CN111393583B - Amino propane sulfonic acid inner salt type amphoteric concrete water reducer and preparation method thereof - Google Patents
Amino propane sulfonic acid inner salt type amphoteric concrete water reducer and preparation method thereof Download PDFInfo
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- CN111393583B CN111393583B CN202010218873.5A CN202010218873A CN111393583B CN 111393583 B CN111393583 B CN 111393583B CN 202010218873 A CN202010218873 A CN 202010218873A CN 111393583 B CN111393583 B CN 111393583B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 68
- 150000003839 salts Chemical class 0.000 title claims abstract description 48
- ZIRURAJAJIQZFG-UHFFFAOYSA-N 1-aminopropane-1-sulfonic acid Chemical compound CCC(N)S(O)(=O)=O ZIRURAJAJIQZFG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000001603 reducing effect Effects 0.000 claims abstract description 21
- 239000004568 cement Substances 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- IUXKEHURPNDODV-UHFFFAOYSA-N 3-(dimethylamino)-1-(2-methylprop-2-enoyloxy)pentane-3-sulfonic acid Chemical compound CN(C)C(CC)(S(=O)(=O)O)CCOC(C(=C)C)=O IUXKEHURPNDODV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 24
- 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 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 230000000977 initiatory effect Effects 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 12
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 9
- 229930003268 Vitamin C Natural products 0.000 claims description 9
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 9
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 9
- 235000019154 vitamin C Nutrition 0.000 claims description 9
- 239000011718 vitamin C Substances 0.000 claims description 9
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 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
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 16
- 150000001768 cations Chemical class 0.000 abstract description 6
- 150000001450 anions Chemical class 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 239000010881 fly ash Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 abstract 1
- 229920005646 polycarboxylate Polymers 0.000 description 19
- 125000002091 cationic group Chemical group 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 description 6
- 239000013068 control sample Substances 0.000 description 5
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000008030 superplasticizer Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 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 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- -1 sulfonate anion Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004804 winding 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses an amino propane sulfonic acid inner salt type amphoteric concrete water reducing agent and a preparation method thereof, wherein the amino propane sulfonic acid inner salt type amphoteric concrete water reducing agent is prepared by polymerizing acrylic acid, itaconic acid, sodium methallyl sulfonate, polyether macromonomer and N, N-dimethyl (methacryloyloxyethyl) amino propane sulfonic acid inner salt under the action of a peroxide initiator, the prepared polycarboxylic acid water reducing agent contains an amino propane sulfonic acid inner salt type amphoteric structure, the stability and the dispersing water reducing effect of the polycarboxylic acid water reducing agent are not influenced, when the polycarboxylic acid water reducing agent is used, the inner salt structure can display electric neutrality or release cations and anions along with the acidity and alkalinity of an environmental system, and can respectively form stable structures with cation and anion areas on particles such as cement, fly ash, mineral powder and the like in a concrete body system, and the polycarboxylic acid water reducing agent has the advantages of good water reducing performance, good mud resisting performance, scientific and reasonable preparation process, no pollution, high water reducing rate, high mud resisting performance and the like, and high cost performance ratio, and good market application prospect.
Description
Technical Field
The invention relates to a concrete admixture, in particular to an amino propane sulfonic acid inner salt type amphoteric concrete water reducer and a preparation method thereof.
Background
The polycarboxylate water reducer is the cement water reducer with the largest current dosage and the most extensive application, has the advantages of high water reducing rate, good dispersibility, low doping amount, larger selection range of the monomer for preparation, capability of regulating and controlling the performance of the polycarboxylate water reducer by selecting the monomer and changing the proportion, and no pollution in the preparation process; the polycarboxylic acid water reducer has the defects of being sensitive to cement and sand and gravel content in a concrete system, easily causing bleeding and segregation and seriously affecting the stable use of the polycarboxylic acid water reducer. The polycarboxylic acid water reducer is usually obtained by free radical polymerization of acrylic monomers, carboxylic acid containing double bonds and polyether macromonomer, and the components and the proportion of the current polycarboxylic acid water reducer need to be adjusted according to the actual application requirements because of the large variety of the acrylic monomers, the carboxylic acid monomers containing double bonds and the polyether macromonomer, and in fact, different manufacturers have the selected proportion and the process condition according to the application when producing the polycarboxylic acid water reducer. Therefore, the polycarboxylate water reducer is a hot spot of research in recent years, and the formula and the synthesis process of the polycarboxylate water reducer are continuously explored and regulated.
