CN115010876A - Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof - Google Patents
Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 42
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 28
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 21
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims abstract description 13
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims abstract description 13
- MOFPFBKKJKOCJG-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.CCCCOC(C)COC(C)CO MOFPFBKKJKOCJG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims description 21
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 10
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002211 L-ascorbic acid Substances 0.000 claims description 5
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 claims description 4
- 238000000034 method Methods 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
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 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
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 230000001603 reducing effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention belongs to the technical field of polycarboxylic acid water reducing agents, and particularly discloses a shrinkage-reducing polycarboxylic acid water reducing agent and a preparation method thereof. The invention firstly reacts unsaturated acid with diethylene glycol dipropylene glycol monobutyl ether and dipropylene glycol in a specific proportion to prepare a mixed functional monomer, and then reacts unsaturated alcohol polyoxyethylene ether, unsaturated acid, mixed functional monomer and other auxiliary agents to prepare the shrinkage-reducing polycarboxylic acid water reducer. The shrinkage-reducing polycarboxylate superplasticizer prepared by the invention has excellent shrinkage-reducing effect and water-reducing effect, and also has the characteristic of small addition amount, and the preparation process is simple.
Description
Technical Field
The invention relates to the technical field of polycarboxylic acid water reducing agents, and particularly relates to a shrinkage-reducing polycarboxylic acid water reducing agent and a preparation method thereof.
Background
The polycarboxylic acid water reducing agent (PCE) is advocated by researchers and engineering users since the end of the 20 th century and the 80 th generation due to the characteristics of low mixing amount, high water reducing rate (not less than 25%), good reinforcing effect, strong molecular adjustability, no use of formaldehyde in the synthesis process and the like. Particularly, after the popularization and application of the PCE in the high-speed railway and dam engineering in China at the beginning of the 21 st century, a wave is raised in the PCE research aspect and is not settled for a long time. With regard to PCE research, most scholars focus on the explanation of the action mechanism, the further improvement of the performance, the development of derivative products and the optimization of application technology, and aim to thoroughly solve the technical problem of actual construction of cement concrete, improve the comprehensive performance (high workability, high strength, high toughness and high durability) of the concrete and furthest realize the aims of saving resources, utilizing waste, saving energy and reducing emission. Although PCE has been studied to some extent today, many problems need to be solved because PCE is still poorly understood.
After the concrete is poured, a series of shrinkage, such as plastic dry shrinkage, chemical shrinkage, self-shrinkage and hardening dry shrinkage, occurs, so that shrinkage cracks are generated, and the mechanical property and durability of the structure are seriously affected. Although some multifunctional polycarboxylic acid water reducing agents are disclosed, the multifunctional polycarboxylic acid water reducing agents are not ideal for reducing shrinkage cracking of concrete, and have the problems of large mixing amount and high cost. Therefore, how to provide a shrinkage-reducing polycarboxylate water reducer and a preparation method thereof, which ensure the excellent shrinkage-reducing performance of the polycarboxylate water reducer on the premise of less mixing amount is a difficult problem to be solved in the field.
Disclosure of Invention
In view of the above, the invention provides a reduction type polycarboxylate water reducer and a preparation method thereof, which are used for solving the problems of large using amount and poor reduction effect of the traditional reduction type polycarboxylate water reducer.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a shrinkage-reducing polycarboxylate superplasticizer comprises the following steps:
1) mixing unsaturated acid, diethylene glycol dipropylene glycol monobutyl ether, dipropylene glycol, hydroquinone and p-toluenesulfonic acid, and reacting to obtain a mixed functional monomer;
2) mixing and dropwise adding unsaturated acid, mixed functional monomer and molecular weight regulator into the mixed solution, and then dropwise adding a reducing agent for reaction to obtain a reaction solution;
3) adding alkali liquor into the reaction solution to obtain a shrinkage-reducing polycarboxylic acid water reducing agent;
the mixed solution comprises unsaturated alcohol polyoxyethylene ether, an oxidant and water.
