CN113637122A - Polycarboxylic acid compound and preparation method and application thereof - Google Patents
Polycarboxylic acid compound and preparation method and application thereof Download PDFInfo
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- CN113637122A CN113637122A CN202110788131.0A CN202110788131A CN113637122A CN 113637122 A CN113637122 A CN 113637122A CN 202110788131 A CN202110788131 A CN 202110788131A CN 113637122 A CN113637122 A CN 113637122A
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- 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
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- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a polycarboxylic acid compound and a preparation method and application thereof, belonging to the technical field of concrete admixtures. The polycarboxylate water reducer is prepared by polymerizing vinyl calixarene, unsaturated acid ester and polyether macromonomer, and the side chain of the polycarboxylate water reducer has high steric hindrance, so that when the polycarboxylate water reducer is used as a polycarboxylate water reducer, the polycarboxylate water reducer has excellent mud resistance, and has excellent hydrophilic performance and early strength performance because of containing rich sulfonic groups.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a polycarboxylic acid compound and a preparation method and application thereof.
Background
The polycarboxylic acid water reducing agent has the advantages of low mixing amount, high water reducing rate, environmental protection and the like, and is widely used as a concrete admixture. However, polycarboxylic acid water reducing agents are more sensitive to clay in concrete aggregates than naphthalene-based, aliphatic and other water reducing agents, and show problems of a decrease in strength of hardened concrete, cracks and the like due to a severe decrease in dispersing ability, a large water demand, and a rapid loss in slump of concrete when the amount of the clay is large. Meanwhile, with the rapid development of the building industry, high-quality sandstone resources become more and more scarce, and the problems of higher mud content in the sandstone for buildings and the like are increasingly prominent.
For the reasons, research on the mud resistance of the polycarboxylate superplasticizer is increasing in the field, the idea is mainly to introduce functional groups or change raw material monomers, but the mud resistance of the polycarboxylate superplasticizer obtained by the two methods still needs to be improved.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a polycarboxylic acid compound which can have excellent mud resistance when used as a polycarboxylic acid water reducing agent due to the adjustment of the structure of the compound.
The invention also provides a preparation method of the polycarboxylic acid compound.
The invention also provides a polycarboxylic acid water reducing agent containing the polycarboxylic acid compound.
The invention also provides an application of the polycarboxylate superplasticizer as a concrete admixture.
According to one aspect of the present invention, there is provided a polycarboxylic acid compound having a structural formula represented by formula I:
wherein:
R1is-H or-CH3；
R2is-COOH or-H;
R3is-H, -CH2COOH or-CH3One of (1);
R4is-H or-CH3；
R5is-CH2CH2OH、—CH2CH2CH2OH、—CH2CH(OH)CH3、—CH3or-CH2CH3One of (1);
R6is-H or-CH3；
R7is-CH2—、—CH2CH2—、—OCH2CH2-or-OCH2CH2CH2CH2-one of;
R8is-SO3H or-SO3Na；
R9is-COOH or-COONa;
a, b, x, y, m, n are the number of repetitions of the repeating unit,
a:y＝(0.1～1.5):1，b:y＝(2.5～6.0):1，x:y＝(0.5～1.5):1，m＝27～180，n＝4，6，8。
according to a preferred embodiment of the present invention, at least the following advantages are provided:
(1) the polycarboxylic acid compound provided by the invention comprises a sulfonated calix [ n ] arene (USCnA) group and a polyether side chain group, namely the side chain has larger size, so that when the polycarboxylic acid compound is used as a concrete water reducing agent, the steric exclusion of the side chain is higher, the thickness of a hydration layer formed by the side chain is increased, and the water reducing capacity of the product can be further increased;
in addition, calix [ n ] arene is an annular cavity structure, the cavity has the advantage of adjustable size, and the size of a side chain of the polycarboxylic acid compound can be adjusted by adjusting the size of the cavity, so that the polycarboxylic acid compound obtained by the method has wide application range;
(2) the clay contained in the sand is mostly layered clay, the polycarboxylic acid compound provided by the invention has larger side chains, and the polycarboxylic acid compound provided by the invention has larger side chains (steric hindrance), so that the polycarboxylic acid compound is difficult to insert into a clay structure, namely difficult to combine with the clay, which further indicates that the clay hardly influences the performance of the polycarboxylic acid water reducer, and therefore, the polycarboxylic acid compound provided by the invention can improve the mud resistance function of the polycarboxylic acid water reducer;
(3) the polycarboxylic acid compound provided by the invention contains abundant sulfonic acid groups, and the sulfonic acid groups have strong adsorption and positioning effects on calcium ions and the like exposed on the surface of hydrated cement particles, so that the directional adsorption effect of the polycarboxylic acid compound on the cement surface can be enhanced, and the strength of the hardened concrete is further improved; the adsorption effect of the clay on the polycarboxylic acid compound is further reduced due to the competition effect of calcium ions, so that the dispersion and the stability of the clay in the concrete are facilitated due to the existence of the sulfonic acid group, and the influence of the clay on the strength of the concrete is further reduced; in addition, the sulfonic acid group can also improve the hydrophilic property of the polycarboxylic acid compound.
In the formula I, a represents the repetition number of a vinyl sulfonated calixarene monomer, the monomer mainly influences the steric hindrance effect of a polycarboxylic acid compound, the larger the steric hindrance is, the larger the resistance to clay when the monomer is used as a water reducing agent is, and the more obvious the inhibition on the hydration effect of cement is, and when a: y is (0.1-1.5): 1 (representing the molar ratio of raw materials), the hydration effect of the cement and the resistance to the clay can be considered at the same time.