The currently used polycarboxylate superplasticizer is mainly an anionic polycarboxylate superplasticizer obtained by copolymerizing an anionic monomer and a nonionic monomer, and the variety and the dosage of the amphoteric polycarboxylate superplasticizer are small. Research shows that the amphoteric polycarboxylate water reducer has better water reducing and mud resisting effects and other application performances. The preparation of the amphoteric polycarboxylate water reducer is not as simple as adding some cationic monomers into the raw materials, and has strict requirements on the structure, performance, dosage and the like of the cationic monomers. The reason why the amphoteric polycarboxylate water reducer is difficult to prepare is mainly that: (1) The monomer containing quaternary ammonium salt type cations capable of carrying out free radical polymerization double bonds only has few types of diallyl dimethyl ammonium chloride, methacryloyl oxyethyl trimethyl ammonium chloride and the like, the amphoteric polycarboxylate water reducer prepared by the monomer has strong dispersibility and water reducing property, but because the cationic property exists in the form of quaternary ammonium salt and chloride anion bonds, the quaternary ammonium salt cationic property is strong in a water system and has high degree of freedom, the monomer is easy to combine with surrounding anion groups, gel is easy to form by itself and the action of the monomer and cement particles is strong, the using effect is influenced, the content of the cationic monomer in the monomer of the water reducer is generally about 1 percent, and if the content is high, the agglomeration of the polycarboxylate water reducer and the reduction of the water reducing and dispersing effects are caused; (2) If organic amine invisible cationic monomers containing double bonds such as dimethylaminoethyl methacrylate, diallyl amine and the like are selected, the monomers hardly show cationic property in the alkaline environment of concrete, so that the dispersing and water reducing effects of the polycarboxylic acid water reducing agent are limited for hopefully improving through an amphoteric structure; (3) The main cationic monomers such as diallyl dimethyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride and the like which are currently used contain chloride ions which have a corrosive effect on the reinforcing steel bars in concrete, so that the use of such cationic monomers for amphoteric polycarboxylate water reducers is strictly controlled and limited.
Disclosure of Invention
The invention aims to provide an amino propane sulfonic acid inner salt type amphoteric concrete water reducer and a preparation method thereof, and the prepared amphoteric concrete water reducer solves the problems that the existing water reducer is stable and the content of cationic monomers is difficult to regulate and control, and has high water reducing rate and high mud resistance effect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer comprises the following steps of:
firstly, adding 85-95 parts of polyether macromonomer and 90-102 parts of water into a reactor according to parts by weight, uniformly stirring, keeping the temperature in the system at 40-50 ℃, and then adding 0.3-0.5 part of persulfate and uniformly stirring for later use;
step two, mixing 9 to 12 parts of acrylic acid, 2 to 3 parts of itaconic acid, 1 to 2 parts of sodium methacrylate and 5 to 8 parts of N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt with 60 to 70 parts of water, and uniformly stirring to obtain a monomer mixed solution to be added dropwise;
uniformly mixing 0.3-0.5 part of vitamin C, 0.25-0.35 part of mercaptoethanol and 30-40 parts of water to form an initiation regulator solution which needs to be added dropwise;
and step four, respectively dripping the monomer mixed solution prepared in the step two and the step three and the initiation regulator solution into the solution in the step one for 2.5 to 3 hours, continuously stirring and reacting for 2 to 3 hours after dripping, cooling to 30 to 40 ℃, and regulating the pH value to 6.5 to 7.0 by using sodium hydroxide with the mass fraction of 40 percent to obtain the amino propane sulfonic acid inner salt type amphoteric concrete water reducer.
Further, the polyether macromonomer is one or a mixture of several of allyl alcohol polyoxyethylene ether, methyl allyl alcohol polyoxyethylene ether and isopentenyl alcohol polyoxyethylene ether, the molecular weight is 2100-2600, the water content is less than or equal to 1%, the hydroxyl value is 2100-2200 mgKOH/g, the unsaturation degree is 0.3-0.35 mmol, and the pH value of a 1% aqueous solution is 5.0-7.0.
Further, the purity of the acrylic acid, itaconic acid, sodium methacrylate sulfonate and N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt is more than or equal to 98%.
Further, the persulfate is ammonium persulfate, sodium persulfate or potassium persulfate, and the content of the persulfate is more than 99%.
Further, the content of the vitamin C and the mercaptoethanol is more than 99 percent.
An amino propane sulfonic acid inner salt type amphoteric concrete water reducing agent has a molecular structural formula as follows:
wherein a, b, c, d, e is the number of structural units.
