and 10-15 parts of 2-acetaminoacrylic acid to obtain a bottom material;
2) dissolving alpha-sodium alkenyl sulfonate, the rest 2-acetamido acrylic acid, vinyl phosphoric acid, a chain transfer agent and a reducing agent in 70 parts of water to be used as a dropwise adding solution;
3) heating the base solution to 20 +/-2 ℃, starting dropwise adding the solution, controlling the reaction temperature not to exceed 40 +/-2 ℃, keeping the temperature for continuously reacting for 2 hours after the addition is finished, and adding 8 parts of liquid alkali to adjust the pH value to 6-7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
The dropping time of the dropping solution in the step (3) is controlled to be 3 hours.
Each of the raw materials of the present invention is commercially available.
The folding solid content of the water reducing agent is 0.05 percent.
Comparative example 1
The polycarboxylate superplasticizer is prepared from the following raw materials in parts by weight: 400 parts of unsaturated polyoxyethylene ether, 40 parts of acrylic acid, 14 parts of alpha-alkenyl sodium sulfonate, 5 parts of vinyl phosphoric acid, 2.8 parts of chain transfer agent, 6 parts of oxidant, 1.5 parts of reducing agent, 8 parts of NaOH solution and 400 parts of deionized water.
The formulation and preparation of this comparative example is essentially the same as example 4, except that this comparative example uses acrylic acid instead of 2-acetamidoacrylic acid.
Comparative example 2
The polycarboxylate superplasticizer is prepared from the following raw materials in parts by weight: 400 parts of unsaturated polyoxyethylene ether, 40 parts of 2-acetamido acrylic acid, 14 parts of unsaturated sulfonate, 5 parts of vinyl phosphoric acid, 2.8 parts of chain transfer agent, 6 parts of oxidant, 1.5 parts of reducing agent, 8 parts of NaOH solution and 400 parts of deionized water.
The formulation and preparation of this comparative example is essentially the same as example 4, except that this comparative example uses an unsaturated sulfonate instead of sodium alpha-alkenyl sulfonate. The unsaturated sulfonate is one or more selected from sodium vinylsulfonate, sodium allylsulfonate, sodium methallyl sulfonate and sodium propyl ethylene sulfonate.
Comparative example 3
The viscosity-reducing polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 400 parts of unsaturated polyoxyethylene ether, 40 parts of acrylic acid, 14 parts of unsaturated sulfonate, 2.8 parts of chain transfer agent, 6 parts of oxidant, 1.5 parts of reducing agent, 8 parts of NaOH solution and 400 parts of deionized water.
The formulation and preparation of this comparative example is essentially the same as example 4, except that this comparative example: using acrylic acid instead of 2-acetamidoacrylic acid; using an unsaturated sulfonate instead of sodium alpha-alkenyl sulfonate; vinyl phosphoric acid was not added. The unsaturated sulfonate is one or more selected from sodium vinylsulfonate, sodium allylsulfonate, sodium methallyl sulfonate and sodium propyl ethylene sulfonate.
In order to compare the viscosity reduction performance and the dispersion retention performance of the water reducer prepared by the invention, a cement paste fluidity test is carried out according to the GB8077-2012 standard, 300g of cement and 87g of water are added, the cement paste fluidity is measured on flat glass after stirring for 4 minutes, and the paste fluidity at different times is tested. And (3) detecting the apparent viscosity of the cement paste by adopting an SNB intelligent rotor viscometer. The results are shown in Table 1
TABLE 1 Cement Net-paste fluidity and loss over time for the different samples
Testing of concrete Properties
According to the GB8076-2008 concrete admixture test method, the water reducing agent prepared in the example 1-8 is subjected to concrete experiment test. The sand is common river sand, the fineness modulus is 2.9, and the mixing amount is 0.15 percent of the cement dosage. Workability is divided into: good (slump greater than 220 and spreading greater than 500), normal (slump 180-220 and spreading 480-500) and poor (slump less than 180 and spreading less than 480). The C30 standard mix ratio was used.
