CN113980206A - Preparation method of anti-mud slow-release polycarboxylate superplasticizer - Google Patents
Preparation method of anti-mud slow-release polycarboxylate superplasticizer Download PDFInfo
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 30
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 33
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 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 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 20
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 20
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 20
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 20
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 20
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 19
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 claims abstract description 15
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 11
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 17
- 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 12
- 229910052901 montmorillonite Inorganic materials 0.000 description 12
- 239000004568 cement Substances 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- -1 phosphate ester Chemical class 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—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
Abstract
The application discloses a preparation method of an anti-mud slow-release type polycarboxylate superplasticizer; acrylic acid, hydroxyethyl acrylate, 2-hydroxyethyl methacrylate phosphate and prenol polyoxyethylene ether are used as reaction monomers, hydrogen peroxide/ascorbic acid is used as an initiator, mercaptopropionic acid is used as a chain transfer agent, and a novel mud-resistant slow-release type polycarboxylate water reducer is synthesized through free radical copolymerization.
Description
Technical Field
The invention belongs to the technical field of polycarboxylic acid water reducing agents for concrete, and particularly relates to a preparation method of a mud-resistant slow-release polycarboxylic acid water reducing agent.
Background
The polycarboxylic acid high-performance water reducing agent (PCE) has the characteristics of low mixing amount, high water reducing rate, strong controllability of molecular structure and the like, and is widely applied to concrete engineering. However, compared with naphthalene-based, melamine-based and sulfamic acid-based water reducers, polycarboxylic acid water reducers are more sensitive to the mud content of aggregates, and a small amount of clay can greatly reduce the dispersing performance of the polycarboxylic acid water reducers.
Common clays include montmorillonite, kaolinite, illite, and the like, wherein montmorillonite has the most significant effect on PCE dispersion performance. The strong interaction exists between the montmorillonite and the PCE, when the PCE meets the montmorillonite, the PCE is adsorbed by the montmorillonite, so that the dispersion performance of the PCE is reduced, and the higher the concentration of the PCE is, the larger the adsorption quantity of the montmorillonite is. In addition, montmorillonite itself is a clay with strong water-absorbing swelling capacity, and water molecules are adsorbed on the surface and between layers of the clay. Therefore, under the condition of high mud content, the problems of water reducing rate, slump retaining property and the like cannot be solved by simply increasing the mixing amount of the PCE.
Disclosure of Invention
In order to solve the problems, the invention discloses a polycarboxylate superplasticizer which has strong mud resistance, good adaptability and a slow release function and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
using Acrylic Acid (AA), hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate phosphate (HEMAP) and isopentenol polyoxyethylene ether (TPEG) as reaction monomers, and hydrogen peroxide (H)2O2) The novel anti-mud slow-release type polycarboxylate superplasticizer is synthesized by taking ascorbic acid (VC) as an initiator and mercaptopropionic acid (MPA) as a chain transfer agent through free radical copolymerization, and comprises the following components in parts by weight: 100 parts of prenyl alcohol polyoxyethylene ether, 6-12 parts of acrylic acid, 4.8-9.6 parts of hydroxyethyl acrylate, 1-3 parts of 2-hydroxyethyl methacrylate phosphate, 1.05-1.26 parts of an initiator, 0.5-0.8 part of a chain transfer agent and 183 parts of water 173-.
Further, the initiator is ascorbic acid and hydrogen peroxide.
Further, the chain transfer agent is mercaptopropionic acid.
Further, the molecular weight of the prenol polyoxyethylene ether is 2400.
The invention also aims to provide a preparation method of the anti-mud slow-release type polycarboxylate superplasticizer, which comprises the following steps:
(1) adding water into prenyl polyoxyethylene ether (TPEG), heating and stirring to form a base solution;
(2) dissolving Acrylic Acid (AA), hydroxyethyl acrylate (HEA) and 2-hydroxyethyl methacrylate phosphate (HEMAP) in water to form solution A;
(3) mixing ascorbic acid (VC) and mercaptopropionic acid, and dissolving in water to form solution B;
(4) heating the base solution to 60-70 ℃, adding hydrogen peroxide, then beginning to dropwise add the solution A and the solution B into the base solution at a constant speed, stopping stirring after dropwise addition is finished, and carrying out heat preservation reaction;
(5) and after the heat preservation reaction is finished, adjusting the pH value of the synthesized water reducing agent to 6-7 by using a sodium hydroxide solution to obtain the water reducing agent with the solid content of 35-45%, wherein the water reducing agent is light yellow viscous liquid.
