CN114044860B - Viscosity-reducing ether polycarboxylate superplasticizer and preparation method thereof - Google Patents
Viscosity-reducing ether polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- 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
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- 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
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Abstract
The invention relates to the field of concrete additives, in particular to a viscosity-reducing ether polycarboxylate water reducer and a preparation method thereof. The viscosity-reducing ether polycarboxylate water reducer comprises an esterification product, an ether macromonomer, acrylic acid, an unsaturated ester monomer and a functional monomer B; the esterification product is prepared by esterification reaction of a functional monomer A and unsaturated acid, wherein the functional monomer A is a monomer with benzene ring, borate and hydroxyl; the functional monomer B is a monomer with a silane group, a double benzene ring and a fluorocarbon bond structure. According to the invention, the self-made esterification product and (1-fluorovinyl) methyl diphenyl silane participate in copolymerization reaction, so that the polycarboxylate water reducer has a plurality of silane groups in molecules, the silane functional groups are hydrolyzed to generate silicon hydroxyl groups, the condensation of the silicon hydroxyl groups and the hydroxyl groups on the surfaces of cement particles generates chemical adsorption, the adsorption capacity is greater than the electrostatic adsorption of carboxyl groups, the dispersion capacity of the polycarboxylate water reducer can be greatly improved, and the polycarboxylate water reducer has an excellent viscosity reduction effect.
Description
Technical Field
The invention relates to the field of concrete additives, in particular to a viscosity-reducing ether polycarboxylate water reducer and a preparation method thereof.
Background
In recent years, along with the vigorous development of the building industry in China, the building tends to be large-sized and super-high-rise, concrete is developed towards high performance directions such as high strength, high durability and the like, and the viscosity of the concrete is increased due to the application of a large amount of mineral admixture technology and the reduction of the water-cement ratio of the concrete. In addition, because of the shortage of river sand resources, a large amount of machine-made sand is applied to the preparation of concrete, the machine-made sand has more edges and corners and poorer grading, so that the viscosity problem is more remarkable, and the pumping and construction of high-rise concrete are not facilitated. The strength of the concrete can be improved by methods of reducing the water-cement ratio, increasing the consumption of the cementing material, improving the proportion of the mineral admixture and the like, but the measures can also cause the increase of the viscosity of the concrete, the reduction of the fluidity and the influence on the workability of the concrete.
The polycarboxylic acid water reducer in the market has high water reducing rate, can effectively reduce the water consumption of concrete, but can not well solve the problem of the increase of the viscosity of the concrete caused by the water-cement ratio. The popularization and the application of the high-performance concrete on the super high-rise building are restricted to a great extent.
For example, publication number CN109455975B, publication day 2021, month 07 and day 13 disclose the use of viscosity-reducing polycarboxylic acid water reducer in preparing tailing sand concrete, which uses methallyl alcohol, alkylene oxide, ethyl epoxyphenylpropionate and sodium hydride to prepare viscosity-reducing active macromonomer D, and then uses reaction monomer a, reaction monomer B, reaction monomer C and viscosity-reducing monomer D to make free radical polymerization under the action of oxidant, reducer and chain transfer agent, mainly by introducing hydrophobic viscosity-reducing groups methyl and phenyl, etc. to give viscosity-reducing effect, but the reaction steps are complex and have no guidance.
For another example, publication number CN112979887a, publication date is 2021, 6 and 18, and a preparation method thereof, a modified polycarboxylic acid is disclosed, firstly, a vinyl silane coupling agent and a fluorosilane coupling agent are subjected to hydrolytic polycondensation under isopropanol solvent and normal temperature to obtain a silane modified monomer, and then, a polyether macromonomer, acrylic acid and the silane modified monomer are subjected to polymerization under the action of an initiator to prepare the polycarboxylic acid water reducer with high dispersion slump retaining performance, but the reaction steps are complex, and no viscosity reduction effect is mentioned.
In addition, the viscosity reduction effect is achieved by compounding the air entraining agent with the water reducer and doping the mineral admixture in the prior art, but the two methods respectively have the problems of adverse effect on the strength of concrete and limited viscosity reduction effect. Therefore, development of viscosity-reducing polycarboxylic acid water reducer is urgently needed, and the problem of high-performance concrete in practical engineering application is solved.
