CN114044858A - Comprehensive polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Comprehensive polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
- Publication number
- CN114044858A CN114044858A CN202111473515.XA CN202111473515A CN114044858A CN 114044858 A CN114044858 A CN 114044858A CN 202111473515 A CN202111473515 A CN 202111473515A CN 114044858 A CN114044858 A CN 114044858A
- Authority
- CN
- China
- Prior art keywords
- parts
- water
- solution
- reducing agent
- comprehensive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002253 acid Substances 0.000 title description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 34
- 239000008030 superplasticizer Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 25
- 239000007800 oxidant agent Substances 0.000 claims abstract description 24
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 19
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 19
- 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 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- POLZHVHESHDZRD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(=O)OCCO POLZHVHESHDZRD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 5
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002211 L-ascorbic acid Substances 0.000 claims description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 15
- 239000004576 sand Substances 0.000 abstract description 8
- 150000007942 carboxylates Chemical class 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- 239000004575 stone Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 hydroxyethyl methacrylate phosphate ester Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 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
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a comprehensive polycarboxylate superplasticizer and a preparation method thereof, and solves the technical problems that the carboxylate superplasticizer in the prior art is poor in adaptability, and the condition, the dispersing capacity and the dispersion maintaining capacity of concrete are easy to change when cement mixed materials are changed, so that the use of the polycarboxylate superplasticizer in construction and masonry is influenced. The catalyst comprises 380 parts of ethylene glycol polyoxyethylene ether 340-containing materials, 400 parts of water 360-containing materials, 20-30 parts of acrylic acid, 18-25 parts of hydroxyethyl methacrylate phosphate, 3-6 parts of an oxidant, 1-3 parts of a chain transfer agent, 1-3 parts of a reducing agent and 0.2-0.5 part of a catalyst. The water reducing rate of the prepared comprehensive polycarboxylate superplasticizer is over 36 percent, the workability and the performance are excellent, the slump retaining and water reducing capabilities are good, and the product performance of the phosphate polycarboxylate superplasticizer is realized; the water reducing agent has good adaptability to the change of materials such as concrete sand and stone.
Description
Technical Field
The invention relates to the technical field of water reducing agent formulas and processes, in particular to a comprehensive polycarboxylic acid water reducing agent and a preparation method thereof.
Background
The polycarboxylate superplasticizer is a cement dispersant applied to cement concrete, can obviously improve the rheological property and the mechanical property of the concrete, has the advantages of environmental protection, nonflammability, non-explosiveness, capability of being transported for a long distance by using vehicles and the like, and is widely applied to various fields of building engineering.
However, the polycarboxylic acid water reducing agent has some problems in practical application, for example, when concrete sand, rubber, cement, coal ash and the like are changed, the state, the dispersing capacity, the dispersion maintaining capacity and the like of the concrete are changed, which imposes certain difficulty on the aspects of transportation, plasticity maintaining and the like of the concrete in the construction process. The method aims to solve the problems that the dispersion, the workability and the bleeding resistance of the water reducing agent are improved by adjusting the mixing ratio of monomers to change the length of a main chain or the density of a side chain and changing the type, the quantity and the like of macromonomers.
Disclosure of Invention
The invention aims to provide a comprehensive polycarboxylic acid water reducing agent and a preparation method thereof, which aim to solve the defects in the prior art and provide a polycarboxylic acid water reducing agent with high water reducing rate and better workability and adaptability to materials such as machine-made sand and the like and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a comprehensive polycarboxylic acid water reducing agent which comprises the following components in parts by weight: 380 parts of ethylene glycol monovinyl polyoxyethylene ether, 400 parts of water, 20-30 parts of acrylic acid, 18-25 parts of hydroxyethyl methacrylate phosphate, 3-6 parts of an oxidizing agent, 1-3 parts of a chain transfer agent, 1-3 parts of a reducing agent and 0.2-0.5 part of a catalyst.
Alternatively or preferably, the ethylene glycol monovinyl polyoxyethylene ether has a number average molecular weight of 2400-3000 g/mol.
Optionally or preferably, the oxidant is 25-30% hydrogen peroxide by mass concentration.
Alternatively or preferably, the catalyst is 0.5-1% FeSO4And (3) solution.
