CN113372507A - Cross-linking polyether ester amide water reducing agent and preparation method thereof - Google Patents
Cross-linking polyether ester amide water reducing agent and preparation method thereof Download PDFInfo
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- CN113372507A CN113372507A CN202010969302.5A CN202010969302A CN113372507A CN 113372507 A CN113372507 A CN 113372507A CN 202010969302 A CN202010969302 A CN 202010969302A CN 113372507 A CN113372507 A CN 113372507A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 66
- 238000004132 cross linking Methods 0.000 title claims abstract description 42
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002614 Polyether block amide Polymers 0.000 claims abstract description 26
- 150000001408 amides Chemical group 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 18
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 3
- 239000004567 concrete Substances 0.000 abstract description 18
- 239000004568 cement Substances 0.000 abstract description 16
- 125000004185 ester group Chemical group 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 6
- 229920000570 polyether Polymers 0.000 abstract description 6
- 238000010494 dissociation reaction Methods 0.000 abstract description 3
- 230000005593 dissociations Effects 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 125000003827 glycol group Chemical group 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 14
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical group C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 125000003368 amide group Chemical group 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 101100012019 Mus musculus Etv4 gene Proteins 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003077 polyols Chemical group 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229940057950 sodium laureth sulfate Drugs 0.000 description 1
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement 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
- 230000007306 turnover Effects 0.000 description 1
- 238000005303 weighing 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a polyether ester amide water reducing agent and a preparation method thereof, the polyether ester amide water reducing agent obtained by the method adopts ester group crosslinking, when the system is strongly alkaline, partial ester group is dissociated, a single-chain comb-shaped polycarboxylic acid structure, polyether amide and polyether glycol structure are gradually released, the amide structure can enable the slump retention capacity of concrete to be better, and carboxyl and ester groups are monomers with a plastic-retaining function, so that the water reducing agent has the functions of early strength and slump retention, the dissociation is gradually carried out, water reducing agent molecules capable of being adsorbed by cement particles can be released in a longer time, the initial fluidity of cement can be improved, and the cement can be kept stable for a longer time.
Description
Technical Field
The invention relates to the technical field of water reducer preparation, in particular to a cross-linking polyether ester amide water reducer and a preparation method thereof.
Background
For large-scale engineering construction, the production efficiency of the prefabricated part is the key for shortening the construction period and saving the cost, and the strength, especially the early strength, of the concrete is improved by using the water reducing agent or the water reducing composite additive, so that the energy conservation and the consumption reduction are facilitated, the turnover rate of a mold can be accelerated, and the production efficiency of the prefabricated part is improved. In addition, commercial concrete mixing plant keeps away from the urban area, usually transports with the help of the mixing transport vechicle, high slump loss becomes the factor that must consider again, the slump in concrete long distance transportation is in the state of continuous loss, if increase water cement ratio, can improve the slump, but at the same time the structure of cement mortar becomes loose, the porosity increases, the setting time prolongs, direct influence concrete later stage intensity, if adopt methods such as compound slump retaining agent, early strength agent, make compound component difficult to control again, the problem such as compatibility is poor, can't satisfy the requirement of early strength type water reducing agent to the slump.
In view of the above problems, patent CN102924733A discloses an amido-crosslinked polycarboxylic acid water reducing agent, which improves initial fluidity in a manner of slowly releasing carboxylic acid molecules by amide base hydrolysis, and does not have significant slump retaining and early strength effects. Tankouhua has studied a kind of early strong slump retaining type polycarboxylate water reducing agent to methallyl polyoxyethylene ether and N-hydroxymethyl acrylamide are raw materials, add the function macromonomer that contains more carboxyl and hydroxyl of self-control, have early strong and slump retaining effect concurrently, if nevertheless long distance transport, the slump can have obvious loss, and later stage intensity also can not obviously improve.
Disclosure of Invention
In order to solve the problems, the following technical scheme is provided:
a cross-linking polyether ester amide water reducing agent and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
s1: the initiator allyl amine and ethylene oxide or propylene oxide are subjected to nucleophilic substitution reaction to generate an intermediate;
s2, after the reaction is finished, continuously adding ethylene oxide or propylene oxide into the system, and continuously performing substitution reaction on the intermediate and the ethylene oxide or the propylene oxide under the action of an alkaline catalyst to obtain unsaturated polyether amide;
s3: under the action of an initiator and a chain transfer agent, the unsaturated polyether amide prepared by S2, unsaturated amide and unsaturated carboxylic acid are subjected to micromolecule aggregation;
s4: and (3) after the system is cooled, adding a cross-linking agent and an emulsifier, controlling the cross-linking degree, finally adjusting the pH value to be neutral, adding water to dilute the solid content to 40-50%, and preparing the cross-linked polyether ester amide water reducer.