Further, in the step (1), the temperature of the heating and stirring is 60-70 ℃, and the time of the heating and stirring is 10 min.
Further, in the step (3) and the step (4), the mass ratio of the hydrogen peroxide to the ascorbic acid is 2.4-2.6. .
Further, in the step (4), the dropping time of the solution A is 2.0h-3.0h, and the dropping time of the solution B is 2.5h-3.5 h.
Further, in the step (4), the reaction time is 1.5-2.5 h.
Compared with the prior art, the invention has the beneficial effects that:
the anti-mud slow-release polycarboxylate superplasticizer of the invention introduces hydroxyethyl acrylate (HEA) and phosphate functional groups, and the phosphate contains PO with negative electricity4 3-And a negative PO4 3-The cement particles and cement hydrated particles are quickly wrapped to form a layer of protective film, so that the cement hydration is prevented, and the dispersing performance of the cement particles to the cement is improved. Meanwhile, as the hydration degree of cement is deepened, the cement paste is in an alkaline environment, and the alkaline environment can promote ester bonds in phosphate and HEA to be hydrolyzed and can slow downReleasing a large amount of carboxyl groups, and continuously adsorbing the carboxyl groups to the surface of cement particles to play a role of uniform dispersion. Therefore, the water reducing agent synthesized by the invention has good mud resistance and good slow release function.
Drawings
FIG. 1 is an infrared spectrum of macromonomer TPEG and the water reducing agent synthesized in example 2;
FIG. 2 is a TG plot of the synthetic water reducer of example 2;
FIG. 3 is a synthetic route diagram of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Example 1
(1) Weighing the following raw material components in parts by weight: 100g of prenyl alcohol polyoxyethylene ether TPEG (molecular weight of 2400), 6g of acrylic acid, 12.6g of hydroxyethyl acrylate, 1g of 2-hydroxyethyl methacrylate phosphate, 0.5g of mercaptopropionic acid, 0.30g of ascorbic acid, 0.72g of 30wt.% hydrogen peroxide, 173g of deionized water and a proper amount of 30wt.% sodium hydroxide.
(2) Dissolving 100g of prenyl polyoxyethylene ether in 63g of deionized water, stirring and heating to 60 ℃ to obtain a base solution.
(3) 6g of acrylic acid, 4.8g of hydroxyethyl acrylate and 1g of 2-hydroxyethyl methacrylate phosphate were dissolved in 60g of deionized water to obtain solution A.
(4) 0.30g of ascorbic acid and 0.5g of mercaptopropionic acid were dissolved in 50g of deionized water to obtain solution B.
(5) 0.72g of 30wt.% hydrogen peroxide is added into the base solution, and simultaneously the solution A and the solution B are dropwise added into the base solution at a constant speed to 60 ℃, wherein the dropwise adding time of the solution A is 2.0 hours, and the dropwise adding time of the solution B is 2.5 hours. After the dropwise addition, the stirring of the base solution is stopped, and the temperature is kept for 1.5 h.
(6) And (3) after the heat preservation is finished, adjusting the pH value of the base solution to 6-7 by using sodium hydroxide to obtain light yellow viscous liquid with the solid content of 35-45%, wherein the light yellow viscous liquid is the anti-mud slow-release type polycarboxylate superplasticizer.
Example 2
(1) Weighing the following raw material components in parts by weight: 100g of prenyl alcohol polyoxyethylene ether (molecular weight 2400), 9g of acrylic acid, 9.6g of hydroxyethyl acrylate, 2g of 2-hydroxyethyl methacrylate phosphate, 0.65g of mercaptopropionic acid, 0.33g of ascorbic acid, 0.83g of 30wt.% hydrogen peroxide, 178g of deionized water and a proper amount of 30wt.% sodium hydroxide.
(2) Dissolving 100g of prenyl polyoxyethylene ether in 63g of deionized water, stirring and heating to 65 ℃ to obtain a base solution.
(3) 6.0g of acrylic acid, 9.6g of hydroxyethyl acrylate and 2g of 2-hydroxyethyl methacrylate phosphate were dissolved in 65g of deionized water to obtain solution A.
