CN109970920B - Sulfonic acid modified polycarboxylic acid water reducing agent and preparation method thereof - Google Patents

Sulfonic acid modified polycarboxylic acid water reducing agent and preparation method thereof Download PDF

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CN109970920B
CN109970920B CN201810591736.9A CN201810591736A CN109970920B CN 109970920 B CN109970920 B CN 109970920B CN 201810591736 A CN201810591736 A CN 201810591736A CN 109970920 B CN109970920 B CN 109970920B
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sulfonic acid
hydroxynaphthalene
hydroxymethylnaphthalene
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CN109970920A (en
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蒋卓君
郭鑫祺
尤仁良
官梦芹
陈晓彬
李祥河
林添兴
郭元强
麻秀星
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Kezhijie New Material Group Guizhou Co ltd
Kezhijie New Material Group Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a sulfonic acid modified polycarboxylate superplasticizer and a preparation method thereof, wherein the molecular weight of the sulfonic acid modified polycarboxylate superplasticizer is 10000-150000, and the structural formula of the sulfonic acid modified polycarboxylate superplasticizer is as follows:

Description

Sulfonic acid modified polycarboxylic acid water reducing agent and preparation method thereof
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a sulfonic acid modified polycarboxylic acid water reducing agent and a preparation method thereof.
Background
Concrete is one of the most used engineering materials in the world at present, and a water reducing agent is one of key technologies for preparing high-performance concrete and is an indispensable component for preparing modern high-performance concrete with good durability. The basic function of the concrete is to improve the workability of fresh concrete and improve the fluidity without changing the unit water consumption, thereby improving the mechanical property and durability of the concrete.
The volume ratio of the sand to the stone in the cement concrete is about 60-75%, and the mass ratio is 70-80%, and the sand to the stone is an important component of the concrete. The current production situation of concrete raw materials shows that sand inevitably contains mud. On one hand, the sand and the mud are due to argillaceous and weathered rocks deposited in mountain rock fractures and cannot be completely removed before being crushed; on the other hand, the silt interlayer between the sand and egg layers of the ancient river bed cannot be thoroughly cleaned by adopting crushing and screening processes and the like, and the influence of natural factors and human factors causes that the silt is inevitably brought into the production process of the sand and stone. Secondly, along with the continuous shortage of resources, the occurrence of machine-made sand and the high mud content in the machine-made sand, the problems of insufficient water reducing rate, sensitivity and poor slump retaining effect of the polycarboxylic acid water reducing agent in the application process are caused, and in order to meet the market demand, a product which is insensitive to the mud content and the powder content of sand and stones, high in water reducing rate and good in slump retaining is required to be developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a sulfonic acid modified polycarboxylic acid water reducing agent.
The invention also aims to provide a preparation method of the sulfonic acid modified polycarboxylic acid water reducing agent.
The technical scheme of the invention is as follows:
a sulfonic acid modified polycarboxylic acid water reducing agent has a molecular weight of 10000-150000 and a structural formula as follows:
Figure BDA0001690054720000021
wherein R is1Is H or CH3，R2Is C1-C4 alkyl, R3Is empty or C1-C4 alkyl, R4Is empty or C1-C4 alkyl, R5Is H or COOM, R6Is H or CH3，R7Is H or COOM, R8Is H or CH3，R9Is empty or C1-C4 alkyl, R10Is a naphthalene ring having one alkylcarboxylate substituent, M is H, Na, K or NH4；R3And R4The relationship with respect to the benzene ring is ortho, meta or para.