Preferably, the unsaturated polyether amide in step S2 has the structure:
preferably, the structural formula of the cross-linking type polyether ester amide water reducing agent obtained in the step S4 is as follows:
Preferably, in the step S4, the molar ratio of the cross-linking agent to the emulsifier is 1: 1-5, and the dosage of the cross-linking agent is 0.1-5.0% of the total mass of the reactants.
Preferably, the alkaline catalyst in step S2 is selected from one or a mixture of K, Na and NaOH, and the amount of the alkaline catalyst is 0.2-1.5% of the total mass of the reactants.
Preferably, in step S1, the substitution reaction temperature is 90-160 ℃, and the reaction pressure is 0.1-0.5 MPa.
Preferably, in step S3, the unsaturated carboxylic acid is one or more of acrylic acid, methacrylic acid and isopentenoic acid, and the mass ratio of the unsaturated polyether amide to the unsaturated carboxylic acid and the unsaturated amide is (30-60): 45-90): 5-10.
Preferably, the initiator in step S3 is selected from one or more of potassium persulfate, sodium persulfate and ammonium persulfate, and the amount of the initiator is 0.2-2.0% of the total mass of the reactants.
Preferably, in step S3, the chain transfer agent is one or more of thioglycolic acid, mercaptopropionic acid, isopropanol, and n-butanol, and the amount of the chain transfer agent is 0.1% to 1.0% of the total mass of the reactants.
The invention has the beneficial effects that:
1. according to the invention, polyether containing an amido main chain is adopted, and then cross-linking and grafting of functional groups are carried out on the branched chain, so that the main chain structure contains the functional groups, and the technical short plate that the functional release is influenced if the side chains are intertwined because the main chain structure does not contain the functional groups in the prior art is overcome.
2. The structure of the water reducing agent contains an early strength functional amide group, and the amide group and calcium ions in cement form a soluble calcium salt complex, so that the generation of ettringite is promoted, and the hydration process of cement is accelerated.
3. According to the invention, through ester group crosslinking, ester group dissociation and bond breaking are carried out under an alkaline condition to form hydrophobic water reducing agent molecules, a single-chain comb-shaped polycarboxylic acid structure is gradually released, the water reducing agent molecules have a slow release function, the released water reducing agent molecules can have more aiming groups, the initial fluidity of concrete is obviously improved, and the water reducing agent molecules can be kept stable for a long time.
Detailed Description
A cross-linking type polyether ester amide water reducing agent and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
s1: the initiator allyl amine and ethylene oxide or propylene oxide are subjected to nucleophilic substitution reaction to generate an intermediate;
s2, after the reaction is finished, continuously adding ethylene oxide or propylene oxide into the system, and continuously performing substitution reaction on the intermediate and the ethylene oxide or the propylene oxide under the action of an alkaline catalyst to obtain unsaturated polyether amide;
s3: under the action of an initiator and a chain transfer agent, the unsaturated polyether amide prepared by S2, unsaturated amide and unsaturated carboxylic acid are subjected to micromolecule aggregation at the temperature of 50-60 ℃;
s4: and (3) after cooling the system, adding a cross-linking agent and an emulsifier, controlling the degree of cross-linking, finally adjusting the pH value to 6-7, and adding water to dilute the solid content to 40% -50%, thereby preparing the cross-linked polyether ester amide water reducer.
Wherein, the unsaturated polyether amide in the step S2 has the structure:
in the structural formula, x is 0-10, n is 1-45, m is 0-15, and x and m are not 0 at the same time.
The structural formula of the cross-linking polyether ester amide water reducing agent obtained in the step S4 is as follows:
Wherein, in the step S4, the molar ratio of the cross-linking agent to the emulsifier is 1: 1-5, and the dosage of the cross-linking agent is 0.1-5.0% of the total mass of reactants.
Wherein the basic catalyst in step S2 is selected from K, Na, NaOH, KOH, K2O、NaH、CH3ONa、CH3In OK, the dosage of the alkaline catalyst is 0.2 to 1.5 percent of the total mass of reactants.
Wherein, in the step S1, the replacement reaction temperature is 90-160 ℃, and the reaction pressure is 0.1-0.5 MPa.