(4) 0.33g of ascorbic acid and 0.65g of mercaptopropionic acid were dissolved in 50g of deionized water to obtain solution B.
(5) 0.83g of 30% hydrogen peroxide is added into the base solution, and simultaneously the solution A and the solution B are dropwise added into the base solution at the temperature of 65 ℃ at a constant speed, wherein the dropwise adding time of the solution A is 2.5 hours, and the dropwise adding time of the solution B is 3 hours. After the dropwise addition is finished, stopping stirring the base solution, and keeping the temperature for 2 hours.
(6) And (3) after the heat preservation is finished, adjusting the pH value of the base solution to 6-7 by using sodium hydroxide to obtain light yellow viscous liquid with the solid content of 35-45%, wherein the light yellow viscous liquid is the anti-mud slow-release type polycarboxylate superplasticizer.
From the comparison in FIG. 1, it can be seen that the water reducing agent is at 1650cm-1The stretching vibration peak of the carbon-carbon double bond around the peak almost disappears, indicating that most of the monomers are polymerized. 1730cm-1Is treated as the stretching vibration peak of the carboxylic ester on the phosphate side chain, 1570cm-1And the peak is the antisymmetric stretching vibration peak of carboxyl C = O. The above characteristic peaks indicate that the respective monomers have been successfully polymerized to give the copolymer.
As can be seen from FIG. 2, the decomposition temperature of the water-reducing agent at which 5% weight loss occurs is 321.9 ℃, and the unreacted monomers in the water-reducing agent decompose at this temperature. The decomposition temperature of the water reducing agent when the weight loss of the water reducing agent is 10 percent is 362.5 ℃, and the water reducing agent starts to decompose at the temperature. The synthesized water reducing agent has high thermal decomposition temperature, and can meet the requirements of concrete preparation and application temperature in most environments.
Example 3
(1) Weighing the following raw material components in parts by weight: 100g of prenyl alcohol polyoxyethylene ether (molecular weight 2400), 12g of acrylic acid, 6.6g of hydroxyethyl acrylate, 3g of 2-hydroxyethyl methacrylate phosphate, 0.8g of mercaptopropionic acid, 0.36g of ascorbic acid, 0.94g of 30wt.% hydrogen peroxide, 183g of deionized water and a proper amount of 30wt.% sodium hydroxide.
(2) Dissolving 100g of prenyl polyoxyethylene ether in 63g of deionized water, stirring and heating to 70 ℃ to obtain a base solution.
(3) 12g of acrylic acid, 4.8g of hydroxyethyl acrylate and 3g of 2-hydroxyethyl methacrylate phosphate were dissolved in 70g of deionized water to obtain solution A.
(4) 0.36g of ascorbic acid and 0.8g of mercaptopropionic acid were dissolved in 50g of deionized water to obtain solution B.
(5) 0.94g of 30 mass percent hydrogen peroxide is added into the base solution, and simultaneously the solution A and the solution B are dropwise added into the base solution at 70 ℃ at a constant speed, wherein the dropwise adding time of the solution A is 3.0 hours, and the dropwise adding time of the solution B is 3.5 hours. After the dropwise addition, the stirring of the base solution is stopped, and the temperature is kept for 2.5 h.
(6) And (3) after the heat preservation is finished, adjusting the pH value of the base solution to 6-7 by using sodium hydroxide to obtain light yellow viscous liquid with the solid content of 35-45%, wherein the light yellow viscous liquid is the anti-mud slow-release type polycarboxylate superplasticizer.
Comparative example
Compare with example 2. The main difference between comparative examples 1 to 3 is mainly in the amount of functional monomer incorporated. Wherein comparative example 1 does not contain a phosphate functional monomer; comparative example 2 contained an excess of phosphate ester monomer; comparative example 3 contained no phosphate and hydroxyethyl acrylate functional monomers; in order to further verify the performance of the prepared mud-resistant slow-release type polycarboxylate superplasticizer, a commercial slow-release type polycarboxylate superplasticizer Q8084 is taken as a comparative example 4 for performance experiment comparison.
Comparative example 1
(1) Weighing the following raw material components in parts by weight: 100g of prenyl alcohol polyoxyethylene ether (molecular weight 2400), 9g of acrylic acid, 9.6g of hydroxyethyl acrylate, 0.65g of mercaptopropionic acid, 0.33g of ascorbic acid, 0.83g of 30wt.% hydrogen peroxide, 175g of deionized water and a proper amount of 30wt.% sodium hydroxide.