The preparation method of the sulfonic acid modified polycarboxylic acid water reducing agent comprises the following steps:
(1) a first esterification reaction: mixing unsaturated polyether and a first compound, heating to 70-90 ℃ under the protection of nitrogen, adding a catalyst, carrying out heat preservation reaction for 0.5-3.0 h, removing water by vacuumizing or introducing nitrogen and water, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an esterification product and unreacted unsaturated polyether; the unsaturated polyether is at least one of allyl polyethylene glycol, 3-methyl-3-butylene-1-polyethylene glycol and 2-methylallyl polyethylene glycol with the molecular weight of 600-5000; the structural formula of the first compound is as follows:
Figure BDA0001690054720000022
(2) second esterification reaction: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, hydroxynaphthalene carboxylic acid and a polymerization inhibitor, heating to 90-120 ℃ under the protection of nitrogen, adding a catalyst, carrying out heat preservation reaction for 0.5-3.0 h, removing water by vacuumizing or introducing nitrogen and carrying water, and cooling to room temperature after the reaction is finished to obtain a second mixture containing an esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride; the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is at least one of acrylic acid, methacrylic acid, maleic acid and maleic anhydride; the hydroxynaphthalene sulfonic acid is 1-hydroxynaphthalene-4 sulfonic acid, 1-hydroxynaphthalene-5 sulfonic acid, 1-hydroxynaphthalene-6 sulfonic acid, 1-hydroxynaphthalene-7 sulfonic acid, 2-hydroxynaphthalene-4 sulfonic acid, 2-hydroxynaphthalene-5 sulfonic acid, 2-hydroxynaphthalene-6 sulfonic acid, 2-hydroxynaphthalene-7 sulfonic acid, 1-hydroxymethylnaphthalene-4 sulfonic acid, 1-hydroxymethylnaphthalene-5 sulfonic acid, 1-hydroxymethylnaphthalene-6 sulfonic acid, 1-hydroxymethylnaphthalene-7 sulfonic acid, 2-hydroxymethylnaphthalene-4 sulfonic acid, 2-hydroxymethylnaphthalene-5 sulfonic acid, 2-hydroxymethylnaphthalene-6 sulfonic acid, 2-hydroxymethylnaphthalene-7 sulfonic acid, 1-hydroxynaphthalene-4 methanesulfonic acid, 1-hydroxynaphthalene-5 methanesulfonic acid, At least one of 1-hydroxynaphthalene-6 methanesulfonic acid, 1-hydroxynaphthalene-7 methanesulfonic acid, 2-hydroxynaphthalene-4 methanesulfonic acid, 2-hydroxynaphthalene-5 methanesulfonic acid, 2-hydroxynaphthalene-6 methanesulfonic acid, 2-hydroxynaphthalene-7 methanesulfonic acid, 1-hydroxymethylnaphthalene-4 methanesulfonic acid, 1-hydroxymethylnaphthalene-5 methanesulfonic acid, 1-hydroxymethylnaphthalene-6 methanesulfonic acid, 1-hydroxymethylnaphthalene-7 methanesulfonic acid, 2-hydroxymethylnaphthalene-4 methanesulfonic acid, 2-hydroxymethylnaphthalene-5 methanesulfonic acid, 2-hydroxymethylnaphthalene-6 methanesulfonic acid, and 2-hydroxymethylnaphthalene-7 methanesulfonic acid;
(3) monomer blending: mixing the first mixture prepared in the step (1) and the second mixture prepared in the step (2) in a mass ratio of 100: 6-18, and adding water to dissolve the mixture to obtain a comonomer mixture solution;
(4) and (3) copolymerization reaction: dripping the comonomer mixture solution, the initiator aqueous solution and the molecular weight regulator aqueous solution into water for reaction at the reaction temperature of 10-60 ℃ for 0.2-6.0 h, and preserving heat for 0-3.0 h after dripping to obtain a copolymerization product;
(5) and (3) neutralization reaction: and (4) adjusting the pH of the copolymerization product prepared in the step (3) to 5-7 by using alkali to obtain the sulfonic acid modified polycarboxylic acid water reducing agent.
In a preferred embodiment of the present invention, in the step (1), the molar ratio of the unsaturated polyether to the first compound is 1-1.5: 1, and the amount of the catalyst is 0.05-0.3% of the total mass of the unsaturated polyether and the first compound.
In a preferred embodiment of the present invention, in the step (2), the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and hydroxynaphthalene carboxylic acid is 2-7: 1, and the amount of the catalyst is 0.03-0.3% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and hydroxynaphthalene carboxylic acid; the dosage of the polymerization inhibitor is 0.2-3.0% of the total mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride and the hydroxynaphthalene carboxylic acid.
In a preferred embodiment of the present invention, the total amount of water used in the steps (3) and (4) is such that the mass concentration of the copolymerization product is 20 to 70%, the amount of the initiator is 0.5 to 3.0% of the total mass of the solutes in the comonomer mixture solution, and the amount of the molecular weight modifier is 0.2 to 2.0% of the total mass of the solutes in the comonomer mixture solution.
Further preferably, the catalyst is at least one of mellitic acid, azethioic acid and trinitrobenzenesulfonic acid.
Further preferably, the polymerization inhibitor is at least one of hydroquinone, phenothiazine and diphenylamine.
Further preferably, the initiator is a water-soluble redox initiation system or a water-soluble azo initiator.
