CN110713573A - Method for synthesizing polycarboxylate superplasticizer slump-retaining mother liquor - Google Patents
Method for synthesizing polycarboxylate superplasticizer slump-retaining mother liquor Download PDFInfo
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 229920005646 polycarboxylate Polymers 0.000 title claims description 16
- 239000008030 superplasticizer Substances 0.000 title claims description 16
- 239000000178 monomer Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 35
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 34
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 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
- 239000010413 mother solution Substances 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011782 vitamin Substances 0.000 claims 1
- 229940088594 vitamin Drugs 0.000 claims 1
- 229930003231 vitamin Natural products 0.000 claims 1
- 235000013343 vitamin Nutrition 0.000 claims 1
- 150000003722 vitamin derivatives Chemical class 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 20
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 239000004576 sand Substances 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 125000005394 methallyl group Chemical group 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 4
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 3
- 229930003268 Vitamin C Natural products 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 235000019154 vitamin C Nutrition 0.000 description 3
- 239000011718 vitamin C Substances 0.000 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 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- -1 carboxylate ions Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- VGPXMTPKYDNMQA-UHFFFAOYSA-N furan-2,5-dione;prop-2-enamide Chemical compound NC(=O)C=C.O=C1OC(=O)C=C1 VGPXMTPKYDNMQA-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting 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
- C04B24/24—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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a method for synthesizing a slump-retaining mother liquor of a polycarboxylic acid water reducing agent, which belongs to the field of cement/concrete admixtures and is characterized in that a solution I prepared from an unsaturated monomer A1, an unsaturated monomer A2, a molecular weight regulator B and a molecular weight regulator C and a solution II prepared from a chain transfer agent, a reducing agent and water are dripped into a solution of an unsaturated polyoxyethylene ether monomer, water and an initiator, after the reaction is finished, the temperature is kept, and the pH value is regulated to 5 ~ 7.
Description
Technical Field
The invention relates to the field of cement/concrete admixtures, in particular to a method for synthesizing a slump-retaining mother liquor of a polycarboxylic acid water reducing agent.
Background
At present, the polycarboxylic acid water reducing agent is the water reducing agent with the largest use amount in concrete admixtures, has the advantages of designable structure, low mixing amount, high water reducing rate and the like, and is more and more widely applied to concrete engineering.
With the rapid development of the building industry in China, the consumption of the sandstone is huge, and high-quality sandstone resources are scarce. With the increasingly strict requirements of the country on environmental protection, the exploitation of river sand is forbidden, the quality of sand and stone aggregates used in concrete at present is poor, the sand content, the machine-made sand with large powder content, mountain sand, lake sand, river sand or sand and stones obtained by processing and crushing construction waste are greatly influenced by the application of the aggregates on the concrete state and slump retaining time, and troubles are brought to the concrete site construction.
The existing polycarboxylate superplasticizer has insufficient slump loss resistance, so that the slump loss resistant time of concrete is not too long, and therefore, the development of the polycarboxylate superplasticizer capable of improving the workability, the durability and the slump loss resistant time of concrete construction is a problem to be solved urgently.
Disclosure of Invention
In order to make up the defects of the prior art, the invention provides a method for synthesizing a slump-retaining mother liquor of a polycarboxylic acid water reducing agent.
The technical scheme of the invention is as follows:
a method for synthesizing a polycarboxylate superplasticizer slump-retaining mother solution comprises the following steps:
1) adding unsaturated polyoxyethylene ether monomer and water into a reaction kettle, stirring and dissolving, heating to 50 ~ 60 ℃, and adding an initiator;
2) uniformly stirring an unsaturated monomer A1, an unsaturated monomer A2, a molecular weight regulator B, a molecular weight regulator C and water to prepare a solution I; the molecular regulator B is acrylamide, and the molecular weight regulator C is one of hydroxyethyl acrylate and hydroxypropyl acrylate;
3) uniformly stirring a chain transfer agent, a reducing agent and water to prepare a solution II;
4) dropwise adding a solution I and a solution II into a reaction kettle, controlling the reaction temperature to be 55 ~ 65 ℃, and dropwise adding the solution II for 5 ~ 15min in advance of the solution I, wherein the mass ratio of the unsaturated polyoxyethylene ether monomer aqueous solution to the solution I to the solution II is (350-360) to (20-30) to (1.5-2);
5) after the reaction is finished, keeping the temperature for 1 ~ 3 hours, then cooling to below 40 ℃, and adding alkali liquor to adjust the pH value of the solution to 5 ~ 7.