Preferably, the unsaturated acid in step 1) and step 2) is one or more of acrylic acid, methacrylic acid and maleic anhydride.
Preferably, the molar ratio of the unsaturated acid, the dipropylene glycol and the diethylene glycol dipropylene glycol monobutyl ether in the step 1) is 3-5: 0.8-1: 1.2-1.5, wherein the mass ratio of hydroquinone to unsaturated acid is 2-5: 100, the mass ratio of p-toluenesulfonic acid to unsaturated acid is 2-5: 100, respectively;
the reaction temperature in the step 1) is 110-130 ℃, and the reaction time is 4-6 h.
Preferably, the unsaturated alcohol polyoxyethylene ether comprises one or two of isopentenol polyoxyethylene ether and isobutenol polyoxyethylene ether, the oxidant comprises one or more of hydrogen peroxide solution, ammonium persulfate solution and potassium persulfate solution, and the mass concentration of the oxidant is 10-30 g/mL.
Preferably, the mass ratio of the unsaturated alcohol polyoxyethylene ether to the oxidant is 1: 0.06-0.08, wherein the mass concentration of the unsaturated alcohol polyoxyethylene ether in the mixed solution is 35-50%.
Preferably, the molecular weight regulator in step 2) comprises thioglycolic acid, 3-mercaptopropionic acid, mercaptoethanol and sodium hypophosphite; the reducing agent comprises one or more of L-ascorbic acid, sodium formaldehyde sulfoxylate and Mohr's salt.
Preferably, the mass volume ratio of the unsaturated acid, the mixed functional monomer, the molecular weight regulator, the reducing agent to the mixed solution is 15-20 g: 120-140 g: 2-3 g: 0.35-0.5 g: 550-700 mL.
Preferably, the dropping time of the mixture of the unsaturated acid, the mixed functional monomer and the molecular weight regulator is 2.5-3 h, and the dropping time of the reducing agent is 2.5-3 h.
Preferably, the reaction temperature in the step 2) is 50-70 ℃, and the reaction time is 0.8-1.2 h; adding alkali liquor in the step 3), wherein the pH value of the system is 6.5-7.
The invention also aims to provide a preparation method of the reduction type polycarboxylate superplasticizer to prepare the reduction type polycarboxylate superplasticizer.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the prepared shrinkage-reducing polycarboxylate superplasticizer has excellent water reducing effect and stronger shrinkage reducing performance, can greatly avoid shrinkage cracks generated after concrete is poured, and improves the later mechanical property and durability of the concrete;
2. unsaturated acid can react with macromolecular dipropylene glycol monobutyl ether and micromolecular dipropylene glycol under the same condition to prepare a mixed functional monomer with a specific proportion, so that a special comb-shaped structure is formed, and the shrinkage of concrete is avoided to a great extent while a high water reducing effect is kept;
3. the preparation process disclosed by the invention is simple and easy to implement industrially.
Detailed Description
The invention provides a preparation method of a shrinkage-reducing polycarboxylic acid water reducing agent, which comprises the following steps:
1) mixing unsaturated acid, diethylene glycol dipropylene glycol monobutyl ether, dipropylene glycol, hydroquinone and p-toluenesulfonic acid, and reacting to obtain a mixed functional monomer;
2) mixing and dropwise adding unsaturated acid, mixed functional monomer and molecular weight regulator into the mixed solution, and then dropwise adding a reducing agent for reaction to obtain a reaction solution;
3) adding alkali liquor into the reaction solution to obtain a reduction type polycarboxylate superplasticizer;
the mixed solution comprises unsaturated alcohol polyoxyethylene ether, an oxidant and water.
In the invention, the unsaturated acid in the step 1) and the step 2) is independently one or more of acrylic acid, methacrylic acid and maleic anhydride.