Further preferably, the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, sodium formate, sodium acetate, and dodecanethiol.
The invention has the beneficial effects that:
1. according to the invention, an esterification product of an unsaturated polyether monomer and a first compound is used for synthesis of a polycarboxylate water reducer, a benzene ring and a sulfonic group structure are introduced at the tail end of a branched chain of a polycarboxylate water reducer molecule, the benzene ring structure enhances the steric hindrance effect of the branched chain of the polycarboxylate water reducer molecule, and the sulfonic group structure enables the branched chain of the polycarboxylate water reducer molecule to have not only the steric hindrance effect but also the electrostatic repulsion effect, so that the prepared polycarboxylate water reducer has higher water reduction rate;
2. the invention also introduces the naphthalenesulfonic acid side group on the main chain of the polycarboxylate water reducer molecule by using the esterification product of unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and hydroxynaphthalenesulfonic acid for the synthesis of polycarboxylate water reducer, so that the adsorption effect of polycarboxylate water reducer on cement, mud and stone powder is changed, and the prepared polycarboxylate water reducer has the effect of low sensitivity to mud and powder content in concrete aggregate;
3. the ester group structure in the polycarboxylate superplasticizer can be gradually hydrolyzed under the alkaline environment of concrete to release part of carboxylic acid groups with the water reducing effect, so that the prepared polycarboxylate superplasticizer also has a certain slump retaining effect.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
The molecular weight of the sulfonic acid modified polycarboxylate superplasticizer prepared in the following embodiment is 10000-150000, and the structural formula is as follows:
Figure BDA0001690054720000051
wherein R is1Is H or CHs，R2Is C1-C4 alkyl, R3Is empty or C1-C4 alkyl, R4Is empty or C1-C4 alkyl, R5Is H or COOM, R6Is H or CH3，R7Is H or COOM, R8Is H or CH3，R9Is empty or C1-C4 alkyl, R10Is a naphthalene ring having one alkylcarboxylate substituent, M is H, Na, K or NH4；R3And R4The relationship with respect to the benzene ring is ortho, meta or para.
Example 1
(1) A first esterification reaction: mixing 500.00g of allyl polyethylene glycol with the molecular weight of 1000 and 100.00g of ortho-carboxyl benzenesulfonic acid, heating to 70 ℃ under the protection of nitrogen, adding 0.45g of mellitic acid, carrying out heat preservation reaction for 2.0h, removing water by vacuumizing or introducing nitrogen to carry out water-carrying reaction, and cooling to room temperature after the reaction is finished to obtain a first mixture containing the esterification product and unreacted allyl polyethylene glycol.
(2) Second esterification reaction: mixing 70.00g of acrylic acid, 100.00g of 1-hydroxynaphthalene-4-sulfonic acid and 2.00g of hydroquinone, heating to 95 ℃ under the protection of nitrogen, adding 0.15g of mellitic acid, carrying out heat preservation reaction for 2.5h, removing water by vacuumizing or introducing nitrogen to carry water, and cooling to room temperature after the reaction is finished to obtain a second mixture containing an esterification product and unreacted acrylic acid;
(3) monomer blending: mixing 100.00g of the first mixture obtained in step (1) and 8.00g of the second mixture obtained in step (2), and adding 40.00g of water to dissolve them, to obtain a comonomer mixture solution;
(4) and (3) copolymerization reaction: dripping the comonomer mixture solution, a hydrogen peroxide aqueous solution (wherein 0.80g of hydrogen peroxide and 10.00g of water), an ascorbic acid aqueous solution (wherein 0.20g of water and 10.00g of water) and a thioglycolic acid aqueous solution (wherein 0.80g of thioglycolic acid and 10.00g of water) into 40.00g of water for reaction at the reaction temperature of 50 ℃ for 3.0h, and preserving heat for 0.5h after dripping to obtain a copolymerization product;
(5) and (3) neutralization reaction: and (3) adjusting the pH of the copolymerization product prepared in the step (4) to 5-7 by using alkali to obtain the sulfonic acid modified polycarboxylic acid water reducing agent PCE-1.
Example 2
(1) A first esterification reaction: 1030.00g of 3-methyl-3-butene-1-polyethylene glycol with molecular weight of 2000 and 100.00g of m-carboxymethyl benzenesulfonic acid are mixed, the temperature is raised to 70 ℃ under the protection of nitrogen, 0.90g of nitrogen-sulfur squaric acid is added, the mixture is kept for reaction for 2.0h, water is removed by vacuumizing or introducing nitrogen to carry out water, and the temperature is reduced to room temperature after the reaction is finished to obtain a first mixture containing the esterification product and unreacted 3-methyl-3-butene-1-polyethylene glycol.