Disclosure of Invention
In order to solve the problem that the existing water reducer has a viscosity reducing effect and can cause adverse effect on the strength of concrete, the invention provides a viscosity reducing ether polycarboxylate water reducer, which comprises an esterification product, an ether macromonomer, acrylic acid, an unsaturated ester monomer and a functional monomer B;
the esterification product is prepared by esterification reaction of a functional monomer A and unsaturated acid, wherein the functional monomer A is a monomer with benzene ring, borate and hydroxyl;
the functional monomer B is a monomer with a silane group, a double benzene ring and a fluorocarbon bond structure.
In some embodiments, the preparation process of the esterified product comprises adding unsaturated acid and functional monomer A into a reaction vessel, mixing, adding catalyst and polymerization inhibitor under nitrogen, and adjusting temperature t 1 Reaction T at 120-135 DEG C 1 4-6 h to obtain the esterified product.
In some embodiments, the functional monomer a is 4-hydroxyphenylboronic acid pinacol ester having the structural formula:
in some embodiments, the unsaturated acid is one of acrylic acid, methacrylic acid.
In some embodiments, the catalyst is one of cerium sulfate, concentrated sulfuric acid, and p-toluenesulfonic acid.
In some embodiments, the polymerization inhibitor comprises one of hydroquinone, diphenylamine, methyl hydroquinone.
In some embodiments, the molar ratio of the functional monomer A to the unsaturated acid is 1:1.5-4, the mass of the catalyst is 0.8-2.5% of the total mass of the unsaturated acid and the functional monomer A, and the mass of the polymerization inhibitor is 0.5-3% of the total mass of the unsaturated acid and the functional monomer A.
In some embodiments, the functional monomer B is (1-fluorovinyl) methyldiphenylsilane.
In some embodiments, the ether macromer is one of isobutenyl alcohol polyoxyethylene ether, isopentenyl alcohol polyoxyethylene ether, methallyl monomethyl ether polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether with a molecular weight of 1000-2000.
In some embodiments, the unsaturated ester monomer is one of hydroxyethyl acrylate, methyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate.
In some embodiments, the mass ratio of the esterification product, the ether macromonomer, the acrylic, the unsaturated ester monomer, and the functional monomer B is 2.5-5.5:100:4.5-12:2.5-5:1-3.
In some embodiments, the composition further comprises an emulsifier, an oxidizing agent, a reducing agent, and a chain transfer agent; the amount of the emulsifier is 1-3% of the total mass of the ether macromonomer, the amount of the oxidant is 1-3% of the total mass of the ether macromonomer, the amount of the reducer is 1-3.5% of the total mass of the ether macromonomer, and the amount of the chain transfer agent is 1-3% of the total mass of the ether macromonomer.
In some embodiments, the oxidizing agent is one of ammonium persulfate, sodium persulfate, hydrogen peroxide, and t-butyl hydroperoxide;
the reducing agent is one of sodium hypophosphite, ascorbic acid, ammonium bisulfate and disodium 2-hydroxy-2-sulfinylacetate;
the chain transfer agent is one of mercaptoethanol, n-dodecyl mercaptan, 2-mercaptopropionic acid and sodium hypophosphite.
The invention also provides a preparation method of the viscosity-reducing ether polycarboxylate superplasticizer, which comprises the following steps:
adding the esterified product, the ether macromonomer, the functional monomer B and the emulsifier into a reaction vessel for mixing, respectively dripping an oxidant solution, a mixed solution of a reducing agent solution and a chain transfer agent, reacting the mixed solution of acrylic acid and an unsaturated ester monomer at room temperature, preserving heat after the reaction is finished, and adding liquid alkali to adjust the pH value to 6-7 to obtain the viscosity-reducing ether polycarboxylic acid water reducer.
Preferably, the reaction is carried out at room temperature for 1 to 2 hours.
Preferably, the liquid base is a 32% strength by mass sodium hydroxide solution.