Further, the molecular weight is 7-11 ten thousand, when the solid mixing amount of the water reducing agent is 0.15-0.17% of the mass of cement, the water reducing rate is 38-45%, and the mud resistance content is 12-15%.
Compared with the prior art, the invention has the beneficial effects that:
(1) The amphoteric polycarboxylate water reducer is prepared by selecting N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt type amphoteric monomer N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt polymer as cationic monomer, and has the advantages of being nonionic in appearance, being a nonionic inner salt type structure when in the polycarboxylate water reducer molecule, and not affecting the stability of the polycarboxylate water reducer.
(2) When the prepared aminopropanesulfonic acid inner salt type amphoteric concrete water reducer is used with a concrete system, the inner salt structure of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer can show non-ions, cations and anions along with the different pH values of an environmental system, and under the stronger alkaline environment of the cement system, the annular inner salt type electroneutral structure of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer is opened to form a quaternary ammonium cation and sulfonate anion zwitterionic structure, and the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer can be respectively combined with anions and cations on particles such as cement, fly ash, mineral powder and the like in the concrete system, so that the effect of forming adsorption, dispersion, blocking and winding layers on cement by polycarboxylic acid water reducer molecules is improved, and the aminopolycarboxylic acid water reducer has better dispersion and water reduction effects compared with the traditional anion-non-ionic polycarboxylic acid water reducer.
(3) The traditional anionic polycarboxylate water reducer has an electric double layer structure formed on cement and other particles, and the polycarboxylate water reducer prepared by the method can form an adsorption layer structure of a three-electric layer on the surface of cement, has better dispersion effect, and further has higher water reducing, mud resisting, viscosity reducing and fluidity increasing effects.
(4) Compared with the products obtained by adopting dimethyl diallyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride, the product does not contain chloride ions, and has better durability when being used for concrete.
(5) The molecular weight of the invention is 7-11 ten thousand, the solid mixing amount is 0.15-0.17% of the cement mass, the water reducing rate can reach 38-45%, the mud resisting content can reach 12-15%, the blank time for reducing the viscosity of C60 concrete is characterized by 6-8 seconds, and the compressive strength and the flexural strength are respectively improved by 12-18% and 14-19% compared with the corresponding polycarboxylic acid water reducing agent without cations.
(6) The preparation process is scientific and reasonable, pollution is avoided, and the product has the performances of micro air entraining, high water reducing rate, high mud resistance and the like, has high cost performance and has good market application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but is not limited thereto.
The invention provides a preparation method of an amino propane sulfonic acid inner salt type amphoteric concrete water reducer, which specifically comprises the following steps:
step one, adding 85 to 95 parts of polyether macromonomer and 90 to 102 parts of water into a reactor according to parts by weight, uniformly stirring, keeping the temperature in the system at 40 to 50 ℃, and then adding 0.3 to 0.5 part of persulfate and uniformly stirring for standby.
Step two, mixing and stirring 9 to 12 parts of acrylic acid, 2 to 3 parts of itaconic acid, 1 to 2 parts of sodium methacrylate and 5 to 8 parts of N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt with 60 to 70 parts of water uniformly, thus obtaining a monomer mixed solution to be added dropwise.
And step three, uniformly mixing 0.3 to 0.5 part of vitamin C, 0.25 to 0.35 part of mercaptoethanol and 30 to 40 parts of water to form an initiation regulator solution which needs to be added dropwise.
And step four, respectively dripping the monomer mixed solution prepared in the step two and the step three and the initiation regulator solution into the solution in the step one for 2.5 to 3 hours, continuously stirring and reacting for 2 to 3 hours after dripping, cooling to 30 to 40 ℃, neutralizing the product obtained in the step four by using sodium hydroxide with the mass fraction of 40 percent, and regulating the pH value to 6.5 to 7.0, wherein the product is the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer.
The polyether macromonomer is one or a mixture of allyl alcohol polyoxyethylene ether, methyl allyl alcohol polyoxyethylene ether and isopentenyl alcohol polyoxyethylene ether, and is industrial grade, the molecular weight is 2100-2600, the water content is less than or equal to 1%, the hydroxyl value is 2100-2200 mgKOH/g, the unsaturation degree is 0.3-0.35 mmol, and the pH value of a 1% aqueous solution is 5.0-7.0.
The purity of the acrylic acid, itaconic acid, sodium methacrylate sulfonate and N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt is more than or equal to 98%.