Wherein, in the step S3, the unsaturated carboxylic acid is one or a mixture of more of acrylic acid, methacrylic acid and isopentenoic acid, and the mass ratio of the unsaturated polyether amide to the unsaturated carboxylic acid and the unsaturated amide is (30-60): 45-90): 5-10.
Wherein, the initiator in the step S3 is selected from one or more of potassium persulfate, sodium persulfate and ammonium persulfate, and the dosage of the initiator is 0.2-2.0% of the total mass of the reactants.
Wherein, the chain transfer agent in the step S3 is one or a mixture of more of thioglycolic acid, mercaptopropionic acid, isopropanol and n-butanol, and the dosage of the chain transfer agent is 0.1-1.0% of the total mass of reactants.
The invention adopts a solvent extraction method to determine the degree of crosslinking, and the specific method comprises the steps of firstly placing a to-be-measured object and a standard sample on a watch glass respectively, naturally drying for 48h, drying and drying for 12h at 80 ℃, taking down the object, dissolving the object with equivalent distilled water, drying according to the same method, and weighing, thereby calculating the degree of crosslinking.
The polymerization method of the crosslinking polyether ester amide compound is an emulsifier precipitation polymerization method, and the crosslinking agent is preferably ethylene glycol diacrylate.
The emulsifier in the invention is selected from anionic surfactants with emulsification and dispersion effects, such as one or a mixture of sodium dodecyl sulfate and sodium laureth sulfate.
According to an embodiment of the present invention, the water reducing agent according to embodiments 1, 2, 4, 5, 6 further comprises the following units:
the invention utilizes the prepared polyether amide and the compound containing the amide group to carry out crosslinking through the unsaturated esterified substance to obtain the crosslinking polyether ester amide water reducing agent, ester group crosslinking is carried out, when the system is strong alkaline, partial ester group is dissociated, a single-chain comb-shaped polycarboxylic acid structure, polyether amide and polyether polyol structure are gradually released, the amide structure can enable the slump retaining capability of concrete to be better, carboxyl and ester group are monomers with plastic protection function, so that the water reducing agent has the functions of early strength and slump retaining, the dissociation is carried out gradually, water reducing agent molecules capable of being adsorbed by cement particles can be released in a longer time, the initial fluidity of cement can be improved, and the cement can be kept stable for a longer time.
Examples
Example 1
57g of allylamine, 1.2g of NaOH as catalyst and N2After replacing the reaction kettle, gradually raising the temperature to 90 ℃, and then introducing 1.5mol of propylene oxide and 10mol of ethylene oxide into the reaction kettle, wherein the pressure of the reaction kettle is 0.35MPa, and the reaction temperature is 150 ℃. And after the feeding is finished, stopping heating when the kettle pressure is reduced to 0.15MPa, keeping the kettle temperature at 100 ℃, aging for 30min, discharging when the kettle pressure is reduced to zero to obtain the polyether amide, wherein the measured weight average molecular weight is 1039.1 and is marked as PA-1.
Taking 300g of prepared PA-1 polyether amide, 47.5g of N-isopropyl acrylamide, 11.7g of emulsifier sodium dodecyl sulfate and 3.2g of initiator sodium persulfate, adding 240g of deionized water, stirring at a constant speed, heating to 50 ℃, simultaneously beginning to dropwise add 44g of acrylic acid and 1.3g of mercaptopropionic acid, wherein the dropwise adding time is 60-120 min, continuing to react for 120-180 min after the dropwise adding is finished, and stopping heating. Cooling to 25-35 ℃, dropwise adding 2.5g of cross-linking agent ethylene glycol diacrylate for 30-60 min, continuously reacting for 60-90 min after dropwise adding, controlling the cross-linking degree to be 10-20%, adding 30% NaOH to adjust the pH value to be 6-7, adding water to dilute the solid content to 40%, and preparing the cross-linking polyether ester amide water reducer PEA-1.
Example 2
To the reactor was added 57g of allylamine, 2.8g of KOH as catalyst, N2After replacing the reaction kettle, gradually raising the temperature to 90 ℃, and then introducing 2mol of propylene oxide and 12mol of ethylene oxide into the reaction kettle, wherein the pressure of the reaction kettle is 0.35MPa, and the reaction temperature is 150 ℃. Stopping heating when the pressure of the kettle is reduced to 0.15MPa after the feeding is finished, keeping the temperature of the kettle at 100 ℃ for aging for 30min, and aging when the pressure of the kettle is zeroDischarging to obtain the polyether amide, wherein the weight average molecular weight is 1247.3 and is marked as PA-2.