Based on the above, the invention has the following beneficial effects:
1. the invention utilizes 4-hydroxyphenylboronic acid pinacol ester and unsaturated acid to prepare an esterification product, has the advantages of low cost and simple operation, the esterification product contains a mixture prepared by monohydroxy esterification or dihydroxyl esterification, the prepared esterification product participates in the next copolymerization reaction, so that the main chain of the polycarboxylate water reducer is provided with benzene rings, boric acid, hydroxyl groups and other groups, and a rigid benzene ring is introduced into the main chain, so that the main chain has a rigid and inflexible structure, and the molecules of the water reducer are not easy to be buried by stone powder in machine-made sand, thereby improving the workability of concrete; the hydroxyl complex calcium ion has strong capability, enhances the adsorption capability of the water reducer, can continuously combine calcium ions released during cement hydration, and inhibits the hydration of hydrated minerals and the growth of hydration products, thereby greatly delaying the cement hydration process and finally reducing the hydration heat; for the monomer obtained after partial dihydroxyl esterification is a crosslinking monomer, partial crosslinking is realized in the polymerization process, so that the water reducer molecules have long-chain branches, the steric hindrance effect of the system is increased, the capillary effect of the long-chain branches enables a hydration film to be stably wrapped around cement particles, the lubrication effect is achieved in the whole mixture system, the water retention effect is further enhanced, and the workability of the machine-made sand concrete is ensured;
and under the alkaline condition of cement, the carboxylic acid groups contributing to the water reducing effect are gradually released through gradual hydrolysis along with the extension of time, so that the lost water reducing rate is compensated, and the slump retaining effect is achieved.
2. According to the invention, the self-made esterification product and (1-fluorovinyl) methyl diphenyl silane participate in copolymerization reaction, so that a polycarboxylic acid water reducer molecule is provided with a plurality of silane groups, silane functional groups are hydrolyzed to generate silicon hydroxyl groups, the condensation of the silicon hydroxyl groups and the hydroxyl groups on the surfaces of cement particles generates chemical adsorption, the adsorption capacity is greater than the electrostatic adsorption of carboxyl groups, and the dispersion capacity of the polycarboxylic acid water reducer and the adaptability to cement, aggregate impurities and environment can be greatly improved, so that the workability of concrete is improved;
by introducing the biphenyl rings, the rigid structure of the main chain is further enhanced, the main chain structure can be unfolded, the adsorption area of cement particles is increased, agglomeration is not easy to occur, and the adsorption efficiency is improved. The electronegativity of fluorine is large, and the organic fluorine is introduced to increase the hydrogen bonding degree of polycarboxylic acid molecules, improve the crosslinking degree of molecules, increase the thickness of hydration film and improve the lubricity among particles. Meanwhile, the fluorocarbon structure has good hydrophobic property, can better release free water and reduce viscosity.
3. The preparation method of the viscosity-reducing ether polycarboxylate water reducer provided by the invention has the advantages of simple technological operation, mild reaction conditions, easiness in large-scale production, safety and no pollution in the production process, and belongs to an environment-friendly product.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure and/or components pointed out in the written description and claims.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in conjunction with the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some, but not all, embodiments of the present invention; the technical features designed in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention provides the following examples
Example 1
A1, preparing an esterification product: adding 127.6 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 5.7 parts of cerium sulfate and 5.9 parts of methyl hydroquinone under the protection of nitrogen, regulating the reaction temperature to 125 ℃, and reacting for 5 hours to obtain an esterification product;
a2, copolymerization reaction: according to parts by weight, adding 2.5 parts of the esterification product prepared by A1, 100 parts of isobutylether polyoxyethylene ether with the molecular weight of 1000, 1 part of (1-fluorovinyl) methyldiphenylsilane, 3 parts of sorbitol polyoxyethylene ether tetraoleate and 122 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2.1 parts of ammonium persulfate and 20 parts of water into a first dropwise adding device; 2.1 parts of sodium hypophosphite, 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 4.5 parts of acrylic acid, 5 parts of hydroxypropyl acrylate and 20 parts of water are uniformly mixed in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and A3, adding 12 parts of sodium hydroxide with the mass concentration of 32% into the mixture to adjust the pH to 6-7, thereby obtaining the viscosity-reducing ether polycarboxylate superplasticizer with the concentration of 40%.