Alternatively or preferably, the chain transfer agent is a mixture of one or more of thioglycolic acid, mercaptopropionic acid and mercaptoethanol.
Alternatively or preferably, the reducing agent is one or more of L-ascorbic acid, sodium formaldehyde sulfoxylate, N-ethylaniline and N, N-dimethylaniline.
The invention provides a preparation method of a comprehensive polycarboxylate superplasticizer, which comprises the following steps:
s1, adding water and ethylene glycol monovinyl polyoxyethylene ether into a reaction container, heating, stirring and dissolving;
after S2 is dissolved, adding an oxidant into the reaction vessel;
s3, mixing acrylic acid, hydroxyethyl methacrylate phosphate, a chain transfer agent and water to prepare a solution A, and dropwise adding the solution A into a reaction container;
s4, mixing a reducing agent, a catalyst and water to prepare a solution B, and dripping the solution B into the reaction container together with the solution A;
after the S5 reaction is finished, preserving the heat for a period of time and cooling to room temperature to obtain the finished product
Alternatively or preferably, the mass ratio of the water used in the steps S1, S3 and S4 is: 4.8-5.0: 1: 1.8-2.0.
Alternatively or preferably, in the step S1, the temperature of the reaction vessel is heated to 20 to 50 ℃.
Optionally or preferably, in the step S5, the heat preservation time is 30-40 min.
Optionally or preferably, in the step S3, the dropping time is 40-60 min.
Alternatively or preferably, in step S4, the dropping time is 50 to 70 min.
Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:
(1) according to the comprehensive polycarboxylate water reducer and the preparation method thereof provided by the invention, a hydroxyethyl methacrylate phosphate ester monomer is connected to a polycarboxylate water reducer molecule through a chemical method, the electronegativity of phosphate groups is stronger than that of carboxylate groups, a monomer containing phosphate groups is introduced into a polymer, the phosphate groups can be preferentially adsorbed to the surfaces of cement particles, and the adsorption of the carboxylate groups is reduced, so that the workability of the water reducer and different aggregates is improved, and the slump retaining effect of the water reducer is enhanced.
(2) The comprehensive polycarboxylate superplasticizer and the preparation method thereof provided by the invention have the advantages that the polycarboxylate superplasticizer with comprehensive performance is prepared by jointly polymerizing the polyether macromonomer EPEG, acrylic acid and hydroxyethyl methacrylate phosphate, the synthesis time of the polycarboxylate superplasticizer is short, the polycarboxylate superplasticizer has excellent water reducing and slump retaining capabilities for concrete, the water reducing rate is over 36%, the workability and the performance are excellent, the good slump retaining and water reducing capabilities are realized, and the product performance of the polycarboxylate superplasticizer with phosphate is realized; meanwhile, the water reducing agent has good adaptability to the change of materials such as concrete sand stone, rubber materials, cement, coal ash and the like, and solves the problems of transportation, plasticity maintenance and the like of concrete.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
1.1 raw materials (by weight)
360 parts of ethylene glycol monovinyl polyoxyethylene ether (EPEG, the number average molecular weight is 3000g/mol), 400 parts of water, 20 parts of acrylic acid, 20 parts of hydroxyethyl methacrylate phosphate (HEMAP), 5 parts of an oxidizing agent, 2 parts of a chain transfer agent, 2 parts of a reducing agent and 0.3 part of a catalyst.
Water: deionized water is adopted;
chain transfer agent: adopting mercaptopropionic acid;
reducing agent: l-ascorbic acid is adopted;
oxidizing agent: hydrogen peroxide with the concentration of 26 percent;
catalyst: FeSO of concentration 0.6%4And (3) solution.
1.2 preparation method
The method comprises the following steps:
s1, adding 250 parts by weight of water and ethylene glycol monovinyl polyoxyethylene ether into a reaction vessel, heating to 50 ℃, stirring for dissolving, and cooling to 20 ℃;
after S2 is dissolved, adding an oxidant into the reaction vessel;
s3, mixing acrylic acid, hydroxyethyl methacrylate phosphate, a chain transfer agent and 50 parts (by weight) of water to prepare a solution A, dropwise adding the solution A into a reaction container, and finishing dropping within 50 min;
s4, mixing a reducing agent, a catalyst and 100 parts (by weight) of water to prepare a solution B, and dripping the solution B into the reaction container together with the solution A for 70 min;
and (5) after the S5 reaction is finished, preserving the heat for 30min, and cooling to room temperature to obtain the finished product.