350g of prepared PA-2 polyether amide, 86g of N-isopropyl acrylamide, 13g of sodium lauryl polyoxyethylene ether sulfate and 5.9g of potassium persulfate serving as an initiator are added into a reactor, 240g of deionized water is added, the mixture is stirred at a constant speed and heated to 50-60 ℃, 62g of methacrylic acid and 2.2g of mercaptoacetic acid are dropwise added at the same time, the dropwise adding time is 60-120 min, the reaction is continued for 120-180 min after the dropwise adding is finished, and the heating is stopped. Cooling to 25-35 ℃, adding 30% NaOH to adjust the pH value to 6-7, adding water to dilute the solid content to 40%, and obtaining the cross-linked polyether ester amide water reducing agent PEA-2.
Example 3
300g of methyl allyl polyoxyethylene ether with the molecular weight of 2400, 98g of N-isopropylacrylamide, 21.8g of sodium dodecyl sulfate as an emulsifier and 4.1g of ammonium persulfate as an initiator are added into a reactor, 240g of deionized water is added, the mixture is stirred at a constant speed and heated to 55 ℃, 52g of methacrylic acid and 2.8g of mercaptopropionic acid are added dropwise at the same time, the dropping time is 60-120 min, the reaction is continued for 120-180 min after the dropping is finished, and the heating is stopped. Cooling to 25-35 ℃, dropwise adding 3.5g of cross-linking agent ethylene glycol diacrylate for 30-60 min, continuously reacting for 60-90 min after dropwise adding, controlling the cross-linking degree to be 10-20%, adding 30% NaOH to adjust the pH value to be 6-7, adding water to dilute the solid content to 40%, and preparing the cross-linking polyether ester amide water reducer PEA-3.
Example 4
To the reactor was added 57g of allylamine, 2.9g of KOH as catalyst, N2After replacing the reaction kettle, gradually raising the temperature to 90 ℃, and then introducing 3mol of propylene oxide and 11mol of ethylene oxide into the reaction kettle, wherein the pressure of the reaction kettle is 0.35MPa, and the reaction temperature is 150 ℃. And after the feeding is finished, stopping heating when the kettle pressure is reduced to 0.15MPa, keeping the kettle temperature at 100 ℃, aging for 30min, discharging when the kettle pressure is zero to obtain the polyether amide, wherein the measured weight average molecular weight is 1272.2 and is marked as PA-4.
Taking 300g of prepared PA-4 polyether amide and 65g of N-isopropyl acrylamide, 18.8g of emulsifier sodium lauryl polyoxyethylene ether sulfate and 4.5g of initiator sodium persulfate into a reactor, adding 240g of deionized water, stirring at a constant speed, raising the temperature to 55 ℃, simultaneously beginning to dropwise add 35g of methacrylic acid and 2.6g of N-butyl alcohol for 60-120 min, continuing to react for 120-180 min after dropwise addition is finished, and stopping heating. Cooling to 25-35 ℃, dropwise adding 3.2g of cross-linking agent ethylene glycol diacrylate for 30-60 min, continuously reacting for 60-90 min after dropwise adding, controlling the cross-linking degree to be 10-20%, adding 30% NaOH to adjust the pH value to be 6-7, adding water to dilute the solid content to 40%, and preparing the cross-linking polyether ester amide water reducer PEA-4.
Example 5
To the reactor was added 57g of allylamine, 0.9g of NaOH as catalyst, N2After replacing the reaction kettle, gradually raising the temperature to 90 ℃, introducing 6mol of ethylene oxide into the reaction kettle, wherein the pressure of the reaction kettle is 0.35MPa, and the reaction temperature is 150 ℃. And after the feeding is finished, stopping heating when the kettle pressure is reduced to 0.15MPa, keeping the kettle temperature at 100 ℃, aging for 30min, discharging when the kettle pressure is zero to obtain the polyether amide, wherein the measured weight average molecular weight is 777.6 and is marked as PA-5.