The persulfate is ammonium persulfate, sodium persulfate and potassium persulfate, and the content of the persulfate is more than 99%.
The initiator is vitamin C, and the content is more than 99%;
the molecular weight regulator is one of mercaptoethanol, mercaptoacetic acid and mercaptopropionic acid, and the content is more than 98%;
the molecular weight of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer is 7-11 ten thousand, the solid doping amount is 0.15-0.17% of the cement mass, the water reducing rate can reach 38-45%, and the mud resisting content can reach 12-15%.
The reaction equation for preparing the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer is as follows:
embodiment one:
step one, adding 90 parts of polyether macromonomer and 96 parts of water into a reactor according to parts by weight, uniformly stirring, keeping the temperature in the system at 45 ℃, and then adding 0.4 part of persulfate and uniformly stirring for standby.
And step two, mixing and uniformly stirring 11 parts of acrylic acid, 2.5 parts of itaconic acid, 1.5 parts of sodium methacrylate and 6.5 parts of N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt with 65 parts of water, thus obtaining a monomer mixed solution to be added dropwise.
And step three, uniformly mixing 0.4 part of vitamin C, 0.30 part of mercaptoethanol and 35 parts of water to form a solution of the initiation regulator to be added dropwise.
And step four, respectively dripping the monomer mixed solution prepared in the step two and the step three and the initiation regulator solution into the solution in the step one for 2.8 hours, continuously stirring for 2.5 hours after dripping, cooling to 35 ℃, neutralizing the product obtained in the step four by using sodium hydroxide with the mass fraction of 40%, and regulating the pH value to 6.7, thus obtaining the amino propane sulfonic acid inner salt type amphoteric concrete water reducer.
The molecular weight of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer is 7 ten thousand, the solid doping amount is 0.17% of the cement mass, the water reducing rate can reach 38%, the mud resisting content can reach 12%, the viscosity of high-grade C60 concrete is obviously reduced, the viscosity is characterized by 8 seconds by the blank time, and the compressive strength and the flexural strength are respectively improved by 12% and 18% compared with a control sample.
The molecular structural formula of the prepared aminopropanesulfonic acid inner salt type amphoteric concrete water reducer is as follows:
embodiment two:
adding 85 parts of polyether macromonomer and 90 parts of water into a reactor according to parts by weight, uniformly stirring, keeping the temperature in the system at 40 ℃, and adding 0.3 part of persulfate and uniformly stirring for standby.
And step two, mixing and uniformly stirring 9 parts of acrylic acid, 2 parts of itaconic acid, 1 part of sodium methacrylate and 5 parts of N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt with 60 parts of water, thus obtaining a monomer mixed solution to be added dropwise.
And step three, uniformly mixing 0.3 part of vitamin C, 0.25 part of mercaptoethanol and 30 parts of water to form a solution of the initiation regulator to be added dropwise.
And step four, respectively dripping the monomer mixed solution prepared in the step two and the step three and the initiation regulator solution into the solution in the step one for 2.5 hours, continuously stirring for reaction for 2 hours after dripping, cooling to 30 ℃, neutralizing the product in the step four by using 40% sodium hydroxide by mass fraction, and regulating the pH value to 6.5, wherein the product is the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer.
The molecular weight of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer is 9 ten thousand, the solid doping amount is 0.17% of the cement mass, the water reducing rate can reach 42%, the mud resisting content can reach 13%, the viscosity of high-grade C60 concrete is obviously reduced, the viscosity is characterized by 7 seconds by the blank time, and the compressive strength and the flexural strength are respectively improved by 15% and 16% compared with a control sample.
Embodiment III:
step one, adding 95 parts of polyether macromonomer and 102 parts of water into a reactor according to parts by weight, uniformly stirring, keeping the temperature in the system at 50 ℃, and then adding 0.5 part of persulfate and uniformly stirring for standby.
And step two, mixing and uniformly stirring 12 parts of acrylic acid, 3 parts of itaconic acid, 2 parts of sodium methacrylate and 8 parts of N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt with 70 parts of water, thus obtaining a monomer mixed solution to be added dropwise.
And step three, uniformly mixing 0.5 part of vitamin C, 0.35 part of mercaptoethanol and 40 parts of water to form a solution of the initiation regulator to be added dropwise.
And step four, respectively dripping the monomer mixed solution prepared in the step two and the step three and the initiation regulator solution into the solution in the step one for 3 hours, continuously stirring for reaction for 3 hours after dripping, cooling to 40 ℃, neutralizing the product in the step four by using sodium hydroxide with the mass fraction of 40%, and regulating the pH value to 7.0, thus obtaining the amino propane sulfonic acid inner salt type amphoteric concrete water reducer.