In the step 4) of the invention, the solution II is dripped in advance of the solution I, so that a chain transfer agent and a reducing agent are uniformly doped in a bottom material, and when acrylic acid is dripped, the polymerization of acrylic acid molecules and polyether molecules is facilitated.
Preferably, in the step 1), the mass of the water is 85% ~ 90% of the mass of the unsaturated polyoxyethylene ether monomer, and the mass ratio of the unsaturated polyoxyethylene ether monomer to the initiator is 65 ~ 75: 1.
Preferably, in the step 2), the mass ratio of the unsaturated monomer A1, the unsaturated monomer A2, the molecular weight regulator B, the molecular weight regulator C and the water is 1 (0.5 ~ 1) to (0.5 ~ 1) to (1-2).
Preferably, in the step 3), the mass ratio of the chain transfer agent, the reducing agent and the water is (1-1.5) to 1: 100.
Preferably, the unsaturated polyoxyethylene ether monomer is accelerated allyl polyoxyethylene ether or prenol polyoxyethylene ether, and the relative molecular weight is 2400 ~ 3000.
Preferably, the unsaturated acid monomer a1 is acrylic acid.
Preferably, the unsaturated monomer A2 is maleic anhydride.
Preferably, the initiator is ammonium persulfate and hydrogen peroxide.
Preferably, the chain transfer agent is one of thioglycolic acid and mercaptopropionic acid.
The synthesis of the polycarboxylic acid mother liquor is to generate free radicals by oxidation-reduction reaction, attack double bonds of acrylic acid and polyether monomers and add the free radicals with the monomers to form monomer free radicals. Under the action of chain transfer agent, the monomer is combined with other monomer molecules to form more chain free radicals. In the radical polymerization process, a chain radical may abstract one atom from a low molecule or a large molecule such as a monomer, a solvent, an initiator, etc. to terminate, and the atom-lost molecule may become a radical, and a new chain may continue to grow, thereby proceeding the polymerization reaction. This reaction is called chain transfer. Free radical polymerization reactions are microscopically distinguishable as chain initiation, propagation, termination, transfer, and other radical reactions. Where the initiation rate is minimal, is critical to control the overall polymerization rate. In the polymerization process, the prolonged polymerization time is mainly to increase the conversion rate and has little influence on the molecular weight. In the synthesis process of the polycarboxylic water reducer, the free radicals are increased continuously, and the main chain and the side chain are increased continuously, so that the water reducer has the capability of steric hindrance.
The mercaptopropionic acid is used as a chain transfer agent, and the function of the mercaptopropionic acid is to enable chain growth free radicals to generate free radical transfer in the polymerization process of the water reducing agent, so that the molecular weight of the water reducing agent is controlled.
Preferably, the reducing agent is vitamin C.
The vitamin C contains a large number of strong polar functional groups of carboxyl and hydroxyl, the groups provide dispersing and flowing properties for cement particles through surface active effects of adsorption, dispersion, wetting and the like, and the workability of fresh concrete is improved by reducing the frictional resistance among the cement particles and reducing the free energy of the cement particles and a water interface. Meanwhile, polycarboxylic acid substances are adsorbed on the surfaces of cement particles, and carboxylate ions enable the cement particles to carry negative charges, so that electrostatic repulsion is generated among the cement particles, the cement particles are dispersed, the coagulation tendency of cement paste is inhibited, the contact area of the cement particles and water is increased, and the cement is fully hydrated. In the process of dispersing cement particles, free water surrounded by the aggregates is discharged, workability is improved, and the amount of water mixing is reduced.
The invention has the beneficial effects that:
the invention introduces ester bond, amido bond, acid anhydride bond and other three functional groups simultaneously, the molecular structure of the maleic anhydride-acrylamide copolymer contains acid anhydride and amide groups, the groups are continuously hydrolyzed under alkaline conditions, acid liver and amide groups are changed into carboxyl, the amide groups are hydrolyzed to generate carboxylic acid groups with water reducing effect, carboxylic acid type negative ions are absorbed by cement particles, the electronegativity of the surfaces of the cement particles is increased, the cement particles are prevented from being condensed, and thus the slump loss is controlled.