Example 2
2.1 raw materials (by weight)
360 parts of ethylene glycol monovinyl polyoxyethylene ether (EPEG, the number average molecular weight is 3000g/mol), 400 parts of water, 20 parts of acrylic acid, 20 parts of hydroxyethyl methacrylate phosphate (HEMAP), 4 parts of an oxidizing agent, 2 parts of a chain transfer agent, 2 parts of a reducing agent and 0.4 part of a catalyst.
Water: deionized water is adopted;
chain transfer agent: adopting thioglycolic acid;
reducing agent: sodium formaldehyde sulfoxylate is adopted;
oxidizing agent: hydrogen peroxide with the concentration of 28 percent;
catalyst: FeSO of concentration 0.7%4And (3) solution.
2.2 preparation method
The method comprises the following steps:
s1, adding 250 parts by weight of water and ethylene glycol monovinyl polyoxyethylene ether into a reaction vessel, heating to 50 ℃, stirring for dissolving, and cooling to 20 ℃;
after S2 is dissolved, adding an oxidant into the reaction vessel;
s3, mixing acrylic acid, hydroxyethyl methacrylate phosphate, a chain transfer agent and 50 parts by weight of water to prepare a solution A, dropwise adding the solution A into a reaction container, and finishing dropping within 55 min;
s4, mixing a reducing agent, a catalyst and 100 parts (by weight) of water to prepare a solution B, dripping the solution B into the reaction container together with the solution A, and finishing dripping within 65 min;
and (8) after the S5 reaction is finished, preserving the heat for 40min, and cooling to room temperature to obtain the finished product.
Example 3
3.1 raw materials (by weight portion)
360 parts of ethylene glycol monovinyl polyoxyethylene ether (EPEG, the number average molecular weight is 2800g/mol), 390 parts of water, 25 parts of acrylic acid, 18 parts of hydroxyethyl methacrylate phosphate (HEMAP), 3 parts of an oxidizing agent, 2 parts of a chain transfer agent, 2 parts of a reducing agent and 0.4 part of a catalyst.
Water: deionized water is adopted;
chain transfer agent: mercaptoethanol is adopted;
reducing agent: adopting N-ethyl aniline;
oxidizing agent: 29% hydrogen peroxide;
catalyst: FeSO of concentration 0.9%4And (3) solution.
3.2 preparation method
The method comprises the following steps:
s1, adding 240 parts by weight of water and ethylene glycol monovinyl polyoxyethylene ether into a reaction vessel, heating to 50 ℃, stirring for dissolving, and cooling to 20 ℃;
after S2 is dissolved, adding an oxidant into the reaction vessel;
s3, mixing acrylic acid, hydroxyethyl methacrylate phosphate, a chain transfer agent and 50 parts (by weight) of water to prepare a solution A, dropwise adding the solution A into a reaction container, and finishing dropping within 50 min;
s4, mixing a reducing agent, a catalyst and 100 parts (by weight) of water to prepare a solution B, and dripping the solution B into the reaction container together with the solution A for 70 min;
and (5) after the S5 reaction is finished, preserving the heat for 30min, and cooling to room temperature to obtain the finished product.
Example 4
4.1 raw materials (by weight portion)
360 parts of ethylene glycol monovinyl polyoxyethylene ether (EPEG, number average molecular weight 2600g/mol), 380 parts of water, 30 parts of acrylic acid, 25 parts of hydroxyethyl methacrylate phosphate (HEMAP), 3 parts of an oxidizing agent, 1.5 parts of a chain transfer agent, 2 parts of a reducing agent and 0.4 part of a catalyst.
Water: deionized water is adopted;
chain transfer agent: mercaptoethanol is adopted;
reducing agent: adopting N-ethyl aniline;
oxidizing agent: 25% hydrogen peroxide;
catalyst: FeSO of concentration 0.5%4And (3) solution.