(2) Dissolving 100g of prenyl polyoxyethylene ether in 63g of deionized water, stirring and heating to 65 ℃ to obtain a base solution.
(3) 6g of acrylic acid and 9.6g of hydroxyethyl acrylate were dissolved in 62g of deionized water to obtain solution A.
(4) 0.33g of ascorbic acid and 0.65g of mercaptopropionic acid were dissolved in 50g of deionized water to obtain solution B.
(5) 0.83g of 30% hydrogen peroxide is added into the base solution, and simultaneously the solution A and the solution B are dropwise added into the base solution at the temperature of 65 ℃ at a constant speed, wherein the dropwise adding time of the solution A is 2.5 hours, and the dropwise adding time of the solution B is 3 hours. After the dropwise addition is finished, stopping stirring the base solution, and keeping the temperature for 2 hours.
(6) And (3) after the heat preservation is finished, adjusting the pH value of the base solution to 6-7 by using sodium hydroxide to obtain light yellow viscous liquid with the solid content of 35-45%, wherein the light yellow viscous liquid is the anti-mud slow-release type polycarboxylate superplasticizer.
Comparative example 2
(1) Weighing the following raw material components in parts by weight: 100g of prenyl alcohol polyoxyethylene ether (molecular weight 2400), 9g of acrylic acid, 9.6g of hydroxyethyl acrylate, 4g of 2-hydroxyethyl methacrylate phosphate, 0.65g of mercaptopropionic acid, 0.33g of ascorbic acid, 0.83g of 30wt.% hydrogen peroxide, 175g of deionized water and a proper amount of 30wt.% sodium hydroxide.
(2) Dissolving 100g of prenyl polyoxyethylene ether in 63g of deionized water, stirring and heating to 65 ℃ to obtain a base solution.
(3) 6g of acrylic acid and 9.6g of hydroxyethyl acrylate were dissolved in 62g of deionized water to obtain solution A.
(4) 0.33g of ascorbic acid and 0.65g of mercaptopropionic acid were dissolved in 50g of deionized water to obtain solution B.
(5) 0.83g of 30% hydrogen peroxide is added into the base solution, and simultaneously the solution A and the solution B are dropwise added into the base solution at the temperature of 65 ℃ at a constant speed, wherein the dropwise adding time of the solution A is 2.5 hours, and the dropwise adding time of the solution B is 3 hours. After the dropwise addition is finished, stopping stirring the base solution, and keeping the temperature for 2 hours.
(6) And (3) after the heat preservation is finished, adjusting the pH value of the base solution to 6-7 by using sodium hydroxide to obtain light yellow viscous liquid with the solid content of 35-45%, wherein the light yellow viscous liquid is the anti-mud slow-release type polycarboxylate superplasticizer.
Comparative example 3
(1) Taking the following raw material components by weight: 100g of prenyl alcohol polyoxyethylene ether (molecular weight 2400), 12g of acrylic acid, 0.65g of mercaptopropionic acid, 0.33g of ascorbic acid, 0.83g of 30wt.% hydrogen peroxide, 169g of deionized water and a proper amount of 30wt.% sodium hydroxide.
(2) Dissolving 100g of prenyl polyoxyethylene ether in 63g of deionized water, stirring and heating to 65 ℃ to obtain a base solution.
(3) 12g of acrylic acid was dissolved in 56g of deionized water to obtain solution A.
(4) 0.33g of ascorbic acid and 0.65g of mercaptopropionic acid were dissolved in 50g of deionized water to obtain solution B.
(5) 0.83g of 30% hydrogen peroxide is added into the base solution, and simultaneously the solution A and the solution B are dropwise added into the base solution at 65 ℃ at a constant speed, wherein the dropwise adding time of the solution A is 2.5 hours, and the dropwise adding time of the solution B is 3 hours. After the dropwise addition is finished, stopping stirring the base solution, and keeping the temperature for 2 hours.
(6) And (3) after the heat preservation is finished, adjusting the pH value of the base solution to 6-7 by using sodium hydroxide to obtain light yellow viscous liquid with the solid content of 35-45%, wherein the light yellow viscous liquid is the anti-mud slow-release type polycarboxylate superplasticizer.
Comparative example 4
Adopts a commercial slow-release polycarboxylate superplasticizer Q8084.