Detailed Description
Example 1:
a method for synthesizing a polycarboxylate superplasticizer slump-retaining mother solution comprises the following steps:
1) adding methyl allyl polyoxyethylene ether and water into a reaction kettle, stirring and dissolving, heating to 55 ℃, and adding an initiator ammonium persulfate; the relative molecular weight of the methallyl polyoxyethylene ether is 2400.
The mass of the water is 88% of that of the unsaturated polyoxyethylene ether monomer, and the mass ratio of the unsaturated polyoxyethylene ether monomer to the initiator is 70: 1.
2) Uniformly stirring unsaturated monomer A1 (acrylic acid), unsaturated monomer A2 (maleic anhydride), molecular weight regulator B (acrylamide), molecular weight regulator C (hydroxyethyl acrylate) and water to prepare solution I; the mass ratio of the unsaturated monomer A1, the unsaturated monomer A2, the molecular weight regulator B, the molecular weight regulator C and the water is 1:0.5:0.5:1: 1.
3) Uniformly stirring a chain transfer agent (thioglycolic acid), a reducing agent (sodium hypophosphite) and water to prepare a solution II; the mass ratio of the chain transfer agent to the reducing agent to the water is 1:1: 100.
4) And (3) dropwise adding the solution I and the solution II into the reaction kettle, wherein the mass ratio of the unsaturated polyoxyethylene ether monomer aqueous solution to the solution I to the solution II is 350:20:1.5, controlling the reaction temperature to be 55 ~ 60 ℃, dropwise adding the solution II into the reaction kettle 10min earlier than the solution I, and dropwise adding the solution I for 30min and dropwise adding the solution II for 35 min.
5) And (3) after the reaction is finished, keeping the temperature for 2 hours, cooling the reaction kettle by using circulating water, adding sodium hydroxide for neutralization when the temperature is reduced to be below 40 ℃, and adjusting the pH value to be 5 to obtain the polycarboxylic acid slump-retaining mother liquor.
Example 2
Compared with the example 1, the pH value is adjusted to 6 in the step 5), and the polycarboxylic acid slump-retaining mother liquor is obtained. The rest is the same as example 1.
Example 3
Compared with the example 1, the pH value is adjusted to 7 in the step 5), and the polycarboxylic acid slump-retaining mother liquor is obtained. The rest is the same as example 1.
Examples 1, 2 and 3 are applicable to different cements, the cement is alkaline, the pH value of the polycarboxylic acid slump-retaining mother liquor is different, the combination of the polycarboxylic acid slump-retaining mother liquor and calcium ions is influenced, the hydration process of the cement is influenced, and if the cement is lack of alkali, the pH value of the water reducer slump-retaining mother liquor is slightly higher, and the fluidity and the workability are better.
Example 4
The relative molecular weight of methallyl polyoxyethylene ether was 2600 compared to that of example 1, and the rest was the same as example 1.
Example 5
The relative molecular weight of methallyl polyoxyethylene ether was 3000 as compared with example 1, and the rest was the same as example 1.
The relative molecular weights of the methyl allyl polyoxyethylene ethers of the polycarboxylic acid slump-retaining mother liquor obtained in the embodiments 1, 4 and 5 are different, so that the synthesized polycarboxylic acid water reducer slump-retaining mother liquor has different side chain degrees.
Example 6
Compared with example 1, the methyl allyl polyoxyethylene ether is replaced by isoamyl alcohol polyoxyethylene ether, and the rest is the same as example 1.
Example 7
Compared with the example 1, the mass ratio of the unsaturated monomer A1, the unsaturated monomer A2, the molecular weight regulator B, the molecular weight regulator C and the water in the step 2) is 1:0.8:0.5:1:1, and the same as the example 1 is carried out. That is, the amount of the unsaturated monomer A2 was increased.
Example 8
Compared with the example 1, the mass ratio of the unsaturated monomer A1, the unsaturated monomer A2, the molecular weight regulator B, the molecular weight regulator C and the water in the step 2) is 1:0.3:0.5:1:1, and the same as the example 1 is carried out. That is, the amount of the unsaturated monomer A2 was reduced.