In the formula I, b is the repetition number of an acrylic monomer, the monomer is combined with a polyoxyethylene ether monomer to play a role in improving cement dispersion, and the larger the value of b is, the stronger the complexing ability of the polycarboxylic acid compound to cement is when the polycarboxylic acid compound is used for a polycarboxylic acid water reducing agent, but the dispersing ability to cement is reduced; the smaller the value of b, the weaker the ability to complex with cement, but the more the ability to disperse with cement increases, and when b: y is (2.5 to 6.0):1, both of the above-mentioned performances can be achieved.
In the formula I, x is the repetition number of the acrylate monomer, the ester structure is slowly hydrolyzed under the alkaline condition to expose carboxyl, the function of the acrylate monomer is consistent with that of the acrylate monomer, and when x: y ═ 1.5-0.5, the hydration effect of cement and clay resistance can be considered.
In some embodiments of the invention, R in formula I8is-SO3Na。
In some embodiments of the present invention, the polycarboxylic acid compound has an average molecular weight of 20000 to 80000.
If the average molecular weight of the polycarboxylic acid compound is 20000-80000, the polycarboxylic acid water reducing agent has the optimal performance after being applied to the polycarboxylic acid water reducing agent; when the average molecular weight is smaller (<20000), the dispersing ability of the polycarboxylate superplasticizer is weaker, so that the concrete dispersing effect is insufficient, and the concrete expansion degree is smaller; when the average molecular weight is larger (>80000), the viscosity of the polycarboxylic acid water reducing agent is larger, the concrete is thicker, and the expansion degree is also smaller; therefore, if the average molecular weight is outside the range of 20000 to 80000, the performance of the polycarboxylic acid water reducing agent is deteriorated.
According to another aspect of the present invention, a preparation method of the polycarboxylic acid compound is provided, which comprises polymerizing vinyl sulfonated calix [ n ] arene, polyether macromonomer, unsaturated acid monomer and unsaturated acid ester monomer under the action of a chain transfer agent and an initiator to obtain the polycarboxylic acid compound.
The preparation method according to a preferred embodiment of the present invention has at least the following advantageous effects:
compared with the existing preparation method, the preparation method provided by the invention introduces calixarene into the polycarboxylic acid water reducing agent, so that the water reducing rate can be ensured, the adsorption of clay to polycarboxylic acid molecules is reduced, the sensitivity to the soil content in concrete ground materials is low, the workability of the concrete can be improved, and the preparation method has better adaptability and soil adsorption resistance. Meanwhile, the USCnA structural unit has rich sulfonic acid groups, and has strong adsorption and positioning effects on calcium ions and the like exposed on the surface of hydrated cement particles, so that the directional adsorption of the USCnA structural unit on the cement surface can be enhanced, the strength of the hardened concrete can be improved, and the influence of clay on the strength of the concrete can be reduced.
In some preferred embodiments of the present invention, the method for preparing the polycarboxylic acid compound comprises the steps of:
s1, reacting p-tert-butylphenol and formaldehyde under the action of an alkaline catalyst to obtain calix [ n ] arene;
s2, sulfonating and modifying the calix [ n ] arene by using a sulfonating agent to obtain sulfonated calix [ n ] arene;
s3, reacting the sulfonated calix [ n ] arene with methacryloyl chloride to obtain vinyl sulfonated calix [ n ] arene;
and S4, under the action of a chain transfer agent and an initiator, carrying out polymerization reaction on the vinyl sulfonated calix [ n ] arene, the polyether macromonomer, the unsaturated acid monomer and the unsaturated acid ester monomer to obtain the polycarboxylic acid compound.
In some embodiments of the present invention, the synthesis route of the vinylsulfonated calix [ n ] arene is as follows (corresponding to steps S1-S3):
in some embodiments of the present invention, the synthetic route of the polycarboxylate superplasticizer is as follows (corresponding to step S4):
the calix [ n ] arene means that the calix arene contains n benzene rings.
In some embodiments of the present invention, in step S1, the molar ratio of the p-tert-butylphenol to the formaldehyde is from (1:1.05) to (1: 1.25).
In some preferred embodiments of the present invention, in step S1, the molar ratio of the p-tert-butylphenol to the formaldehyde is 1: 1.2.
In some embodiments of the invention, in step S1, the reaction is at a temperature of 110 ℃.
In some embodiments of the invention, in step S1, the reaction is preferably for 2 hours.
In some embodiments of the invention, in step S1, the basic catalyst comprises at least one of sodium hydroxide and potassium hydroxide.
In some embodiments of the present invention, in step S1, the mass of the basic catalyst is 0.8% to 1.5% of the mass of the tert-butyl phenol.
In some embodiments of the present invention, in step S1, the mass of the basic catalyst is 1.0% of the mass of the tert-butyl phenol.
In some embodiments of the present invention, step S1 further comprises performing a purification operation of the calix [ n ] arene after the reaction is completed.
In some embodiments of the present invention, the purification operation of calix [ n ] arene comprises the following steps:
s1a, cooling the reaction system of the step S1 to room temperature (about 25 ℃);
s1b, adding diphenyl ether into the system obtained in the step S1a in a nitrogen atmosphere, heating to 170 ℃, reacting for 10min, and condensing and refluxing for reaction for 2 h;
s1c, cooling the system obtained in the step S1b to room temperature, adding an extracting agent to adjust the polarity of the system, and precipitating a crude product of calix [ n ] arene;
and S1d, washing the crude product obtained in the step S1c to obtain the calix [ n ] arene.