The molecular weight of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer is 11 ten thousand, the solid doping amount is 0.15% of the cement mass, the water reducing rate can reach 45%, the mud resisting content can reach 15%, the viscosity of high-grade C60 concrete is obviously reduced, the viscosity is characterized by 6 seconds by the blank time, and the compressive strength and the flexural strength are respectively improved by 18% and 19% compared with a control sample.
Comparative example:
(1) The control sample is the polycarboxylic acid water reducer without cationic monomer, and the synthesis process conditions and the synthesis method are the same as those of the invention. The molecular weight of the polycarboxylic acid water reducer of the control sample is 6-11 ten thousand, the solid mixing amount is 0.17-0.19% of the cement mass, the water reducing rate can reach 21-35%, the mud resisting content can reach 6-10%, the high-grade C60 concrete viscosity is characterized by 18-24 seconds, and the compressive strength and the flexural strength are respectively improved by 22-25% and 18-23% compared with a blank sample.
(2) The formula of C60 concrete: 42.5 cement 440 parts, fly ash 80 parts, river sand 603 parts, continuous base crushed stone 1073 parts, 8% polycarboxylate superplasticizer 13.5 parts and water 150 parts.
Finally, it should be noted that: the above embodiments are only for illustrating the technical aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: modifications and equivalents may be made to the specific embodiments of the invention without departing from the spirit and scope of the invention, which are intended to be covered by the scope of the claims.
Claims (6)
1. The preparation method of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer is characterized by comprising the following steps of:
firstly, adding 85-95 parts of polyether macromonomer and 90-102 parts of water into a reactor according to parts by weight, uniformly stirring, keeping the temperature in the system at 40-50 ℃, and then adding 0.3-0.5 part of persulfate and uniformly stirring for later use;
step two, mixing 9 to 12 parts of acrylic acid, 2 to 3 parts of itaconic acid, 1 to 2 parts of sodium methacrylate and 5 to 8 parts of N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt with 60 to 70 parts of water, and uniformly stirring to obtain a monomer mixed solution to be added dropwise;
uniformly mixing 0.3-0.5 part of vitamin C, 0.25-0.35 part of mercaptoethanol and 30-40 parts of water to form an initiation regulator solution which needs to be added dropwise;
and step four, respectively dripping the monomer mixed solution prepared in the step two and the step three and the initiation regulator solution into the solution in the step one for 2.5 to 3 hours, continuously stirring and reacting for 2 to 3 hours after dripping, cooling to 30 to 40 ℃, and regulating the pH value to 6.5 to 7.0 by using sodium hydroxide with the mass fraction of 40 percent to obtain the amino propane sulfonic acid inner salt type amphoteric concrete water reducer.
2. The preparation method of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer as claimed in claim 1, which is characterized by comprising the following steps: the purity of the acrylic acid, itaconic acid, sodium methacrylate sulfonate and N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt is more than or equal to 98%.
3. The preparation method of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer as claimed in claim 1, which is characterized by comprising the following steps: the persulfate is ammonium persulfate, sodium persulfate or potassium persulfate, and the content of the persulfate is more than 99%.
4. The preparation method of the aminopropanesulfonic acid inner salt type amphoteric concrete water reducer as claimed in claim 1, which is characterized by comprising the following steps: the content of the vitamin C and the mercaptoethanol is more than 99 percent.
5. An aminopropanesulfonic acid inner salt type amphoteric concrete water reducer prepared by the preparation method according to any one of claims 1 to 4, which is characterized by having a molecular structural formula:
wherein a, b, c, d, e is the number of structural units.
6. The aminopropanesulfonic acid inner salt type amphoteric concrete water reducer according to claim 5, wherein: the molecular weight is 7-11 ten thousand, when the solid mixing amount of the water reducing agent is 0.15-0.17% of the mass of cement, the water reducing rate is 38-45%, and the mud resistance content is 12-15%.
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| CN110305262A (en) * | 2018-11-02 | 2019-10-08 | 湖北工业大学 | A kind of amphoteric early-strength polycarboxylate superplasticizer mother liquor for C30 concrete |
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| CN110305262A (en) * | 2018-11-02 | 2019-10-08 | 湖北工业大学 | A kind of amphoteric early-strength polycarboxylate superplasticizer mother liquor for C30 concrete |
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