Example 2
B1, preparation of an esterification product: adding 132.9 parts of methacrylic acid and 100 parts of 4-hydroxyphenylboric acid pinacol ester into a first reaction vessel for mixing, adding 3.7 parts of concentrated sulfuric acid and 1.2 parts of diphenylamine under the protection of nitrogen, regulating the reaction temperature to 130 ℃, and reacting for 4 hours to obtain an esterification product;
b2, copolymerization reaction: according to parts by weight, adding 5.5 parts of the esterified product prepared by the B1, 100 parts of isopentenol polyoxyethylene ether with molecular weight of 1500, 3 parts of (1-fluorovinyl) methyldiphenylsilane, 1 part of sorbitol polyoxyethylene ether tetraoleate and 135 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 3 parts of hydrogen peroxide and 20 parts of water into a first dropwise adding device; 1.7 parts of ascorbic acid, 1 part of n-dodecyl mercaptan and 20 parts of water are uniformly mixed in a second dripping device; mixing 12 parts of acrylic acid, 4.1 parts of methyl methacrylate and 20 parts of water uniformly in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and B3, adding 12 parts of sodium hydroxide with the mass concentration of 32% into the mixture to obtain the viscosity-reducing ether polycarboxylate superplasticizer with the concentration of 40%.
Example 3
C1, preparation of an esterification product: adding 93.8 parts of methacrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 2.3 parts of p-toluenesulfonic acid and 5.8 parts of methyl hydroquinone under the protection of nitrogen, regulating the reaction temperature to 135 ℃, and reacting for 6 hours to obtain an esterified product;
c2, copolymerization reaction: according to parts by weight, adding 4 parts of an esterification product prepared by C1, 100 parts of methyl allyl monomethyl ether polyoxyethylene ether with a molecular weight of 2000, 2 parts of (1-fluorovinyl) methyl diphenyl silane, 2 parts of sorbitol polyoxyethylene ether tetraoleate and 123 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 1.6 parts of tert-butyl hydroperoxide and 20 parts of water into a first dripping device; 1 part of 2-hydroxy-2-sulfinylacetic acid disodium salt, 0.5 part of 3-mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; mixing 9 parts of acrylic acid, 3.5 parts of hydroxypropyl methacrylate and 20 parts of water uniformly in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 2 hours, and reacting at constant temperature for 0.5 hour;
and C3, adding 12 parts of sodium hydroxide with the mass concentration of 32% into the mixture to obtain the viscosity-reducing ether polycarboxylate superplasticizer with the concentration of 40%.
Example 4
D1, preparation of an esterification product: adding 52.3 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 1.3 parts of cerium sulfate and 1.8 parts of hydroquinone under the protection of nitrogen, regulating the reaction temperature to 120 ℃, and reacting for 5 hours to obtain an esterification product;
d2, copolymerization reaction: according to parts by weight, adding 3 parts of the esterification product prepared in the step D1, 100 parts of allyl polyoxyethylene polyoxypropylene ether with the molecular weight of 1200, 1.5 parts of (1-fluorovinyl) methyl diphenyl silane, 1.5 parts of sorbitol polyoxyethylene ether tetraoleate and 121 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 1 part of sodium persulfate with 20 parts of water in a first dripping device; 3.5 parts of ammonium bisulfate, 2.5 parts of sodium hypophosphite and 20 parts of water are uniformly mixed in a second dripping device; mixing 7 parts of acrylic acid, 2.5 parts of hydroxyethyl acrylate and 20 parts of water uniformly in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 2 hours, and reacting at constant temperature for 0.5 hour;
and D3, adding 12 parts of sodium hydroxide with the mass concentration of 32% into the mixture to obtain the viscosity-reducing ether polycarboxylate superplasticizer with the concentration of 40%.
The invention also provides the following comparative examples
Comparative example 1
And (3) selecting commercial Poi nt-500 type polycarboxylate superplasticizer mother liquor and GYQ-I air entraining agent, and adjusting the expansion degree after compounding to verify the concrete.
Comparative example 2
And (3) selecting commercial Poi nt-500 type polycarboxylate superplasticizer mother liquor and boric acid, and adjusting the expansion degree after compounding to verify the concrete.