In some embodiments of the present invention, in step S1b, the diphenyl ether functions as an organic high temperature heat carrier, and can rapidly conduct heat after being added.
In some embodiments of the present invention, in step S1b, the mass ratio of the diphenyl ether to the p-tert-butylphenol is (3:1) to (6: 1).
In some embodiments of the present invention, diphenyl ether may not be added in step S1b, which reduces the heat transfer efficiency and still achieves the corresponding experimental results.
In some embodiments of the invention, in step S1c, the extractant is at least one of ethyl acetate, diethyl ether/methyl acetate, and chloroform/acetone.
In some embodiments of the present invention, in step S1c, the extractant is used to extract the diphenyl ether in step S1b, and simultaneously, the calix [ n ] arene is precipitated, so as to facilitate the separation of the intermediate product.
In some embodiments of the present invention, in step S1d, the washing is performed by sequentially washing with ethyl acetate, glacial acetic acid and water.
In some embodiments of the invention, in step S2, the sulfonating agent is concentrated sulfuric acid with a concentration of 98 wt%.
In some embodiments of the present invention, in step S2, the mass ratio of the calix [ n ] arene to concentrated sulfuric acid with a concentration of 98 wt% is in the range of 1: (7.2-15.3).
The sulfonating agent also has the function of an acid catalyst.
In some embodiments of the present invention, in step S2, the sulfonation modification is performed at a reaction temperature of 90 ℃.
In some embodiments of the present invention, in step S2, the sulfonation modification is performed for 4 hours.
In some embodiments of the present invention, step S2 further comprises purification of the sulfonated calix [ n ] arene.
In some embodiments of the present invention, the purification of the sulfonated calix [ n ] arene specifically comprises the following steps:
s2a, after cooling the system obtained in the step S2 to room temperature, slowly dropwise adding the material of the reaction system obtained in the step S2 into saturated salt water under the condition of ice-water bath;
s2b, after the dropwise addition is finished, heating and refluxing for 5 min;
s2c, cooling the system obtained in the step S2b to room temperature, continuing to cool to the temperature range of 0-5 ℃, and standing for 12 hours;
s2d, performing solid-liquid separation on the system obtained in the step S2c, recrystallizing the obtained solid by using deionized water as a solvent, and performing solid-liquid separation again to obtain the solid sulfonated calix [ n ] arene.
In some embodiments of the present invention, step S2a is to adjust the solubility of sulfonated calix [ n ] arene in water to make it more easily precipitate, by virtue of the polarity of the brine.
In some embodiments of the present invention, in step S2b, the heating is performed under reflux at a temperature of 105-120 ℃.
In step S2b, the heating is performed under reflux in order to reduce evaporation of water and to stabilize the amount of solvent.
In some embodiments of the invention, in step S3, the reaction, solvent is N, N-dimethylformamide, which acts as a polar solvent.
In some embodiments of the present invention, in step S3, the reaction is specifically performed by dropping the methacryloyl chloride into the N, N-dimethylformamide solution of the sulfonated calix [ N ] arene at a temperature ranging from 0 to 5 ℃; after the dropwise addition, the system was heated to 25 ℃ and the reaction was continued for 24 hours.
In some embodiments of the present invention, in step S3, the molar ratio of sulfonated calix [4] arene to methacryloyl chloride is 1: (1.05-1.25).
The methacryloyl chloride is used for substituting hydrogen in phenolic hydroxyl on the sulfonated calix [ n ] arene by a substitution agent of the sulfonated calix [ n ] arene, specifically by methacryloyl to obtain the vinyl sulfonated calix [ n ] arene containing double bonds.
In some embodiments of the present invention, step S3 further comprises purification of the vinyl sulfonated calix [ n ] arene; the specific operation is as follows: and (4) adjusting the polarity of the system obtained in the step S3 by using a polarity adjusting solvent, separating out a precipitate, and performing solid-liquid separation to obtain the solid vinylated sulfonated calix [ n ] arene.
In some embodiments of the present invention, the polarity-adjusting solvent is at least one of acetone, methanol/ethyl acetate, and ethanol/ethyl acetate.
The mass of the polarity adjusting solvent is that the mass ratio of the sulfonated calix [ n ] arene is (5-20): 1.
In some preferred embodiments of the present invention, the polarity-adjusting solvent is acetone.
In some embodiments of the present invention, in step S4, the structure of the vinylsulfonated calix [ n ] arene is represented by formula II:
wherein:
R1is-H or-CH3；
n＝4，6，8。
In some embodiments of the present invention, in step S4, the unsaturated acid monomer has a structure represented by formula III:
wherein R is2is-COOH or-H;
R3is-H, -CH2COOH or-CH3One kind of (1).
The unsaturated acid is used as a monomer of the polycarboxylic acid compound, and has a carboxyl group, so that the unsaturated acid can anchor cement particles and control the hydration process of cement.
In some embodiments of the present invention, in step S4, the unsaturated acid ester monomer has a structure represented by formula IV:
wherein R is4is-H or-CH3；
R5is-CH2CH2OH、—CH2CH2CH2OH、—CH2CH(OH)CH3、—CH3or-CH2CH3One kind of (1).