4.2 preparation method
The method comprises the following steps:
s1, adding 240 parts by weight of water and ethylene glycol monovinyl polyoxyethylene ether into a reaction vessel, heating to 50 ℃, stirring for dissolving, and cooling to 20 ℃;
after S2 is dissolved, adding an oxidant into the reaction vessel;
s3, mixing acrylic acid, hydroxyethyl methacrylate phosphate, a chain transfer agent and 50 parts (by weight) of water to prepare a solution A, dropwise adding the solution A into a reaction container, and finishing dropping within 50 min;
s4, mixing a reducing agent, a catalyst and 90 parts (by weight) of water to prepare a solution B, and dripping the solution B into the reaction container together with the solution A for 70 min;
and (5) after the S5 reaction is finished, preserving the heat for 30min, and cooling to room temperature to obtain the finished product.
Example 5
5.1 raw materials (by weight portion)
360 parts of ethylene glycol monovinyl polyoxyethylene ether (EPEG, the number average molecular weight is 2400g/mol), 360 parts of water, 25 parts of acrylic acid, 20 parts of hydroxyethyl methacrylate phosphate (HEMAP), 3 parts of an oxidizing agent, 2 parts of a chain transfer agent, 1.5 parts of a reducing agent and 0.3 part of a catalyst.
Water: deionized water is adopted;
chain transfer agent: mercaptoethanol is adopted;
reducing agent: adopting N-ethyl aniline;
oxidizing agent: 30% hydrogen peroxide;
catalyst: FeSO of concentration 1%4And (3) solution.
5.2 preparation method
The method comprises the following steps:
s1, adding 225 parts by weight of water and ethylene glycol monovinyl polyoxyethylene ether into a reaction vessel, heating to 50 ℃, stirring for dissolving, and cooling to 20 ℃;
after S2 is dissolved, adding an oxidant into the reaction vessel;
s3, mixing acrylic acid, hydroxyethyl methacrylate phosphate, a chain transfer agent and 45 parts by weight of water to prepare a solution A, dropwise adding the solution A into a reaction container, and finishing dropping within 50 min;
s4, mixing a reducing agent, a catalyst and 90 parts (by weight) of water to prepare a solution B, and dripping the solution B into the reaction container together with the solution A for 70 min;
and (5) after the S5 reaction is finished, preserving the heat for 30min, and cooling to room temperature to obtain the finished product.
Comparative example 1
6.1 raw materials (by weight portion)
In contrast to example 1, hydroxyethyl methacrylate phosphate was not used, hydroxyethyl acrylate was used.
360 parts of ethylene glycol monoethyl polyoxyethylene ether (EPEG, the number average molecular weight is 3000g/mol), 400 parts of water, 20 parts of acrylic acid, 20 parts of hydroxyethyl acrylate, 5 parts of an oxidizing agent, 2 parts of a chain transfer agent, 2 parts of a reducing agent and 0.3 part of a catalyst.
Water: deionized water is adopted;
chain transfer agent: adopting mercaptopropionic acid;
reducing agent: l-ascorbic acid was used.
6.2 preparation method
The method comprises the following steps:
s1, adding 250 parts by weight of water and ethylene glycol monovinyl polyoxyethylene ether into a reaction vessel, heating to 50 ℃, stirring for dissolving, and cooling to 20 ℃;
after S2 is dissolved, adding an oxidant into the reaction vessel;
s3, mixing acrylic acid, hydroxyethyl methacrylate phosphate, a chain transfer agent and 50 parts (by weight) of water to prepare a solution A, dropwise adding the solution A into a reaction container, and finishing dropping within 50 min;
s4, mixing a reducing agent, a catalyst and 100 parts (by weight) of water to prepare a solution B, and dripping the solution B into the reaction container together with the solution A for 70 min;
and (5) after the S5 reaction is finished, preserving the heat for 30min, and cooling to room temperature to obtain the finished product.