In the invention, the molar ratio of the unsaturated acid, the dipropylene glycol and the diethylene glycol dipropylene glycol monobutyl ether in the step 1) is 3-5: 0.8-1: 1.2 to 1.5, preferably 3.5 to 4.5: 0.82-0.9: 1.3 to 1.4, and more preferably 4: 0.88: 1.36; the mass ratio of hydroquinone to unsaturated acid is 2-5: 100, preferably 3-4: 100, more preferably 3.5: 100, respectively; the mass ratio of the toluenesulfonic acid to the unsaturated acid is 2-5: 100, preferably 3-4: 100, more preferably 3.5: 100.
in the invention, the reaction temperature in the step 1) is 110-130 ℃, preferably 115-125 ℃, and more preferably 120 ℃; the reaction time is 4-6 h, preferably 5-6 h, and more preferably 6 h.
In the invention, the unsaturated alcohol polyoxyethylene ether comprises one or two of isopentenol polyoxyethylene ether and isobutenol polyoxyethylene ether, the oxidant comprises one or more of hydrogen peroxide solution, ammonium persulfate solution and potassium persulfate solution, and the mass concentration of the oxidant is 10-30 g/mL, preferably 15-25 g/mL, and more preferably 20 g/mL.
In the invention, the mass ratio of the unsaturated alcohol polyoxyethylene ether to the oxidant is 1: 0.06-0.08, preferably 1: 0.07; the mass concentration of the unsaturated alcohol polyoxyethylene ether in the mixed solution is 35-50%, preferably 38-48%, and more preferably 43%.
In the invention, the molecular weight regulator in the step 2) comprises thioglycolic acid, 3-mercaptopropionic acid, mercaptoethanol and sodium hypophosphite; the reducing agent comprises one or more of L-ascorbic acid, sodium formaldehyde sulfoxylate and Mohr's salt.
In the invention, the mass-volume ratio of the unsaturated acid, the mixed functional monomer, the molecular weight regulator, the reducing agent to the mixed solution is 15-20 g: 120-140 g: 2-3 g: 0.35-0.5 g: 550-700 mL, preferably 16-19 g: 128-132 g: 2.4-2.8 g: 0.4-0.45 g: 580 to 650mL, more preferably 18 g: 130 g: 2.6 g: 0.42 g: 620 mL.
In the invention, the dripping time of the mixture of the unsaturated acid, the mixed functional monomer and the molecular weight regulator is 2.5-3 h, preferably 2.6-2.9 h, and further preferably 2.8 h; the dropping time of the reducing agent is 2.5-3 h, preferably 2.6-2.9 h, and more preferably 2.8 h.
In the invention, the dripping process is preferably heating dripping, and the dripping temperature is preferably 50-70 ℃, and more preferably 60 ℃.
In the invention, the reaction temperature in the step 2) is 50-70 ℃, preferably 55-65 ℃, and further preferably 60 ℃; the reaction time is 0.8-1.2 h, preferably 0.9-1.1 h, and further preferably 1 h; after the alkali liquor is added in the step 3), the pH value of the system is 6.5-7, preferably 6.8-7, and further preferably 6.9.
In the invention, the alkali liquor comprises a sodium hydroxide solution, a potassium hydroxide solution or ammonia water, and the mass concentration of the alkali liquor is 20-40 g/mL, preferably 25-35 g/mL, and more preferably 30 g/mL.
The invention also provides a preparation method of the reduction type polycarboxylate superplasticizer.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
And (4) according to molar ratio: 0.88: 1.36 mixing acrylic acid, dipropylene glycol and diethylene glycol dipropylene glycol monobutyl ether, then adding hydroquinone accounting for 2.5 percent of the mass of the acrylic acid and p-toluenesulfonic acid accounting for 2.5 percent of the mass of the acrylic acid, and reacting at 120 ℃ for 6 hours to obtain a mixed functional monomer;
isobutylene polyoxyethylene ether, hydrogen peroxide (20g/mL) and water were mixed to obtain a mixed solution. The mass ratio of the isobutenol polyoxyethylene ether to the hydrogen peroxide is 1: 0.06, the concentration of the isobutylene alcohol polyoxyethylene ether in the mixed solution is 48%;
mixing 18g of maleic anhydride, 120g of mixed functional monomer and 2.5g of thioglycolic acid, dropwise adding into 620mL of mixed solution within 3h at 60 ℃, then dropwise adding 0.38g L-ascorbic acid within 2.8h, keeping the temperature for reaction for 1h after the dropwise adding is finished, and adding alkali liquor to adjust the pH value to 7 to obtain the shrinkage-type polycarboxylate water reducer.