Example 9
Compared with the example 1, the mass ratio of the unsaturated monomer A1, the unsaturated monomer A2, the molecular weight regulator B, the molecular weight regulator C and the water in the step 2) is 1:0.5:0.8:1:1, and the same as the example 1 is carried out. That is, the amount of the molecular weight modifier B is increased.
Example 10
Compared with the example 1, the mass ratio of the unsaturated monomer A1, the unsaturated monomer A2, the molecular weight regulator B, the molecular weight regulator C and the water in the step 2) is 1:0.5:0.3:1:1, and the same as the example 1 is carried out. That is, the amount of the molecular weight modifier B is reduced.
Example 11:
a method for synthesizing a polycarboxylate superplasticizer slump-retaining mother solution comprises the following steps:
1) adding methyl allyl polyoxyethylene ether and water into a reaction kettle, stirring and dissolving, heating to 55 ℃, and adding an initiator ammonium persulfate; the relative molecular weight of the methallyl polyoxyethylene ether is 2800.
The mass of the water is 85% of that of the unsaturated polyoxyethylene ether monomer, and the mass ratio of the unsaturated polyoxyethylene ether monomer to the initiator is 65: 1.
2) Uniformly stirring unsaturated monomer A1 (acrylic acid), unsaturated monomer A2 (maleic anhydride), molecular weight regulator B (acrylamide), molecular weight regulator C (hydroxypropyl acrylate) and water to prepare solution I; the mass ratio of the unsaturated monomer A1, the unsaturated monomer A2, the molecular weight regulator B, the molecular weight regulator C and the water is 1:0.5:0.5:2: 2.
3) Uniformly stirring a chain transfer agent (mercaptopropionic acid), a reducing agent (vitamin C) and water to prepare a solution II; the mass ratio of the chain transfer agent, the reducing agent and the water is 1.2:1: 100.
4) And (3) dropwise adding the solution I and the solution II into the reaction kettle, controlling the reaction temperature to be 60 ~ 65 ℃, dropwise adding the solution II in advance of the solution I for 10min, dropwise adding the solution I for 35min, and dropwise adding the solution II for 40 min, wherein the mass ratio of the unsaturated polyoxyethylene ether monomer aqueous solution to the solution I to the solution II is 360:25: 2.
5) And (3) after the reaction is finished, keeping the temperature for 2 hours, cooling the reaction kettle by using circulating water, adding sodium hydroxide for neutralization when the temperature is reduced to be below 40 ℃, and adjusting the pH value to be 6 to obtain the polycarboxylic acid slump-retaining mother liquor.
Example 12:
a method for synthesizing a polycarboxylate superplasticizer slump-retaining mother solution comprises the following steps:
1) adding methyl allyl polyoxyethylene ether and water into a reaction kettle, stirring and dissolving, heating to 55 ℃, and adding an initiator ammonium persulfate; the relative molecular weight of the methallyl polyoxyethylene ether is 2400.
The mass of the water is 90% of that of the unsaturated polyoxyethylene ether monomer, and the mass ratio of the unsaturated polyoxyethylene ether monomer to the initiator is 75: 1.
2) Uniformly stirring unsaturated monomer A1 (acrylic acid), unsaturated monomer A2 (maleic anhydride), molecular weight regulator B (acrylamide), molecular weight regulator C (hydroxyethyl acrylate) and water to prepare solution I; the mass ratio of the unsaturated monomer A1, the unsaturated monomer A2, the molecular weight regulator B, the molecular weight regulator C and the water is 1:0.5:0.5:2: 1.
3) Uniformly stirring a chain transfer agent (thioglycolic acid), a reducing agent (sodium hypophosphite) and water to prepare a solution II; the mass ratio of the chain transfer agent, the reducing agent and the water is 1.8:1: 100.
4) Dropwise adding the solution I and the solution II into the reaction kettle, controlling the reaction temperature to be 60 ℃, and dropwise adding the solution II for 10min in advance of the solution I; the solution is dripped in 30min for the first time, and is dripped in 35min for the second time; the mass ratio of the unsaturated polyoxyethylene ether monomer aqueous solution to the solution I to the solution II is 355:30: 1.5.