Examples of the experiments
1. Determination of homogeneity index of water reducing agent
The polycarboxylic acid water reducing agents prepared in examples 1 to 5 and comparative example 1 were tested, and a comparative test was carried out using the polycarboxylic acid water reducing agent without HEMAP prepared in the comparative experiment according to GB8076-2008 "concrete admixture", and the test results are shown in Table 1 below:
TABLE 1 determination of various indexes of water reducing agent
| Water reducing agent | Viscosity of the oil | Density (g/mL) | pH value | Solid content (%) | Water loss (%) |
| Example 1 | 210 | 1.082 | 4.1 | 49.4 | 39 |
| Example 2 | 230 | 1.083 | 4.2 | 49.5 | 38 |
| Example 3 | 220 | 1.082 | 4.0 | 48.7 | 38 |
| Example 4 | 205 | 1.081 | 3.8 | 47.4 | 37 |
| Example 5 | 220 | 1.080 | 4.0 | 46.6 | 36 |
| Comparative example 1 | 200 | 1.082 | 4.1 | 49.4 | 33 |
As can be seen from Table 1, the polycarboxylic acid water reducing agents in the embodiments 1 to 5 of the invention have the density of more than 1.080g/ml, the pH values of less than 2.2, the solid contents of more than 46.6 percent and the water reducing rate of more than 36 percent; the water reducing rate of the embodiment 1 of the invention is obviously higher than that of the polycarboxylic acid water reducing agent of the comparative example 1; therefore, the polycarboxylate superplasticizer containing the HEMAP has higher water reducing rate.
2. Test for measuring fluidity of cement paste
The polycarboxylic acid water reducing agent is applied to cement, and comprises the following materials required by a cement paste fluidity determination experiment: 300 g of cement and 87 g of water, and measuring the net slurry fluidity data of which the mixing amount is 0.3 percent of the mass by adopting a circular cutting and sawing die (upper 36mm and lower 64 mm); the cement is 42.5 of Emei PO, 42.5 of Jianbao PO, 42.5 of Yadong PO and 42.5 of New boat city PO; the water is tap water (5 kg of the same batch); and a comparative test is set, the comparative test detects that the polycarboxylate superplasticizer without the HEMAP is prepared, and the experimental result is shown in the table 2:
TABLE 2 Water reducing agent Adaptation test
As can be seen from Table 2, the initial and elapsed time values of the fluidity of 5 samples of the polycarboxylic acid water reducer are higher than those of the water reducer used in the comparative experiment, and the initial net slurry fluidity of the examples can reach 224 mm; the net pulp fluidity can reach 253mm at most with the time and the absolute value of the negative increase of the embodiment is much larger than that of the comparative embodiment. And aiming at different cements, the water reducing and slump retaining effects of the polycarboxylate superplasticizer containing the HEMAP are better than those of the polycarboxylate superplasticizer without the HEMAP in the comparative example.
3. Concrete test
When the polycarboxylate superplasticizer is applied to concrete, the concrete expansion degree determination experiment matching ratio and materials are as follows: the test mixing proportion is that the concrete volume weight is 2400kg/m3The sand rate is 50 percent (machine-made sand), and 250kg/m of Jianbao cement is used360kg/m of Hebang fly ash3. And a comparative test is set, the comparative test detects that the polycarboxylate superplasticizer without the HEMAP is prepared, and the experimental result is shown in the table 3:
TABLE 3 concrete test results
As can be seen from Table 3, the concrete expansion degree values of the 5 samples of the embodiment containing the HEMAP polycarboxylic acid water reducer are all higher than that of the water reducer used in the comparative experiment, and can reach 595mm at most, after 120min loss, the concrete expansion degree values of the 5 samples of the embodiment are still higher than that of the water reducer used in the comparative experiment, and the effect of the polycarboxylic acid water reducer containing the HEMAP in concrete application is better than that of the polycarboxylic acid water reducer containing no HEMAP in the comparative embodiment.