Taking 300g of prepared PA-5 polyether amide, 73g of N-isopropyl acrylamide, 30.3g of emulsifier sodium dodecyl sulfate and 3.3g of initiator potassium persulfate into a reactor, adding 240g of deionized water, stirring at a constant speed, heating to 60 ℃, simultaneously beginning to dropwise add 42g of acrylic acid and 1.3g of thioglycolic acid for 60-120 min, continuing to react for 120-180 min after dropwise addition is finished, and stopping heating. Cooling to 25-35 ℃, dropwise adding 3.9g of cross-linking agent ethylene glycol diacrylate for 30-60 min, continuously reacting for 60-90 min after dropwise adding, controlling the cross-linking degree to be 10-20%, adding 30% NaOH to adjust the pH value to be 6-7, adding water to dilute the solid content to 40%, and preparing the cross-linking polyether ester amide water reducer PEA-5.
Example 6
85.5g of allylamine, 5.6g of sodium methoxide as catalyst, N2After replacing the reaction kettle, gradually raising the temperature to 90 ℃, and then introducing 5.25mol of propylene oxide and 16.5mol of ethylene oxide into the reaction kettle, wherein the pressure of the reaction kettle is 0.35MPa, and the reaction temperature is 150 ℃. When the feeding is finished, the kettle pressureStopping heating when the pressure is reduced to 0.15MPa, keeping the temperature of the kettle at 100 ℃, aging for 30min, discharging when the pressure drop of the kettle is zero, and obtaining the polyether amide, wherein the measured weight average molecular weight is 1985.8 and is marked as PA-6.
Taking 300g of prepared PA-6 polyether amide, 65g of N-isopropyl acrylamide, 29.6g of emulsifier sodium dodecyl sulfate and 5.1g of initiator ammonium persulfate into a reactor, adding 240g of deionized water, stirring at a constant speed, heating to 60 ℃, simultaneously beginning to dropwise add 30g of isopentene acid and 1.9g of isopropanol, dropwise adding for 60-120 min, continuing to react for 120-180 min after dropwise adding is finished, and stopping heating. Cooling to 25-35 ℃, dropwise adding 3.8g of cross-linking agent ethylene glycol diacrylate for 30-60 min, continuously reacting for 60-90 min after dropwise adding, controlling the cross-linking degree to be 10-20%, adding 30% NaOH to adjust the pH value to be 6-7, adding water to dilute the solid content to 40%, and preparing the cross-linking polyether ester amide water reducer PEA-6.
Application example
In the following, a detailed description will be given of a cross-linking polyether ester amide water reducer and a preparation method thereof according to a specific embodiment, a commercially available water reducer is a common polycarboxylic acid water reducer synthesized from methyl allyl polyoxyethylene ether, a control group is an experimental group without adding or subtracting water reducer, and the temperature of test materials and environment is 15-25 ℃. The method for testing the fluidity of the net slurry is carried out according to GB/T8077-2012 'concrete admixture homogeneity test method', each net slurry fluidity test is carried out under the communicating condition, the selected reference cement is ordinary portland cement, and cement, sand, stones and water in the concrete are referred to JGJ55-2011 according to a certain mixing ratio. The compression strength ratio is represented by the ratio of age-matched compression strength of the concrete added with the admixture to that of the reference concrete, the compression strength of the tested concrete and the reference concrete refers to GB/T50081-2019, and the concrete slump test method refers to GB/8076-2008.
1. Determination of cement paste fluidity
The water-reducing agents synthesized in examples 1, 4 and 6 of the present invention and a commercially available polycarboxylic acid water-reducing agent were subjected to a cement paste fluidity test in terms of fluidity extension diameter unit of millimeters (mm) at the same blending amounts, and the results are shown in Table 1.
TABLE 1 comparison of fluidity extended diameter of neat cement slurries using the present invention with commercially available water reducers
The data in Table 1 show that the initial fluidity and the time fluidity of the water reducing agents PEA-1, PEA-4 and PEA-6 are superior to those of the commercial water reducing agents, and particularly the time fluidity is obviously superior to that of the commercial water reducing agents, so that the water reducing agents are more beneficial to long-distance transportation.
2. Determination of concrete Properties
The water reducing agents synthesized in examples 2, 3, 5 and 6 of the present invention and the common water reducing agents of the same type were subjected to concrete working performance and mechanical property tests, and the results of slump loss with time and the compressive strength ratio at each stage are shown in table 2.