Example 2
And (3) according to molar ratio: 0.8: 1.2 mixing methacrylic acid, dipropylene glycol and diethylene glycol dipropylene glycol monobutyl ether, then adding hydroquinone accounting for 2 percent of the mass of the methacrylic acid and p-toluenesulfonic acid accounting for 2 percent of the mass of the methacrylic acid, and reacting for 4 hours at 130 ℃ to obtain a mixed functional monomer;
isobutylene polyoxyethylene ether, hydrogen peroxide (20g/mL) and water were mixed to obtain a mixed solution. The mass ratio of the isobutenol polyoxyethylene ether to the hydrogen peroxide is 1: 0.08, the concentration of the isobutylene alcohol polyoxyethylene ether in the mixed solution is 40%;
mixing 15g of maleic anhydride, 130g of mixed functional monomer and 2g of mercaptoethanol, dropwise adding into 500mL of mixed solution within 3h at 60 ℃, then dropwise adding 0.4g of sodium formaldehyde sulfoxylate within 2.5h, keeping the temperature for reaction for 1h after the dropwise adding is finished, and adding alkali liquor to adjust the pH value to 6.8 to obtain the shrinkage-type polycarboxylic acid water reducer.
Example 3
According to the molar ratio of 5: 1: 1.5 mixing acrylic acid, dipropylene glycol and diethylene glycol dipropylene glycol monobutyl ether, then adding hydroquinone accounting for 5 percent of the mass of the acrylic acid and p-toluenesulfonic acid accounting for 5 percent of the mass of the acrylic acid, and reacting for 6 hours at 110 ℃ to obtain a mixed functional monomer;
mixing prenyl polyoxyethylene ether, hydrogen peroxide (30g/mL) and water to obtain a mixed solution. The mass ratio of the prenyl polyoxyethylene ether to the hydrogen peroxide is 1: 0.06, wherein the concentration of the isopentenol polyoxyethylene ether in the mixed solution is 45 percent;
20g of acrylic acid, 140g of mixed functional monomer and 3g of thioglycolic acid are mixed, the mixture is dripped into 700mL of mixed solution within 3h at 60 ℃, then 0.5g L-ascorbic acid is dripped within 2.8h, the mixture is subjected to heat preservation reaction for 1h after the dripping is finished, and alkali liquor is added to adjust the pH value to 6.8, so that the shrinkage-type polycarboxylate water reducer is obtained.
Comparative example 1
This comparative example differs from example 1 only in that acrylic acid, dipropylene glycol and diethylene glycol dipropylene glycol monobutyl ether are added in a molar ratio of 4: 1.12: 1.12.
experimental example 1
Concrete doped with the shrinkage-reducing polycarboxylic acid water reducing agent of examples 1-3 and the water reducing agent of comparative example 1 is subjected to related performance detection according to GB/8076 + 2008 concrete admixture and GBT/50082 + 2009 standard test method for long-term performance and durability of common concrete, and the detection results are shown in Table 1 (the mixing ratio of the concrete test is m (cement): m (sand): m (stone): m (water): 330: 673: 1000: 140).