(2) Second esterification reaction: mixing 85.00g of methacrylic acid, 100.00g of 1-hydroxynaphthalene-5 sulfonic acid and 1.80g of phenothiazine, heating to 95 ℃ under the protection of nitrogen, adding 0.15g of nitrogen-sulfur squaric acid, keeping the temperature for reaction for 2.0h, removing water by vacuumizing or introducing nitrogen to carry water in the reaction period, and cooling to room temperature after the reaction is finished to obtain a second mixture containing an esterification product and unreacted methacrylic acid;
(3) monomer blending: mixing 100.00g of the first mixture obtained in step (1) and 9.00g of the second mixture obtained in step (2), and adding 40.00g of water to dissolve them, to obtain a comonomer mixture solution;
(4) and (3) copolymerization reaction: dropping the comonomer mixture solution, azobisisobutylamidine hydrochloride aqueous solution (wherein the weight of the azobisisobutylamidine hydrochloride is 1.00g, the weight of the water is 10.00g) and sodium hypophosphite aqueous solution (wherein the weight of the sodium hypophosphite is 0.70g, the weight of the water is 10.00g) into 40.00g of water for reaction, wherein the reaction temperature is 40 ℃, the dropping time is 2.0h, and after the dropping is finished, preserving the heat for 1.0h to obtain a copolymerization product;
(5) and (3) neutralization reaction: and (3) adjusting the pH of the copolymerization product prepared in the step (4) to 5-7 by using alkali to obtain the sulfonic acid modified polycarboxylic acid water reducing agent PCE-2.
Example 3
(1) A first esterification reaction: 1132.00g of 2-methylallyl polyethylene glycol with the molecular weight of 2400 and 100.00g of p-carboxyethyl benzene sulfonic acid are mixed, the temperature is raised to 80 ℃ under the protection of nitrogen, 2.70g of trinitrobenzene sulfonic acid is added, the mixture is kept warm and reacts for 1.5h, water is removed by vacuumizing or introducing nitrogen to carry water in the period, and the temperature is reduced to room temperature after the reaction is finished, so that a first mixture containing the esterification product and unreacted 2-methylallyl polyethylene glycol is obtained.
(2) Second esterification reaction: mixing 155.00g of maleic acid, 100.00g of 1-hydroxynaphthalene-6-sulfonic acid and 1.50g of diphenylamine, heating to 100 ℃ under the protection of nitrogen, adding 0.60g of trinitrobenzenesulfonic acid, carrying out heat preservation reaction for 2.0h, removing water by vacuumizing or introducing nitrogen to carry out water removal in the reaction period, and cooling to room temperature after the reaction is finished to obtain a second mixture containing an esterification product and unreacted maleic acid;
(3) monomer blending: mixing 100.00g of the first mixture obtained in step (1) and 10.00g of the second mixture obtained in step (2), and adding 40.00g of water to dissolve them, to obtain a comonomer mixture solution;
(4) and (3) copolymerization reaction: dripping the comonomer mixture solution, an azodicyano valeric acid aqueous solution (wherein 2.00g of azodicyano valeric acid and 10.00g of water) and a trisodium phosphate aqueous solution (wherein 1.00g of trisodium phosphate and 10.00g of water) into 40.00g of water for reaction at the reaction temperature of 55 ℃ for 2.0h, and preserving heat for 1.0h after finishing dripping to obtain a copolymerization product;
(5) and (3) neutralization reaction: and (3) adjusting the pH of the copolymerization product prepared in the step (4) to 5-7 by using alkali to obtain the sulfonic acid modified polycarboxylic acid water reducing agent PCE-3.
Example 4
(1) A first esterification reaction: 1420.00g of allyl polyethylene glycol with the molecular weight of 3000 and 100.00g of ortho-carboxyl benzyl sulfonic acid are mixed, the temperature is raised to 90 ℃ under the protection of nitrogen, 4.30g of mellitic acid is added, the temperature is kept for reaction for 2.0h, water is removed by vacuumizing or introducing nitrogen to carry out water-carrying reaction in the period, and the temperature is lowered to the room temperature after the reaction is finished, so that a first mixture containing the esterification product and unreacted allyl polyethylene glycol is obtained.