Comparative example 3
E1, preparation of esterification products: adding 127.6 parts of acrylic acid and 100 parts of 4-hydroxyphenyl phosphoric acid into a first reaction vessel, mixing, adding 5.7 parts of cerium sulfate and 5.9 parts of methyl hydroquinone under the protection of nitrogen, regulating the reaction temperature to 125 ℃, and reacting for 5 hours to obtain an esterification product;
e2, copolymerization reaction: according to parts by weight, adding 2.5 parts of an esterification product prepared by E1, 100 parts of isobutylether polyoxyethylene ether with the molecular weight of 1000, 1 part of (1-fluorovinyl) methyldiphenylsilane, 3 parts of sorbitol polyoxyethylene ether tetraoleate and 122 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2.1 parts of ammonium persulfate and 20 parts of water into a first dropwise adding device; 2.1 parts of sodium hypophosphite, 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 4.5 parts of acrylic acid, 5 parts of hydroxypropyl acrylate and 20 parts of water are uniformly mixed in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the viscosity-reducing ether polycarboxylate superplasticizer with the concentration of 40%.
Comparative example 4
F1, copolymerization reaction: according to weight parts, firstly adding 100 parts of isobutylether with molecular weight of 1000, 1 part of (1-fluorovinyl) methyl diphenyl silane, 3 parts of sorbitol polyoxyethylene ether tetraoleate and 119 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2.1 parts of ammonium persulfate and 20 parts of water into a first dripping device; 2.1 parts of sodium hypophosphite, 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 4.5 parts of acrylic acid, 5 parts of hydroxypropyl acrylate and 20 parts of water are uniformly mixed in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the viscosity-reducing ether polycarboxylate superplasticizer with the concentration of 40%.
Comparative example 5
G1, preparation of esterification products: adding 127.6 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 5.7 parts of cerium sulfate and 5.9 parts of methyl hydroquinone under the protection of nitrogen, regulating the reaction temperature to 125 ℃, and reacting for 5 hours to obtain an esterification product;
g2, copolymerization reaction: according to parts by weight, adding 2.5 parts of an esterification product prepared by G1, 100 parts of isobutylether polyoxyethylene ether with the molecular weight of 1000, 3 parts of sorbitol polyoxyethylene ether tetraoleate and 121 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2.1 parts of ammonium persulfate and 20 parts of water in a first dripping device; 2.1 parts of sodium hypophosphite, 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 4.5 parts of acrylic acid, 5 parts of hydroxypropyl acrylate and 20 parts of water are uniformly mixed in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the viscosity-reducing ether polycarboxylate superplasticizer with the concentration of 40%.
Comparative example 6
H1, preparation of esterification products: adding 127.6 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 5.7 parts of cerium sulfate and 5.9 parts of methyl hydroquinone under the protection of nitrogen, regulating the reaction temperature to 125 ℃, and reacting for 5 hours to obtain an esterification product;
h2, copolymerization: according to the weight parts, adding 2.5 parts of an esterification product prepared by H1, 100 parts of isobutylether with the molecular weight of 1000, 1 part of distyrylmethyl silane, 3 parts of sorbitol polyoxyethylene ether tetraoleate and 122 parts of water into a second reaction container, and uniformly stirring; 2.1 parts of ammonium persulfate and 20 parts of water are uniformly mixed in a first dripping device; 2.1 parts of sodium hypophosphite, 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 4.5 parts of acrylic acid, 5 parts of hydroxypropyl acrylate and 20 parts of water are uniformly mixed in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the viscosity-reducing ether polycarboxylate superplasticizer with the concentration of 40%.
Comparative example 7
I1, preparation of an esterification product: adding 127.6 parts of acrylic acid and 100 parts of 4-hydroxyphenylboronic acid pinacol ester into a first reaction vessel for mixing, adding 5.7 parts of cerium sulfate and 5.9 parts of methyl hydroquinone under the protection of nitrogen, regulating the reaction temperature to 125 ℃, and reacting for 5 hours to obtain an esterification product;
and I2, copolymerization reaction: according to parts by weight, adding 2.5 parts of the esterified product prepared by I1, 100 parts of isobutylether polyoxyethylene ether with the molecular weight of 1000, 1 part of (4-fluoro-phenyl) dimethyl alkenyl silicon, 3 parts of sorbitol polyoxyethylene ether tetraoleate and 122 parts of water into a second reaction container, uniformly stirring, and uniformly mixing 2.1 parts of ammonium persulfate and 20 parts of water into a first dropwise adding device; 2.1 parts of sodium hypophosphite, 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 4.5 parts of acrylic acid, 5 parts of hydroxypropyl acrylate and 20 parts of water are uniformly mixed in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the viscosity-reducing ether polycarboxylate superplasticizer with the concentration of 40%.