TABLE 2 comparison of working and mechanical Properties of concrete with commercial Water-reducing Agents Using the present invention
In the table 2, compared with the commercial water reducer, the slump loss of the cross-linking polyether ester amide water reducer synthesized by the PEA-6 water reducer according to the experimental steps is reduced by 62.5%, the extensibility is increased by 35-120 mm after 1h, and good dispersibility and slump resistance are reflected. As can be seen from Table 2, the strength is improved by 32-10% averagely in 1 day and 3 days, the strength is improved by 26% in 28 days, the early strength effect is obviously superior to that of a commercial water reducer, and the requirement standard of the early strength of a prefabricated part is met. In addition, the slump retaining effect of PEA-2 is inferior to that of the commercial water reducer because no cross-linking agent is added in the synthesis process of the water reducer PEA-2, so that the dispersion effect is directly influenced by the number of ester groups and carboxyl groups; the early strength effect of PEA-3 is far from that of the water reducing agent sold in the market, because PEA-3 adopts the water reducing agent synthesized by common polyether, the main chain has no amide group, and the early strength effect is obviously reduced; the comprehensive performance of PEA-5 is not as good as that of PEA-6, because propylene oxide is not introduced in the preparation process of PEA-5 polyether amide, the density of a side chain and the molecular weight of polyether are reduced, and the water reducing effect cannot reach the best, so that all steps and components of the invention are not required.
In conclusion, the amide group, the ester group and the carboxyl group in the cross-linking structure all play a certain role, the amide group endows the concrete with the early strength characteristic, and part of the ester group is subjected to alkaline hydrolysis to release the hydrophobic structural monomer, so that the number of the carboxyl group is increased, the adsorption capacity on the cement is enhanced, and the cement has better time-lapse dispersibility and high slump retention.
Claims (9)
1. A cross-linking type polyether ester amide water reducing agent and a preparation method thereof are characterized in that the preparation method comprises the following steps:
s1: the initiator allyl amine and ethylene oxide or propylene oxide are subjected to nucleophilic substitution reaction to generate an intermediate;
s2, after the reaction is finished, continuously adding ethylene oxide or propylene oxide into the system, and continuously performing substitution reaction on the intermediate and the ethylene oxide or the propylene oxide under the action of an alkaline catalyst to obtain unsaturated polyether amide;
s3: under the action of an initiator and a chain transfer agent, the unsaturated polyether amide prepared by S2, unsaturated amide and unsaturated carboxylic acid are subjected to micromolecule aggregation;
s4: and (3) after the system is cooled, adding a cross-linking agent and an emulsifier, controlling the cross-linking degree, finally adjusting the pH value to be neutral, adding water to dilute the solid content to 40-50%, and preparing the cross-linked polyether ester amide water reducer.
2. The cross-linking polyether ester amide water reducing agent and the preparation method thereof according to claim 1, wherein the unsaturated polyether amide in step S2 has a structure:
3. the cross-linking polyether ester amide water reducer and the preparation method thereof according to claim 1, wherein the cross-linking polyether ester amide water reducer obtained in step S4 has a structural formula:
4. The cross-linking polyether ester amide water reducing agent and the preparation method thereof according to claim 1, wherein in step S4, the molar ratio of the cross-linking agent to the emulsifier is 1: 1-5, and the amount of the cross-linking agent is 0.1-5.0% of the total mass of the reactants.
5. The cross-linking polyether ester amide water reducing agent and the preparation method thereof according to claim 1, wherein the alkaline catalyst in step S2 is selected from one or a mixture of K, Na and NaOH, and the amount of the alkaline catalyst is 0.2-1.5% of the total mass of the reactants.
6. The cross-linking type polyether ester amide water reducing agent and the preparation method thereof according to claim 1, wherein in step S1, the substitution reaction temperature is 90-160 ℃, and the reaction pressure is 0.1-0.5 MPa.
7. The cross-linking polyether ester amide water reducing agent and the preparation method thereof as claimed in claim 1, wherein the unsaturated carboxylic acid in step S3 is one or more of acrylic acid, methacrylic acid, and isopentenoic acid, and the mass ratio of the unsaturated polyether amide to the unsaturated carboxylic acid and the unsaturated amide is (30-60): 45-90): 5-10.
8. The cross-linking polyether ester amide water reducing agent and the preparation method thereof according to claim 1, wherein the initiator in step S3 is selected from one or more of potassium persulfate, sodium persulfate and ammonium persulfate, and the amount of the initiator is 0.2-2.0% of the total mass of the reactants.
9. The cross-linking polyether ester amide water reducing agent and the preparation method thereof according to claim 1, wherein the chain transfer agent in step S3 is one or a mixture of several of thioglycolic acid, mercaptopropionic acid, isopropanol and n-butanol, and the amount of the chain transfer agent is 0.1-1.0% of the total mass of reactants.
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