(2) Second esterification reaction: mixing 175.00g of maleic anhydride, 100.00g of 1-hydroxynaphthalene-7 sulfonic acid and 2.20g of hydroquinone, heating to 100 ℃ under the protection of nitrogen, adding 0.75g of trinitrobenzenesulfonic acid, carrying out heat preservation reaction for 1.0h, removing water by vacuumizing or introducing nitrogen to carry out water removal in the reaction period, and cooling to room temperature after the reaction is finished to obtain a second mixture containing an esterification product and unreacted maleic anhydride;
(3) monomer blending: mixing 100.00g of the first mixture obtained in step (1) and 11.00g of the second mixture obtained in step (2), and adding 40.00g of water to dissolve them, to obtain a comonomer mixture solution;
(4) and (3) copolymerization reaction: dripping the comonomer mixture solution, a hydrogen peroxide aqueous solution (wherein, 0.90g of hydrogen peroxide and 10.00g of water), a trisodium phosphate aqueous solution (wherein, 0.90g of trisodium phosphate and 10.00g of water) and an ascorbic acid aqueous solution (wherein, 0.30 g of ascorbic acid and 10.00g of water) into 40.00g of water for reaction at the reaction temperature of 30 ℃ for 1.5h, and preserving heat for 1.0h after finishing dripping to obtain a copolymerization product;
(5) and (3) neutralization reaction: and (3) adjusting the pH of the copolymerization product prepared in the step (4) to 5-7 by using alkali to obtain the sulfonic acid modified polycarboxylic acid water reducing agent PCE-4.
Example 5
(1) A first esterification reaction: 1890.00g of 3-methyl-3-butene-1-polyethylene glycol with the molecular weight of 4000 and 100.00g of p-carboxymethylbenzylethylsulfonic acid are mixed, the temperature is raised to 85 ℃ under the protection of nitrogen, 5.60g of trinitrobenzenesulfonic acid is added, the mixture is kept for reaction for 2.0h, water is removed by vacuumizing or introducing nitrogen to carry out water, and the temperature is reduced to room temperature after the reaction is finished, so that a first mixture containing the esterification product and the unreacted 3-methyl-3-butene-1-polyethylene glycol is obtained.
(2) Second esterification reaction: mixing 96.00g of acrylic acid, 100.00g of 2-hydroxynaphthalene-4 sulfonic acid and 3.50g of phenothiazine, heating to 110 ℃ under the protection of nitrogen, adding 0.40g of nitrogen-sulfur squaric acid, keeping the temperature for reaction for 1.5h, removing water by using a vacuumizing or nitrogen-introducing water-carrying method during the reaction, and cooling to room temperature after the reaction is finished to obtain a second mixture containing an esterification product and unreacted acrylic acid;
(3) monomer blending: mixing 100.00g of the first mixture obtained in step (1) and 8.00g of the second mixture obtained in step (2), and adding 40.00g of water to dissolve them, to obtain a comonomer mixture solution;
(4) and (3) copolymerization reaction: dripping the comonomer mixture solution and an azodicyano valeric acid aqueous solution (wherein, the azodicyano valeric acid is 2.00g, the water is 10.00g) and a sodium hypophosphite aqueous solution (wherein, the sodium hypophosphite is 1.00g, the water is 20.00g) into 40.00g of water for reaction, wherein the reaction temperature is 40 ℃, the dripping time is 3.0h, and preserving heat for 2.0h after the dripping is finished to obtain a copolymerization product;
(5) and (3) neutralization reaction: and (3) adjusting the pH of the copolymerization product prepared in the step (4) to 5-7 by using alkali to obtain the sulfonic acid modified polycarboxylic acid water reducing agent PCE-5.
According to GB/T8076-2008, when the sulfonic acid modified polycarboxylic acid water reducing agent prepared in the embodiments 1 to 5 is tested, when the folding and solid content is 0.20 wt% (relative to the cement content), the water reducing rate is higher than 44%, the 28d compressive strength ratio is larger than 140%, and the 28d shrinkage ratio is smaller than 110%.
Adopting Fufu P.O 42.5.5 common Portland cement, and the concrete mixing ratio is as follows: cement 300kg/m3100kg/m of fly ash3100kg/m of mineral powder3690kg/m of sand31050kg/m of stones3160kg/m of water33.5 percent of bentonite (relative to the dosage of cement) is added,the sulfonic acid-modified polycarboxylic acid water reducing agent prepared in examples 1 to 5 and a commercially available polycarboxylic acid water reducing agent (PCE) were subjected to a performance test according to a folding blending amount of 0.15%. The initial slump and the expansion degree of the concrete and the 2h slump and the expansion degree of the concrete are tested, and the test results of different additives are shown in Table 1.