4. Adaptability
When the polycarboxylate superplasticizer is applied to concrete, the concrete expansion degree determination experiment matching ratio and materials are as follows: the test mixing proportion is that the concrete volume weight is 2400kg/m3The sand rate is 50 percent, different sands are used for carrying out a comparison test, and 250kg/m of Jianbao cement is used360kg/m of Hebang fly ash3. And a comparative test is set, the comparative test detects that the polycarboxylate superplasticizer without the HEMAP is prepared, and the experimental result is shown in the table 4:
TABLE 4 results of different sand concrete test runs
From table 4, it can be seen that, when different sandstone materials are used for concrete tests, the poorer the sandstone materials are, the poorer the water reducing and slump retaining capabilities of the examples are, while the concrete expansion values of 5 examples containing the HEMAP polycarboxylic acid water reducing agent are higher than those of the water reducing agent used in the comparative experiments, and the influence of material change on the concrete expansion values is small, so that the HEMAP polycarboxylic acid water reducing agent has good adaptability to different materials.
The invention has the beneficial effects that: according to the formula and the preparation method of the polycarboxylate superplasticizer containing the HEMAP, the HEMAP monomer is connected to the polycarboxylate superplasticizer molecules at a lower temperature through a chemical method, so that the problems of poor workability and quick loss of the polycarboxylate superplasticizer under the condition of poor materials are solved. The invention has strong applicability, can be mixed with cement of different types or models for use, and has higher concrete retention capacity; the water reducing rate is high and can reach more than 36 percent, and the workability of concrete can be effectively improved.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The comprehensive polycarboxylate superplasticizer is characterized by comprising the following components in parts by weight: 380 parts of ethylene glycol monovinyl polyoxyethylene ether, 400 parts of water, 20-30 parts of acrylic acid, 18-25 parts of hydroxyethyl methacrylate phosphate, 3-6 parts of an oxidizing agent, 1-3 parts of a chain transfer agent, 1-3 parts of a reducing agent and 0.2-0.5 part of a catalyst.
2. The comprehensive polycarboxylate water reducer of claim 1, which is characterized in that: the number average molecular weight of the ethylene glycol monovinyl polyoxyethylene ether is 2400-3000 g/mol.
3. The comprehensive polycarboxylate water reducer of claim 1, which is characterized in that: the oxidant is hydrogen peroxide with the mass concentration of 25-30%.
4. The comprehensive polycarboxylate water reducer of claim 1, which is characterized in that: the catalyst is 0.5-1% of FeSO4And (3) solution.
5. The comprehensive polycarboxylate water reducer of claim 1, which is characterized in that: the chain transfer agent is one or a mixture of thioglycolic acid, mercaptopropionic acid and mercaptoethanol.
6. The comprehensive polycarboxylate water reducer of claim 1, which is characterized in that: the reducing agent is one or a mixture of L ascorbic acid, sodium formaldehyde sulfoxylate, N-ethylaniline and N, N-dimethylaniline.
7. The preparation method of the comprehensive polycarboxylate superplasticizer according to any one of claims 1 to 6, characterized by comprising the following steps:
s1, adding water and ethylene glycol monovinyl polyoxyethylene ether into a reaction container, heating, stirring and dissolving;
after S2 is dissolved, adding an oxidant into the reaction vessel;
s3, mixing acrylic acid, hydroxyethyl methacrylate phosphate, a chain transfer agent and water to prepare a solution A, and dropwise adding the solution A into a reaction container;
s4, mixing a reducing agent, a catalyst and water to prepare a solution B, and dripping the solution B into the reaction container together with the solution A;
and (S5) after the reaction is finished, keeping the temperature for a period of time, and cooling to room temperature to obtain the finished product.
8. The preparation method of the comprehensive polycarboxylate superplasticizer according to claim 7, which is characterized by comprising the following steps: the mass ratio of the water used in the steps S1, S3 and S4 is as follows: 4.8-5.0: 1: 1.8-2.0.
9. The preparation method of the comprehensive polycarboxylate superplasticizer according to claim 7, which is characterized by comprising the following steps: in the step S1, the heating temperature of the reaction container is 20-50 ℃;
in the step S5, the heat preservation time is 30-40 min.