The unsaturated acid ester, as a monomer of the polycarboxylic acid compound, can slowly release carboxyl in cement and concrete due to the ester group, thereby playing a role in delaying the curing of the concrete.
In some embodiments of the present invention, in step S4, the polyether macromonomer has the structure shown in formula V:
wherein R is6is-H or-CH3；
R7is-CH2—、—CH2CH2—、—OCH2CH2-or-OCH2CH2CH2CH2-one of;
and m is 27-180, namely the average molecular weight of the polyether macromonomer is 1200-8000.
When R is6is-H, R7is-CH2When the compound represented by the formula V is APEG (allyl polyoxyethylene ether);
when R is6is-CH3R7 is-CH2When the compound represented by the formula V is HPEG (methallyl alcohol polyoxyethylene ether);
when R is6is-CH3，R7is-CH2CH2When the compound represented by the formula V is TPEG (isopentenol polyoxyethylene ether);
when R is6is-H, R7is-OCH2CH2When the compound represented by the formula V is EPEG (ethylene glycol monovinyl polyethylene glycol ether);
when R is6is-H, R7is-OCH2CH2CH2CH2And-case (1) -represents VPEG (4-hydroxybutyl vinyl polyoxyethylene ether).
In some embodiments of the present invention, in step S4, the polyether macromonomer has an average molecular weight of 1200 to 8000.
Said poly(s)R in Ether macromonomers7And a repeating unit-CH2CH2O-, can influence the electron cloud distribution of unsaturated double bonds of the polyether macromonomer, and further influence the polymerization reaction rate when R is7is-OCH2CH2-or-OCH2CH2CH2CH2When the oxygen atom of the group is directly connected with the double bond, the electron cloud distribution of the double bond is deviated, thereby improving the charge environment of unsaturated double bond in the macromonomer, leading the reactivity of the double bond in the macromonomer to be much higher than that of the common macromonomer and being easier for polymerization reaction.
The polyether macromonomer has a long chain, so that the dispersion effect on cement can be improved.
When the average molecular weight of the polyether macromonomer is 1200-8000, the performance of the polycarboxylic acid water reducing agent comprising the obtained polycarboxylic acid compound is optimal, and if the average molecular weight is beyond the range, the performance of the polycarboxylic acid water reducing agent is influenced to a certain extent.
In some embodiments of the present invention, in step S4, the molar ratio of the vinylsulfonated calix [ n ] arene to the polyether macromonomer is (0.1-1.5): 1.
In some embodiments of the present invention, in step S4, the molar ratio of the unsaturated acid monomer to the polyether macromonomer is (2.5-6.0): 1.
In some embodiments of the present invention, in step S4, the molar ratio of the unsaturated acid ester monomer to the polyether macromonomer is (0.5-1.5): 1.
In some embodiments of the invention, in step S4, the initiator is at least one of hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, potassium permanganate, ascorbic acid, sodium persulfate, ferrous sulfate, and oxalic acid.
The initiator can cleave a double bond contained in a monomer of the polycarboxylic acid compound to initiate polymerization.
In some embodiments of the present invention, in step S4, the molar ratio of the initiator to the polyether macromonomer is (0.01-0.5): 1.
In some embodiments of the present invention, in step S4, the chain transfer agent is at least one of thioglycolic acid, mercaptopropionic acid, sodium hypophosphite, sodium methallylsulfonate and mercaptoethanol.
The chain transfer agent is capable of controlling the chain transfer in the polymerization reaction and controlling the degree of polymerization of the polycarboxylic acid compound within a certain range.
In some embodiments of the present invention, in step S4, the molar ratio of the chain transfer agent to the polyether macromonomer is (0.05-0.5): 1.
In some embodiments of the present invention, in step S4, the reaction time of the polymerization reaction is between 0.5 and 4.0 hours.
In some preferred embodiments of the present invention, in step S4, the polymerization reaction is specifically performed by:
s4a, mixing the polyether macromonomer with part of initiator to form a primer;
s4b, mixing the unsaturated acid monomer, the unsaturated acid ester monomer and the vinyl sulfonated calix [ n ] arene to form a first dropping material;
s4c, mixing the chain transfer agent with the rest of the initiator to form a second dripping material;
and S4d, dropwise adding the first dropping material and the second dropping material into the base material under the stirring state, and obtaining the polycarboxylic acid compound after the reaction is finished.
According to a further aspect of the invention, a polycarboxylate water reducer is provided, which comprises the polycarboxylate compound.
In some embodiments of the present invention, the polycarboxylate water reducing agent is prepared by adjusting the pH of the system obtained in step S4d with sodium hydroxide having a concentration of 30 wt%, and adjusting the solid content with water.
In some embodiments of the present invention, the pH value of the polycarboxylic acid water reducing agent is between 6 and 8, and the solid content is between 30 and 60%.
In some embodiments of the present invention, the pH value of the polycarboxylic acid water reducing agent is between 6 and 8, and the solid content is 40 to 50%.
In some embodiments of the present invention, the pH of the polycarboxylic acid water reducing agent is between 6 and 8, and the solid content is 40%.
According to a further aspect of the invention, the application of the polycarboxylate superplasticizer as a concrete admixture is provided.
In some embodiments of the invention, the concrete comprises a gel material.
In some preferred embodiments of the present invention, the gel material is cement and at least one of fly ash and mineral powder.
The cement may comprise gypsum.
And if the fly ash and the mineral powder are added, the mass sum of the fly ash and the mineral powder is less than 20% of the mass of the cement.