Comparative example 8
J1, copolymerization reaction: according to the weight parts, firstly adding 2.5 parts of 2-allylphenylboronic acid, 100 parts of isobutenyl alcohol polyoxyethylene ether with the molecular weight of 1000, 1 part of (1-fluorovinyl) methyl diphenyl silane, 3 parts of sorbitol polyoxyethylene ether tetraoleate and 122 parts of water into a second reaction container, and uniformly stirring; 2.1 parts of ammonium persulfate and 20 parts of water are uniformly mixed in a first dripping device; 2.1 parts of sodium hypophosphite, 3 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 4.5 parts of acrylic acid, 5 parts of hydroxypropyl acrylate and 20 parts of water are uniformly mixed in a third dripping device; sequentially starting to dropwise add the materials in the first dropwise adding device, the second dropwise adding device and the third dropwise adding device into the second reaction container at room temperature, respectively dropwise adding the materials in the third dropwise adding device, the second dropwise adding device and the first dropwise adding device in 1.5h, and reacting at constant temperature for 0.5h;
and adding 12 parts by weight of sodium hydroxide with the mass concentration of 32%, thus obtaining the viscosity-reducing ether polycarboxylate superplasticizer with the concentration of 40%.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limited thereto; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.
In addition, unless otherwise specified, the starting materials employed may also be commercially available products conventionally used in the art or may be prepared by methods conventionally used in the art.
The viscosity-reducing ether polycarboxylate water reducer synthesized in examples 1 to 4 is compared with the machine-made sand concrete used in comparative examples 1 to 8, conch PO52.5R cement is adopted, and the mixing amount of the water reducer in examples 1 to 4 and comparative examples 1 to 8 is adjusted to the mixing amount with the expansion degree of 630+/-20 mm. According toGB 50080-2016 Standard for test methods for Properties of general concrete mixtures, GB/T50081-2002 Standard for test methods for mechanical Properties of general concrete, and test the Properties of the concrete mixture. The concrete mixing ratio is as follows: 450kg/m cement 3 50kg/m of fly ash 3 80kg/m of mineral powder 3 730kg/m machine-made sand 3 680kg/m of 16-31.5 mm crushed stone 3 320kg/m of small stone with the diameter of 5-20 mm 3 The concrete test results are shown in table 1.
Table 1 concrete performance test data
As can be seen from the test results of Table 1, the performance of the examples is superior to that of the comparative examples, and the results of the examples and comparative examples 1 and 2 show that compared with the mode of adopting the existing water reducing agent to compound the air entraining agent and retarder, the viscosity-reducing ether polycarboxylic acid water reducing agent provided by the invention has the advantages of lower collapse emptying time and T500 time, good workability and better strength and 1h collapse protection effect;
as can be seen from the combination of comparative example 3, the esterified product of functional monomer a has better dispersibility than 4-hydroxyphenyl phosphoric acid, and the workability, collapse and evacuation time and T500 time are all better than the latter;
the self-made esterified product and the functional monomer B are added to ensure that the prepared polycarboxylate water reducer has better water-reducing and slump-retaining performance, slump-reducing and emptying time, T500 time and viscosity-reducing effect by combining with comparative examples 4 and 5;
as can be seen by combining comparative examples 6 and 7, compared with other silane monomers in the prior art, the functional monomer B adopted by the invention has better viscosity reduction effect, lower collapse emptying time and T500 time and better workability and slump retaining effect;
as can be seen by combining with comparative example 8, compared with the water reducer obtained by directly copolymerizing unsaturated phenylboronic acid monomers, the water reducer copolymerized by the esterification product contains more borate, so that the dispersion capacity and workability of polycarboxylic acid are greatly improved, and meanwhile, the benzene ring is closer to the main chain, so that the main chain is more stretched, the adsorption performance is improved, more free water is released, and the viscosity of concrete is reduced;
in conclusion, the viscosity-reducing ether polycarboxylate water reducer provided by the invention has a better viscosity-reducing effect.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present invention may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Although terms such as esterification products, ester macromers, acrylic acid, unsaturated sulfonates, functional monomers B, etc. are more used herein, the possibility of using other terms is not excluded. These terms are used merely for convenience in describing and explaining the nature of the invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention; the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The viscosity-reducing ether polycarboxylate water reducer is characterized in that: comprises an esterification product, an ether macromonomer, acrylic acid, an unsaturated ester monomer and a functional monomer B;
the esterification product is prepared by esterification reaction of a functional monomer A and unsaturated acid;
the functional monomer B is a monomer with a silane group, a double benzene ring and a fluorocarbon bond structure;
the functional monomer A is 4-hydroxyphenylboronic acid pinacol ester, and the structural formula is as follows:
;
the functional monomer B is (1-fluorovinyl) methyl diphenyl silane.