10. The preparation method of the comprehensive polycarboxylate superplasticizer according to claim 7, which is characterized by comprising the following steps: in the step S3, the dripping time is 40-60 min; in step S4, the dripping time is 50-70 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111473515.XA CN114044858A (en) | 2021-11-29 | 2021-11-29 | Comprehensive polycarboxylic acid water reducing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111473515.XA CN114044858A (en) | 2021-11-29 | 2021-11-29 | Comprehensive polycarboxylic acid water reducing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114044858A true CN114044858A (en) | 2022-02-15 |
Family
ID=80212409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111473515.XA Pending CN114044858A (en) | 2021-11-29 | 2021-11-29 | Comprehensive polycarboxylic acid water reducing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114044858A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403311A (en) * | 2022-08-31 | 2022-11-29 | 三亚瑞泽双林混凝土有限公司 | High slump loss resistant concrete and preparation method thereof |
| CN115521414A (en) * | 2022-09-29 | 2022-12-27 | 贵州石博士科技股份有限公司 | Polycarboxylic slump retaining agent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944101A (en) * | 2020-07-21 | 2020-11-17 | 北京水木佳维科技有限公司 | Preparation method of high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregate |
| CN111961147A (en) * | 2020-07-16 | 2020-11-20 | 佳化化学（茂名）有限公司 | Polycarboxylate superplasticizer powder containing phosphate ester and preparation method thereof |
-
2021
- 2021-11-29 CN CN202111473515.XA patent/CN114044858A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961147A (en) * | 2020-07-16 | 2020-11-20 | 佳化化学（茂名）有限公司 | Polycarboxylate superplasticizer powder containing phosphate ester and preparation method thereof |
| CN111944101A (en) * | 2020-07-21 | 2020-11-17 | 北京水木佳维科技有限公司 | Preparation method of high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403311A (en) * | 2022-08-31 | 2022-11-29 | 三亚瑞泽双林混凝土有限公司 | High slump loss resistant concrete and preparation method thereof |
| CN115521414A (en) * | 2022-09-29 | 2022-12-27 | 贵州石博士科技股份有限公司 | Polycarboxylic slump retaining agent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107325234B (en) | Anti-mud phosphate modified polycarboxylate superplasticizer and preparation method thereof | |
| CN110563891A (en) | Polycarboxylate superplasticizer with mud resistance and viscosity reduction functions and preparation method thereof | |
| CN114044858A (en) | Comprehensive polycarboxylic acid water reducing agent and preparation method thereof | |
| CN114213603B (en) | Mud-resistant slow-release polycarboxylate superplasticizer and preparation method and application thereof | |
| CN111439947A (en) | Low-air-entraining slow-setting type polycarboxylate superplasticizer and preparation method thereof | |
| CN112876619A (en) | Anti-mud polycarboxylate superplasticizer and preparation method thereof | |
| CN116622034A (en) | Slow-release viscosity-reduction type polycarboxylate superplasticizer for high-strength concrete and preparation method thereof | |
| CN109608082B (en) | Anti-mud polycarboxylate superplasticizer, preparation method and application | |
| CN111961148B (en) | Reaction air-entraining type polycarboxylate superplasticizer and preparation method thereof | |
| CN110627972A (en) | Novel mud-resistant polyether polycarboxylic acid water reducer and normal-temperature synthesis process thereof | |
| CN114044856A (en) | Mud-blocking type polycarboxylate superplasticizer and preparation method thereof | |
| CN111808244B (en) | Polycarboxylate superplasticizer with high water reduction and high adaptability and preparation method thereof | |
| CN112794956A (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN102206314B (en) | Polycarboxylic acid and application thereof, and cement water reducing agent containing polycarboxylic acid | |
| CN110003406B (en) | Rosin modified polycarboxylate superplasticizer and preparation method thereof | |
| EP1380554B1 (en) | Hydraulic composition, and method of improving fluidity retention of the same | |
| CN113354782B (en) | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN113956407B (en) | Modified polyether macromonomer and preparation method and use method thereof | |
| CN102093522A (en) | Polycarboxylic acid, use thereof and water reducer containing same | |
| CN113278144B (en) | Viscosity-reducing polycarboxylic acid water reducer and preparation method thereof | |
| CN114133492A (en) | Preparation method of polycarboxylic acid concrete water reducing agent | |
| CN114085336A (en) | Anti-mud viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN109535347B (en) | Preparation method of block water-retaining concrete admixture | |
| CN112250338A (en) | Polycarboxylate superplasticizer for concrete prefabricated part and preparation method thereof | |
| CN112500534A (en) | Amphoteric polycarboxylate superplasticizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220215 |