The concrete test mix ratios are shown in table 2, and the concrete test results are shown in table 3.
TABLE 2 concrete test mix proportions
| Cement | Fly ash | Mineral powder | River sand | Big stone | Small stone | Amount of water used |
| 400kg/m3 | 40kg/m3 | 50kg/m3 | 684kg | 820kg | 335kg | 135kg |
TABLE 3 comparison of concrete Performance tests
| Numbering | Initial slump | Initial degree of expansion | Slump of 1h | Workability |
| Example 1 | 222 | 510 | 215 | Good taste |
| Example 2 | 220 | 506 | 210 | Good taste |
| Example 3 | 232 | 520 | 213 | Good taste |
| Example 4 | 239 | 525 | 218 | Good taste |
| Comparative example 1 | 208 | 489 | 192 | In general |
| Comparative example 2 | 215 | 501 | 198 | Good taste |
| Comparative example 3 | 211 | 492 | 189 | In general |
| Commercial water reducing agent product | 209 | 492 | 202 | In general |
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Claims (9)
1. The viscosity reduction type polycarboxylate superplasticizer is characterized by being prepared from the following raw materials in parts by weight: 400 parts of unsaturated polyoxyethylene ether, 35-40 parts of 2-acetaminoacrylic acid, 7-14 parts of alpha-alkenyl sodium sulfonate, 3-5 parts of vinyl phosphoric acid, 2.5-2.8 parts of chain transfer agent, 4-6 parts of oxidant, 1-1.5 parts of reducing agent, 2-8 parts of NaOH solution and 400 parts of deionized water.
2. The viscosity-reducing polycarboxylate water reducer as claimed in claim 1, wherein the unsaturated polyoxyethylene ether is isobutylene alcohol polyoxyethylene ether or prenol polyoxyethylene ether, and the average molecular weight is 2200-2400.
3. The viscosity-reducing polycarboxylate superplasticizer according to claim 1, wherein the sodium alpha-alkenyl sulfonate is R1-CH- (CH)2)n-SO3Na, where R1 ═ C9-13 and n is 1, 2, 3.
4. The viscosity-reduction type polycarboxylate superplasticizer according to claim 1, wherein the chain transfer agent is one or more of mercaptopropionic acid, thioglycolic acid, mercaptoethanol, sodium hypophosphite and sodium methyl propenyl sulfonate.
5. The viscosity-reduction type polycarboxylate superplasticizer according to claim 1, wherein the oxidant is one or more of hydrogen peroxide, ammonium persulfate and potassium persulfate.
6. The viscosity-reduction type polycarboxylate superplasticizer according to claim 1, wherein the reducing agent is one or more of sodium formaldehyde sulfoxylate, sodium hypophosphite, ascorbic acid and sodium bisulfite.
7. The viscosity-reducing polycarboxylate superplasticizer according to claim 1, wherein the mass concentration of the NaOH solution is 32%.
8. The preparation method of the viscosity-reducing polycarboxylate superplasticizer according to any one of claims 1 to 7 is characterized by comprising the following steps:
1) weighing the components according to the proportion, dissolving the weighed unsaturated polyoxyethylene ether in 300 parts of water containing 200-15 parts of 2-acetamino acrylic acid and adding an oxidant to obtain a substrate;
2) dissolving alpha-sodium alkenyl sulfonate, the rest 2-acetamido acrylic acid, vinyl phosphoric acid, a chain transfer agent and a reducing agent into 70-80 parts of water to be used as dropwise adding solution;
3) heating the base solution to 20 +/-2 ℃, starting dropwise adding the solution, controlling the reaction temperature not to exceed 40 +/-2 ℃, keeping the temperature and continuing to react for 1-2 hours after the addition is finished, and adding 2-8 parts of liquid alkali to adjust the pH value to 6-7 to obtain the viscosity-reducing polycarboxylic acid water reducer.
9. The method for preparing a viscosity-reducing polycarboxylate water reducer according to claim 8, wherein the dropping time of the dropping solution in the step (3) is controlled to be 1.5-3 hours.
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