In some embodiments of the present invention, when the polycarboxylate water reducer is used as a concrete admixture, the folding and fixing amount (based on the solid content in the polycarboxylate water reducer) of the polycarboxylate water reducer is 0.03-0.5% by mass of the gel material.
In some preferred embodiments of the present invention, when the polycarboxylate superplasticizer is used as a concrete admixture, the folding and fixing content of the polycarboxylate superplasticizer is 0.03-0.3% of the mass of the gel material.
In some preferred embodiments of the present invention, when the polycarboxylate superplasticizer is used as a concrete admixture, the folding and fixing content of the polycarboxylate superplasticizer is 0.05-0.3% of the mass of the gel material.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
In the description of the present invention, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present numbers, and the above, below, within, etc. are understood as including the present numbers. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
Example 1
In this example, a polycarboxylic acid compound was prepared by the following specific process:
D1. preparation of calix [4] arene (p-tert-butylcalix [ n ] arene):
d1a, adding 0.4mol of p-tert-butylphenol (about 60g), 0.5mol of formaldehyde solution (the mass concentration is between 35 and 40 percent; the solvent is water, the concentration is 35 percent in the embodiment and about 45mL) and 0.6g of sodium hydroxide into a 1000mL three-neck flask, and reacting for 2 hours at the temperature of about 110 ℃;
d1b, cooling the system obtained in the step D1a to room temperature, adding 300mL of diphenyl ether, heating the system to about 170 ℃ in a nitrogen atmosphere, and reacting for 10 min;
d1c, under the auxiliary action of a reflux condensing tube, condensing and refluxing the system obtained in the step D1b, and reacting for 2 h;
D1D, cooling the system obtained in the step D1c to room temperature, adding 100mL of ethyl acetate, extracting the diphenyl ether, and precipitating to obtain a crude product of calix [ n ] arene (p-tert-butylcalix [ n ] arene);
d1e. washing the crude product from step D1D with 100mL ethyl acetate and 50mL glacial acetic acid, followed by deionized water to obtain calix [4] arene (p-tert-butylcalix [4] arene);
D2. preparation of sulfonated calix [4] arene (sulfonated p-tert-butylcalix [ n ] arene):
d2a, adding 6g of p-tert-butylcalix [4] arene (a product obtained in the step D1) and 50mL of 98 wt% concentrated sulfuric acid into a 250mL three-neck flask, and heating to 90 ℃ to react for 4 hours;
d2b, cooling the system obtained in the step D2a to room temperature, and slowly dripping the reaction system material into 200mL of saturated saline under the condition of ice-water bath; after the dropwise addition, heating and refluxing for 5 min;
d2c, cooling the system obtained in the step D2b to room temperature, standing for 12 hours at the temperature of 0-5 ℃, performing suction filtration, recrystallizing with deionized water, and performing suction filtration again to obtain sulfonated calix [4] arene (solid);
D3. synthesis of vinyl sulfonated calix [4] arene:
under the condition of stirring, adding 0.01mol of sulfonated calix [4] arene (about 8.32g) and 20mL of N, N-dimethylformamide into a 250mL three-neck flask, cooling to 0-5 ℃ (ice-water bath), then slowly dropwise adding 0.012mol of methacryloyl chloride (about 1.255g), heating to 25 ℃ after dropwise adding, and reacting for 24 hours; then acetone is used for precipitation and purification to obtain the vinyl sulfonated calix [4] arene;
D4. polymerization reaction:
d4a. into a flask equipped with a stirrer, macromonomer TPEG (0.125mol) having an average molecular weight of about 2400 and a mass of 300g, ferrous sulfate (initiator) 0.000066mol (1 wt% aqueous solution, 1.0g), 0.0283mol (27.5 wt% hydrogen peroxide (initiator) solution, 3.5g) were charged to obtain a primer;
d4b. mixing 0.5mol acrylic acid (about 36g), 0.055mol vinyl sulfonated calix [4] arene (about 50g) (product of step D3), and 0.125mol hydroxyethyl acrylate (about 14.5g) to form a first drop; 0.01554 moles of mercaptopropionic acid (about 1.65g chain transfer agent) and 0.003974 moles of ascorbic acid (about 0.7g initiator) were mixed to form a second drop;
adjusting the temperature of the bottom material to 30 ℃ under the stirring state of D4 c; dropwise adding a first dropwise material and a second dropwise material into the mixture, wherein the dropwise adding time of the first dropwise material is the same as that of the second dropwise material, the total dropwise adding time of the first dropwise material is 2.0 hours, and the dropwise adding time of the second dropwise material is 2.5 hours; and D, after the two kinds of dropping materials are dripped, preserving the heat for 1.0h to obtain the polycarboxylic acid compound, and dispersing the polycarboxylic acid compound in the system obtained in the step D4c.
Example 2
This example prepared a polycarboxylic acid compound, and the specific procedure differs from example 1 in that:
(1) in step D4a, macromonomer TPEG with an average molecular weight of about 2400 was replaced with macromonomer HPEG with an average molecular weight of about 3000 and a mass of 320g (about 0.1067 mol);
(2) in step D4a, the mass of hydrogen peroxide was changed from 3.5g to 3.2g (about 0.02588 mol);
(3) in step D4b, the chain transfer agent was replaced, specifically, 1.65g of mercaptopropionic acid (about 0.0155mol) was replaced with 3.85g of sodium hypophosphite (about 0.04376 mol).