Performance test
According to GB/T8077-2012, the water reducing agent and the montmorillonite in the examples 1-3 and the comparative examples 1-4 are mixed and then subjected to a net slurry fluidity test, wherein the mixing amount of the water reducing agent is 0.2 percent of the mass of the cement. The higher the fluidity, the higher the effect of the water reducing agent, and the better the mud resistance of the water reducing agent.
TABLE 1 results of Performance test of each example and comparative example
As can be seen from Table 1, compared with other examples, the initial net slurry fluidity of the anti-mud slow-release type polycarboxylate superplasticizer prepared in the example 2 of the present application is not much different between 0% montmorillonite doping amount and 1% montmorillonite doping amount, but the 1h net slurry fluidity of the polycarboxylate superplasticizer is obviously higher than that of other examples, and the example 2 is a better example.
Combining example 2 and comparative example 1, it can be seen that, in the case of no montmorillonite, the initial net slurry fluidity and the 1h net slurry fluidity of example 2 and comparative example 1 are not much different, but in the case of 1% montmorillonite, example 2 is obviously superior to comparative example 1, therefore, the mud resistance of the water reducer can be obviously improved by introducing the phosphate functional monomer into the main chain of the polycarboxylic acid water reducer. Combining example 2 and comparative example 2, it can be seen that an excess of phosphate ester would rather reduce the dispersing properties of the synthesized water-reducing agent. By combining the example 2 with the comparative examples 1 and 3, it can be seen that the slow release capability of the polycarboxylate superplasticizer can be obviously improved by introducing the hydroxyethyl acrylate functional monomer to the main chain of the polycarboxylate superplasticizer.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (9)
1. The mud-resistant slow-release polycarboxylate water reducer is characterized by comprising the following components in parts by weight: 100 parts of prenyl alcohol polyoxyethylene ether, 6-12 parts of acrylic acid, 6.6-12.6 parts of hydroxyethyl acrylate, 1-3 parts of 2-hydroxyethyl methacrylate phosphate, 1.05-1.26 parts of an initiator, 0.5-0.8 part of a chain transfer agent and 183 parts of water 173-.
2. The anti-mud slow-release type polycarboxylate superplasticizer according to claim 1, wherein the initiator is ascorbic acid and hydrogen peroxide.
3. The mud-resistant slow-release type polycarboxylate water reducer according to claim 1, wherein the chain transfer agent is mercaptopropionic acid.
4. The mud-resistant slow-release type polycarboxylate water reducer according to claim 1, wherein the molecular weight of the prenyl polyoxyethylene ether is 2400.
5. The preparation method of the mud-resistant slow-release type polycarboxylate superplasticizer according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) adding water into prenyl alcohol polyoxyethylene ether, heating and stirring to form a base solution;
(2) dissolving acrylic acid, hydroxyethyl acrylate and 2-hydroxyethyl methacrylate phosphate in water to form solution A;
(3) mixing ascorbic acid and mercaptopropionic acid, and dissolving in water to form solution B;
(4) heating the base solution to 60-70 ℃, adding hydrogen peroxide, then beginning to dropwise add the solution A and the solution B into the base solution at a constant speed, stopping stirring after dropwise addition is finished, and carrying out heat preservation reaction;
(5) and after the heat preservation reaction is finished, adjusting the pH value of the synthesized water reducing agent to 6-7 by using a sodium hydroxide solution to obtain the water reducing agent with the solid content of 35-45%, wherein the water reducing agent is light yellow viscous liquid.
6. The preparation method of the anti-mud slow-release type polycarboxylate superplasticizer according to claim 5, wherein in the step (1), the temperature of heating and stirring is 60-70 ℃, and the time of heating and stirring is 10 min.
7. The preparation method of the anti-mud slow-release type polycarboxylate superplasticizer according to claim 5, wherein in the step (3) and the step (4), the mass ratio of the hydrogen peroxide to the ascorbic acid is 2.4-2.6.
8. The preparation method of the anti-mud slow-release type polycarboxylate superplasticizer according to claim 5, wherein in the step (4), the dropping time of the solution A is 2.0h-3.0h, and the dropping time of the solution B is 2.5h-3.5 h.
9. The preparation method of the anti-mud slow-release type polycarboxylate superplasticizer according to claim 5, wherein in the step (4), the heat preservation reaction time is 1.5h-2.5 h.
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