5) And (3) after the reaction is finished, keeping the temperature for 2 hours, cooling the reaction kettle by using circulating water, adding sodium hydroxide for neutralization when the temperature is reduced to be below 40 ℃, and adjusting the pH value to be 6 to obtain the polycarboxylic acid slump-retaining mother liquor.
50g of the polycarboxylic acid water reducer slump-retaining mother liquor obtained in the embodiment 1, the embodiment 11 and the embodiment 12, 250g of the polycarboxylic acid water-reducing mother liquor, 25g of the retarding component, 1g of the air entraining component and 674g of water are compounded to prepare the polycarboxylic acid water reducer. The concrete was formulated and its expansion and slump, and slump loss over time were measured. The results are shown in Table 1.
TABLE 1 Effect of the polycarboxylic acid slump-retaining mother liquor obtained in each example on the expansion and slump of concrete
As can be seen from Table 1, the slump loss of the slump-retaining mother liquor obtained by the method of the invention is very good in slump-retaining performance and can be well controlled.
Claims (10)
1. A method for synthesizing a polycarboxylate superplasticizer slump-retaining mother solution is characterized by comprising the following steps:
1) adding unsaturated polyoxyethylene ether monomer and water into a reaction kettle, stirring and dissolving, heating to 50 ~ 60 ℃, and adding an initiator;
2) uniformly stirring an unsaturated monomer A1, an unsaturated monomer A2, a molecular weight regulator B, a molecular weight regulator C and water to prepare a solution I; the molecular regulator B is acrylamide, and the molecular weight regulator C is one of hydroxyethyl acrylate and hydroxypropyl acrylate;
3) uniformly stirring a chain transfer agent, a reducing agent and water to prepare a solution II;
4) dropwise adding a solution I and a solution II into a reaction kettle, controlling the reaction temperature to be 55 ~ 65 ℃, and dropwise adding the solution II for 5 ~ 15min in advance of the solution I, wherein the mass ratio of the unsaturated polyoxyethylene ether monomer aqueous solution to the solution I to the solution II is (350-360) to (20-30) to (1.5-2);
5) after the reaction is finished, keeping the temperature for 1 ~ 3 hours, then cooling to below 40 ℃, and adding alkali liquor to adjust the pH value of the solution to 5 ~ 7.
2. The method for synthesizing the slump retaining mother liquor of the polycarboxylic acid water reducer as claimed in claim 1, wherein in the step 1), the mass of water is 85% ~ 90% of the mass of the unsaturated polyoxyethylene ether monomer, and the mass ratio of the unsaturated polyoxyethylene ether monomer to the initiator is 65 ~ 75: 1.
3. The method for synthesizing the slump retaining mother liquor of the polycarboxylic acid water reducer as claimed in claim 1 or 2, wherein in the step 2), the mass ratio of the unsaturated monomer A1, the unsaturated monomer A2, the molecular weight regulator B, the molecular weight regulator C and the water is 1 (0.5 ~ 1) (0.5 ~ 1) to (1-2).
4. The method for synthesizing the polycarboxylate superplasticizer slump-retaining mother liquor as claimed in claim 1 or 2, wherein: in the step 3), the mass ratio of the chain transfer agent, the reducing agent and the water is (1-1.5) to 1: 100.
5. The method for synthesizing the slump retaining mother liquor of the polycarboxylate superplasticizer of claim 1, wherein the unsaturated polyoxyethylene ether monomer is urgent allyl polyoxyethylene ether or prenol polyoxyethylene ether, and the relative molecular weight is 2400 ~ 3000.
6. The method for synthesizing the slump-retaining mother liquor of the polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps of: the unsaturated acid monomer A1 is acrylic acid.
7. The method for synthesizing the slump-retaining mother liquor of the polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps of: the unsaturated monomer A2 is maleic anhydride.
8. The method for synthesizing the slump-retaining mother liquor of the polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps of: the initiator is ammonium persulfate and hydrogen peroxide.
9. The method for synthesizing the slump-retaining mother liquor of the polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps of: the chain transfer agent is one of thioglycolic acid and mercaptopropionic acid.
10. The method for synthesizing the slump-retaining mother liquor of the polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps of: the reducing agent is vitamin.
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