Example 3
This example prepared a polycarboxylic acid compound, and the specific procedure differs from example 1 in that:
(1) step D4 is different from example 1, specifically, the polymerization reaction in this example includes:
D4. polymerization reaction:
d4a. into a flask equipped with a stirrer, macromonomer EPEG (about 0.1067mol) having an average molecular weight of about 3000 and a mass of 320g, ferrous sulfate (initiator) 0.1g (1.0% aqueous solution, about 0.00066mol) and 27.5 wt% hydrogen peroxide (initiator) solution 2.8g (about 0.023mol) were charged to obtain a primer;
d4b. mixing 32g of acrylic acid (about 0.44mol), 45g of vinylsulfonated calix [4] arene (product of step D3, about 0.05mol) and 15g of hydroxyethyl acrylate (about 0.13mol) to form a first drop; mixing 1.75g mercaptoethanol (chain transfer agent about 0.0224mol) and 0.7g ascorbic acid (initiator about 0.004mol) to form a second drop;
adjusting the temperature of the base material to 10 ℃ under the stirring state of D4 c; dripping a first dripping material and a second dripping material into the mixture, wherein the dripping starting time of the first dripping material is the same as that of the second dripping material, the total dripping time of the first dripping material is 40min, and the dripping time of the second dripping material is 45 min; and D, after the two kinds of dropping materials are dripped, preserving the heat for 1.0h to obtain the polycarboxylic acid compound, and dispersing the polycarboxylic acid compound in the system obtained in the step D4c.
Example 4
This example prepared a polycarboxylic acid compound, and the specific procedure differs from example 1 in that:
(1) in step D4a, macromonomer TPEG with an average molecular weight of about 2400 was replaced with macromonomer HPEG with an average molecular weight of about 4000 (about 0.095mol) with a mass of 380 g;
(2) in step D4b, the composition of the second drop charge was: 3.85g sodium hypophosphite (about 0.04375mol) and 0.4g sodium formaldehyde sulfoxylate;
(3) in step D4c, the temperature is 40 ℃; the dropping time of the first drop of addition was 2.5h, and the dropping time of the second drop of addition was 3.0 h.
Example 5
This example prepared a polycarboxylic acid compound, and the specific procedure differs from example 1 in that:
(1) in step D4a, macromonomer TPEG with an average molecular weight of about 2400 was replaced with macromonomer TPEG with an average molecular weight of about 4000 (about 0.095mol) with a mass of 380 g;
(2) in step D4a, the hydrogen peroxide was changed to ammonium persulfate with a mass of 3.82g (about 0.0167 mol);
(3) in step D4b, the chain transfer agent was replaced, specifically by replacing 1.65g of mercaptopropionic acid with 1.60g of mercaptoacetic acid (about 0.01737 mol).
(4) In step D4c, the temperature is 40 ℃; the dropping time of the first drop of addition was 3.0h, and the dropping time of the second drop of addition was 3.5 h.
Example 6
This example prepared a polycarboxylic acid compound, and the specific procedure differs from example 1 in that:
(1) in step D4a, macromonomer TPEG with an average molecular weight of about 2400 was replaced by macromonomer VPEG with an average molecular weight of about 3000 and a mass of 320g (about 0.1067 mol).
(2) In step D4a, the hydrogen peroxide mass was changed to 3.0g (about 0.02427 mol).
(3) In step D4b, the composition of the first drop was a mixture of 30g acrylic acid (about 0.4163mol), 18g maleic anhydride (about 0.1836mol), 50g vinylsulfonated calix [4] arene (product of step D3, about 0.0555mol) and 15g hydroxyethyl acrylate (about 0.1292 mol).
(4) In step D4b, the mass of the chain transfer agent mercaptopropionic acid was changed to 1.80g (about 0.017 mol).
(5) In step D4c, the temperature is 15 ℃; the dropping time of the first drop of addition was 60min, and the dropping time of the second drop of addition was 70 min.
Example 7
This example prepared a polycarboxylic acid compound, and the specific procedure differs from example 1 in that:
(1) step D4 is different from example 1, specifically, the polymerization reaction in this example includes:
D4. polymerization reaction:
d4a. into a flask equipped with a stirrer, macromonomer EPEG (about 0.1067mol) having an average molecular weight of about 6000 and a mass of 640g, iron sulfate (initiator) 1.0g (1.0% aqueous solution, about 0.00066mol) and 27.5 wt% hydrogen peroxide (initiator) solution 2.8g (about 0.02265mol) were charged to obtain a primer;
d4b. mixing 32g of acrylic acid (about 0.444mol), 45g of vinylsulfonated calix [4] arene (product of step D3, about 0.05mol) and 10g of ethyl acrylate (about 0.09988mol) to form a first drop; mixing 1.65g of mercaptoethanol (about 0.02119mol) and 0.7g of ascorbic acid (about 0.003975mol) to form a second drop;
adjusting the temperature of the bottom material to 5 ℃ under the stirring state of D4 c; dripping a first dripping material and a second dripping material into the mixture, wherein the dripping starting time of the first dripping material is the same as that of the second dripping material, the total dripping time of the first dripping material is 40min, and the dripping time of the second dripping material is 45 min; and D, after the two kinds of dropping materials are dripped, preserving the heat for 1.0h to obtain the polycarboxylic acid compound, and dispersing the polycarboxylic acid compound in the system obtained in the step D4c.