TABLE 1 concrete Property test results
From table 1, it can be seen that the shrinkage of concrete is significantly reduced after a small amount of the shrinkage-reducing polycarboxylic acid water reducing agent is added, and the addition of the water reducing agent of comparative example 1 has the same shrinkage-reducing effect, but the shrinkage-reducing effect is not as good as that of the shrinkage-reducing polycarboxylic acid water reducing agent defined by the invention, which indicates that diethylene glycol dipropylene glycol monobutyl ether and dipropylene glycol have excellent shrinkage-reducing effect under the defined mixture ratio; after the shrinkage-reducing polycarboxylate superplasticizer is doped, the concrete has good compressive strength and better workability.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a shrinkage-reducing polycarboxylate superplasticizer is characterized by comprising the following steps:
1) mixing unsaturated acid, diethylene glycol dipropylene glycol monobutyl ether, dipropylene glycol, hydroquinone and p-toluenesulfonic acid, and reacting to obtain a mixed functional monomer;
2) mixing and dropwise adding unsaturated acid, mixed functional monomer and molecular weight regulator into the mixed solution, and then dropwise adding a reducing agent for reaction to obtain a reaction solution;
3) adding alkali liquor into the reaction solution to obtain a shrinkage-reducing polycarboxylic acid water reducing agent;
the mixed solution comprises unsaturated alcohol polyoxyethylene ether, an oxidant and water.
2. The method for preparing the reduction type polycarboxylate superplasticizer according to claim 1, wherein the unsaturated acid in the step 1) and the step 2) is one or more of acrylic acid, methacrylic acid and maleic anhydride independently.
3. The preparation method of the reduction type polycarboxylate water reducer according to claim 2, wherein the molar ratio of the unsaturated acid, the dipropylene glycol and the diethylene glycol dipropylene glycol monobutyl ether in the step 1) is 3-5: 0.8-1: 1.2-1.5, wherein the mass ratio of hydroquinone to unsaturated acid is 2-5: 100, the mass ratio of p-toluenesulfonic acid to unsaturated acid is 2-5: 100, respectively;
the reaction temperature in the step 1) is 110-130 ℃, and the reaction time is 4-6 h.
4. The preparation method of the shrinkage-reducing polycarboxylate water reducer according to any one of claims 1-3, wherein the unsaturated alcohol polyoxyethylene ether comprises one or two of isopentenol polyoxyethylene ether and isobutenol polyoxyethylene ether, the oxidant comprises one or more of a hydrogen peroxide solution, an ammonium persulfate solution and a potassium persulfate solution, and the mass concentration of the oxidant is 10-30 g/mL.
5. The preparation method of the reduction type polycarboxylate water reducer according to claim 4, characterized in that the mass ratio of the unsaturated alcohol polyoxyethylene ether to the oxidant is 1: 0.06-0.08, wherein the mass concentration of the unsaturated alcohol polyoxyethylene ether in the mixed solution is 35-50%.
6. The method for preparing the reduction type polycarboxylate superplasticizer according to claim 5, wherein the molecular weight regulators in the step 2) comprise thioglycolic acid, 3-mercaptopropionic acid, mercaptoethanol and sodium hypophosphite; the reducing agent comprises one or more of L-ascorbic acid, sodium formaldehyde sulfoxylate and Mohr's salt.
7. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 5 or 6, wherein the mass-to-volume ratio of the unsaturated acid, the mixed functional monomer, the molecular weight regulator, the reducing agent to the mixed solution is 15-20 g: 120-140 g: 2-3 g: 0.35-0.5 g: 550-700 mL.
8. The preparation method of the reduction type polycarboxylate water reducer according to claim 7, characterized in that the dropping time of the mixture of the unsaturated acid, the mixed functional monomer and the molecular weight regulator is 2.5-3 h, and the dropping time of the reducing agent is 2.5-3 h.
9. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 8, wherein the reaction temperature in the step 2) is 50-70 ℃, and the reaction time is 0.8-1.2 h;
adding alkali liquor in the step 3), wherein the pH value of the system is 6.5-7.
10. The preparation method of the reduction type polycarboxylate water reducer of any one of claims 1-9 is used for preparing the reduction type polycarboxylate water reducer.
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