2. The viscosity reducing ether-type polycarboxylate water reducer as claimed in claim 1, wherein: the preparation process of the esterified product comprises the steps of adding unsaturated acid and functional monomer A into a reaction vessel for mixing, adding a catalyst and a polymerization inhibitor under the condition of protecting gas, and regulating the temperature t 1 Reaction T at a temperature of 1 h, obtaining an esterification product at a temperature t 1 Reaction T at 120-135 DEG C 1 4-6 h.
3. The viscosity reducing ether-type polycarboxylate water reducer as claimed in claim 1, wherein: the unsaturated acid is one of acrylic acid and methacrylic acid.
4. The viscosity reducing ether-type polycarboxylate water reducer as claimed in claim 2, wherein: the molar ratio of the functional monomer A to the unsaturated acid is 1:1.5-4, the mass of the catalyst is 0.8-2.5% of the total mass of the unsaturated acid and the functional monomer A, and the mass of the polymerization inhibitor is 0.5-3% of the total mass of the unsaturated acid and the functional monomer A.
5. The viscosity reducing ether-type polycarboxylate water reducer as claimed in claim 1, wherein: the ether macromonomer is one of isobutenyl alcohol polyoxyethylene ether, isopentenyl alcohol polyoxyethylene ether, methyl allyl monomethyl ether polyoxyethylene ether and allyl polyoxyethylene polyoxypropylene ether with the molecular weight of 1000-2000.
6. The viscosity reducing ether-type polycarboxylate water reducer as claimed in claim 1, wherein: the unsaturated ester monomer is one of hydroxypropyl acrylate, hydroxyethyl acrylate, methyl methacrylate and hydroxypropyl methacrylate.
7. The viscosity reducing ether-type polycarboxylate water reducer as claimed in claim 1, wherein: the mass ratio of the esterification product to the ether macromonomer to the acrylic acid to the unsaturated ester monomer to the functional monomer B is 2.5-5.5:100:4.5-12:2.5-5:1-3.
8. The viscosity reducing ether-type polycarboxylate water reducer as claimed in claim 1, wherein: the components also comprise an emulsifier, an oxidant, a reducing agent and a chain transfer agent; the amount of the emulsifier is 1-3% of the total mass of the ether macromonomer, the amount of the oxidant is 1-3% of the total mass of the ether macromonomer, the amount of the reducer is 1-3.5% of the total mass of the ether macromonomer, and the amount of the chain transfer agent is 1-3% of the total mass of the ether macromonomer.
9. A method for preparing the viscosity-reducing ether polycarboxylate superplasticizer according to any one of claims 1-8, characterized in that: the method comprises the following steps:
adding the esterified product, the ether macromonomer, the functional monomer B and the emulsifier into a reaction vessel for mixing, respectively dripping an oxidant solution, a mixed solution of a reducing agent and a chain transfer agent, and a mixed solution of acrylic acid and an unsaturated ester monomer for reaction at room temperature, preserving heat after the reaction is finished, and adding liquid alkali for regulating pH to obtain the viscosity-reducing ether polycarboxylate water reducer.
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| CN111187226A (en) * | 2020-01-15 | 2020-05-22 | 山西大学 | Antibacterial agent for specifically killing gram-negative bacteria, preparation method and application |
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