Example 8
This example prepared a polycarboxylic acid compound, and the specific procedure differs from example 1 in that:
(1) step D4 is different from example 1, specifically, the polymerization reaction in this example includes:
D4. polymerization reaction:
d4a. into a flask equipped with a stirrer, a macromonomer, VPEG (about 0.09375mol), having an average molecular weight of about 8000 and a mass of 750g, 1g of ferrous sulfate (initiator) (about 0.000067mol, 1g of a 1% by mass aqueous solution), and 2.8g (about 0.02265mol) of a 27.5 wt% hydrogen peroxide (initiator) solution were charged to obtain a primer;
d4b. mixing 36g of acrylic acid (about 0.5mol), 45g of vinylsulfonated calix [4] arene (product of step D3, about 0.05mol) and 10g of hydroxypropyl acrylate (about 0.07868mol) to form a first drop; mixing 1.70g mercaptoethanol (about 0.02176mol) and 0.8g ascorbic acid (about 0.0045mol) to form a second drop;
adjusting the temperature of the base material to 10 ℃ under the stirring state of D4 c; dripping a first dripping material and a second dripping material into the mixture, wherein the dripping starting time of the first dripping material is the same as that of the second dripping material, the total dripping time of the first dripping material is 50min, and the dripping time of the second dripping material is 55 min; and D, after the two kinds of dropping materials are dripped, preserving the heat for 1.0h to obtain the polycarboxylic acid compound, and dispersing the polycarboxylic acid compound in the system obtained in the step D4c.
Example 9
The embodiment prepares the polycarboxylate superplasticizer, and the specific process is as follows:
E1. adjusting the pH of the system containing the polycarboxylic acid compound obtained in example 1 to 6-8 with 30 wt% of sodium hydroxide aqueous solution;
E2. the solids content of the system obtained in step E1 was adjusted to 40% with deionized water.
Examples 10 to 16 each prepare a polycarboxylic acid water reducing agent, and the difference from example 9 is that examples 10 to 16 each employ the system containing the polycarboxylic acid compound obtained in examples 2 to 8.
Comparative example 1
This comparative example prepared a polycarboxylic acid compound, which differs from example 1 in that:
(1) does not include steps D1-D3;
(2) in step D4a, the added mass of hydrogen peroxide was 2.2 g;
(3) in step D4b, the first drop of feed did not include the vinyl sulfonated calix [4] arene;
(4) in step D4b, the amount of mercaptopropionic acid added was changed from 1.65g to 1.5g, and the amount of ascorbic acid added was changed from 0.7g to 0.4 g.
Comparative example 2
This comparative example prepared a polycarboxylic acid compound, which differs from example 1 in that:
(1) does not include steps D1-D3;
(2) step D4 in contrast, specifically, comparative example D4 is:
D4. polymerization reaction:
d4a. adding 300g of macromonomer HPEG, 0.1g of ferrous sulfate (initiator) and 2.5g of 27.5 wt% hydrogen peroxide (initiator) solution into a flask provided with a stirrer to obtain a bottom material, wherein the average molecular weight of the flask is 2400;
forming 9g of acrylic acid into a first drop D4b; 3.8g of sodium hypophosphite (chain transfer agent) and 0.4g of ascorbic acid (initiator) were mixed to form a second drop;
adjusting the temperature of the bottom material to 30 ℃ under the stirring state of D4 c; dropwise adding a first dropwise material and a second dropwise material into the mixture, wherein the dropwise adding time of the first dropwise material is the same as that of the second dropwise material, the total dropwise adding time of the first dropwise material is 2.0 hours, and the dropwise adding time of the second dropwise material is 2.5 hours; and D, after the two kinds of dropping materials are dripped, preserving the heat for 1.0h to obtain the polycarboxylic acid compound, and dispersing the polycarboxylic acid compound in the system obtained in the step D4c.
The polycarboxylate superplasticizers are prepared in comparative examples 3 to 4 respectively, and the difference from example 9 is that the systems containing the polycarboxylate compounds obtained in comparative examples 1 to 2 are adopted in comparative examples 3 to 4 respectively.
Test examples
In the first aspect of this test example, the average molecular weights of the polycarboxylic acid water-reducing agents prepared in examples 9 to 16 and comparative examples 3 to 4 were measured by using a P230 type GPC-gel permeation chromatography system (Elite, Dalian; column PL aquagel-OH MIXED (7.5mm I.D. 30cm) (Agilent, US); injection flow rate: 1.0 ml/min; mobile phase: 0.1M NaNO; (NaNO); sample concentration: 0.5M)3(ii) a Standard samples: polysaccharide): the test results are shown in table 1.
TABLE 1 average molecular weight of polycarboxylic acid water-reducing agent prepared in examples 9 to 16 and comparative examples 3 to 4
| Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | |
| Average molecular weight | 48500 | 50600 | 49200 | 61600 | 61600 |
| Example 14 | Example 15 | Example 16 | Comparative example 3 | Comparative example 4 | |
| Average molecular weight | 61600 | 68300 | 76500 | 36100 | 34200 |
In the second aspect of the test example, the fluidity performance of the cement paste obtained after the polycarboxylic acid water reducing agent obtained in examples 9 to 16 and comparative examples 3 to 4 is used as a concrete admixture is tested;
two groups of tests are carried out, one group is a test without mixing mud, and the other group is a test with mixing mud amount of 1.0 percent (taking the total mass of the mud and the cement as a base number), wherein the mixed mud is montmorillonite;
the adopted cement is south (Taojiang) type PO 42.5 cement, and the folding and solid adding amount of the polycarboxylate superplasticizer is 0.11 percent (the solid polycarboxylate superplasticizer accounts for 0.11 percent of the total mass of the cement (and the doped mud));
the concrete test method is carried out by referring to the national standard document GB/T8077-2012 'concrete admixture homogeneity test method'; the test results are shown in table 2.
TABLE 2 test results of fluidity of cement paste of polycarboxylate superplasticizers obtained in examples 9 to 16 and comparative examples 3 to 4
As can be seen from Table 2, the dispersing ability (the stronger the dispersing ability, the larger the value of the net paste fluidity) of the polycarboxylic acid water reducing agents obtained in examples 9 to 16 and comparative examples 3 to 4 is equivalent without adding clay; as the soil content increases, the dispersing ability of the water reducing agent decreases; however, when the amount of the admixture in the neat cement paste is 1.0%, the fluidity of the neat cement pastes of examples 9 to 16 is slightly reduced, but is significantly higher than that of the neat cement pastes of comparative examples 3 to 4, and particularly in comparative example 4, the fluidity of the neat cement paste is not improved after 60 min; the introduction of calixarene groups in the polycarboxylate superplasticizer provided by the invention can effectively improve the mud resistance of the polycarboxylate superplasticizer; the comparison between comparative examples 3-4 also shows that the mud resistance of the polycarboxylate superplasticizer can be improved to a certain extent by introducing the unsaturated acid ester monomer.
In the second aspect of the test example, the performance of the concrete obtained by using the polycarboxylic acid water reducing agent obtained in examples 9 to 16 and comparative examples 3 to 4 as a concrete admixture was tested;
in the test process, according to an internal mixing method, 5% of sand by mass is replaced by the soil (the mud content of the washed sand is 0, namely the soil mass is 5% of the sum of the soil and the sand mass); the folding and fixing mixing amount of the polycarboxylate superplasticizer is 0.2-0.25%;
the concrete is prepared by mixing 200 parts by weight of cement (southern China (Taojiang), type PO 42.5), 80 parts by weight of mineral powder (first steel S95 grade), 60 parts by weight of fly ash (Changsha second grade ash), 860 parts by weight of machine-made sand (medium sand with fineness modulus of 3.1), 1020 parts by weight of stones (with particle size of 5-25 mm) and 150 parts by weight of water, wherein the stirring time is 120 seconds and the vibrating time is 15 seconds;
concrete performance detection is carried out according to the national standard GB/T50080-2016 Standard test method for the Performance of common concrete mixtures, and the test results are shown in Table 3.
Table 3 concrete Performance results containing the polycarboxylate superplasticizers obtained in examples 9 to 16 and comparative examples 3 to 4
As can be seen from Table 3, the polycarboxylic acid water reducing agent provided by the invention not only has good water reducing performance (the larger the concrete expansion degree is, the better the water reducing effect is compared with the common water reducing agent under the same other conditions), but also can obtain excellent slump retaining capability under the condition of lower mixing amount. No matter the concrete strength is 3d or 28d, the concrete containing the polycarboxylate water reducer obtained in the embodiment 9-16 has higher strength than that of the concrete in the comparative example, and soil influences the strength of the concrete, so that the polycarboxylate water reducer obtained by the invention has excellent early strength and mud resistance.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A polycarboxylic acid compound having the structural formula shown in formula I:
wherein:
R1is-H or-CH3；
R2is-COOH or-H;
R3is-H, -CH2COOH or-CH3One of (1);
R4is-H or-CH3；
R5is-CH2CH2OH、—CH2CH2CH2OH、—CH2CH(OH)CH3、—CH3or-CH2CH3One of (1);
R6is-H or-CH3；
R7is-CH2—、—CH2CH2—、—OCH2CH2-or-OCH2CH2CH2CH2-one of;
R8is-SO3H or-SO3Na；
R9is-COOH or-COONa;
a, b, x, y, m, n are the number of repetitions of the repeating unit,
a:y＝(0.1～1.5):1，b:y＝(2.5～6.0):1，x:y＝(0.5～1.5):1，m＝27～180，n＝4，6，8。
2. the polycarboxylic acid compound according to claim 1, wherein R in formula I8is-SO3Na。
3. The polycarboxylic acid compound according to claim 1 or 2, having an average molecular weight of 20000 to 80000.
4. The method for preparing a polycarboxylic acid compound according to any one of claims 1 to 3, comprising polymerizing a vinyl sulfonated calix [ n ] arene, a polyether macromonomer, an unsaturated acid monomer and an unsaturated acid ester monomer under the action of a chain transfer agent and an initiator to obtain the polycarboxylic acid compound.
5. The method according to claim 4, wherein the polyether macromonomer has an average molecular weight of 1200 to 8000.
6. The preparation method according to claim 4, wherein the molar ratio of the initiator to the polyether macromonomer is (0.01-0.5): 1.
7. The preparation method according to claim 4, wherein the molar ratio of the chain transfer agent to the polyether macromonomer is (0.05-0.5): 1.
8. The preparation method according to claim 4, wherein the polymerization reaction is carried out for 0.5-4.0 h.
9. A polycarboxylic acid water reducing agent characterized by comprising the polycarboxylic acid compound according to any one of claims 1 to 3.
10. Use of the polycarboxylic acid water reducer according to claim 9 as a concrete admixture.
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