TABLE 1 results of different admixtures
Figure BDA0001690054720000081
Figure BDA0001690054720000091
As can be seen from Table 1, for the material doped with bentonite, the synthesized examples of the patent have higher water reducing rate and better slump keeping performance compared with the commercially available polycarboxylate superplasticizer (PCE), and therefore, the polycarboxylate superplasticizer prepared by the patent has lower sensitivity to the material with high mud content.
It is obvious to those skilled in the art that the technical solution of the present invention can still obtain the same or similar technical effects as the above embodiments when changed within the following scope, and still fall into the protection scope of the present invention:
a sulfonic acid modified polycarboxylic acid water reducing agent has a molecular weight of 10000-150000 and a structural formula as follows:
Figure BDA0001690054720000092
wherein R is1Is H or CH3，R2Is C1-C4 alkyl, R3Is empty or C1-C4 alkyl, R4Is empty or C1-C4 alkyl, R5Is H or COOM, R6Is H or CH3，R7Is H or COOM, R8Is H or CH3，R9Is empty or C1-C4 alkyl, R10Is a naphthalene ring having one alkylcarboxylate substituent, M is H, Na, K or NH4；R3And R4The relation of the relative benzene ring is ortho-position, meta-position or para-positionA bit.
The preparation method of the sulfonic acid modified polycarboxylic acid water reducing agent comprises the following steps:
(1) a first esterification reaction: mixing unsaturated polyether and a first compound, heating to 70-90 ℃ under the protection of nitrogen, adding a catalyst, carrying out heat preservation reaction for 0.5-3.0 h, removing water by vacuumizing or introducing nitrogen and water, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an esterification product and unreacted unsaturated polyether; the unsaturated polyether is at least one of allyl polyethylene glycol, 3-methyl-3-butylene-1-polyethylene glycol and 2-methylallyl polyethylene glycol with the molecular weight of 600-5000; the structural formula of the first compound is as follows:
Figure BDA0001690054720000101
(2) second esterification reaction: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, hydroxynaphthalene carboxylic acid and a polymerization inhibitor, heating to 90-120 ℃ under the protection of nitrogen, adding a catalyst, carrying out heat preservation reaction for 0.5-3.0 h, removing water by vacuumizing or introducing nitrogen and carrying water, and cooling to room temperature after the reaction is finished to obtain a second mixture containing an esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride; the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is at least one of acrylic acid, methacrylic acid, maleic acid and maleic anhydride; the hydroxynaphthalene sulfonic acid is 1-hydroxynaphthalene-4 sulfonic acid, 1-hydroxynaphthalene-5 sulfonic acid, 1-hydroxynaphthalene-6 sulfonic acid, 1-hydroxynaphthalene-7 sulfonic acid, 2-hydroxynaphthalene-4 sulfonic acid, 2-hydroxynaphthalene-5 sulfonic acid, 2-hydroxynaphthalene-6 sulfonic acid, 2-hydroxynaphthalene-7 sulfonic acid, 1-hydroxymethylnaphthalene-4 sulfonic acid, 1-hydroxymethylnaphthalene-5 sulfonic acid, 1-hydroxymethylnaphthalene-6 sulfonic acid, 1-hydroxymethylnaphthalene-7 sulfonic acid, 2-hydroxymethylnaphthalene-4 sulfonic acid, 2-hydroxymethylnaphthalene-5 sulfonic acid, 2-hydroxymethylnaphthalene-6 sulfonic acid, 2-hydroxymethylnaphthalene-7 sulfonic acid, 1-hydroxynaphthalene-4 methanesulfonic acid, 1-hydroxynaphthalene-5 methanesulfonic acid, At least one of 1-hydroxynaphthalene-6 methanesulfonic acid, 1-hydroxynaphthalene-7 methanesulfonic acid, 2-hydroxynaphthalene-4 methanesulfonic acid, 2-hydroxynaphthalene-5 methanesulfonic acid, 2-hydroxynaphthalene-6 methanesulfonic acid, 2-hydroxynaphthalene-7 methanesulfonic acid, 1-hydroxymethylnaphthalene-4 methanesulfonic acid, 1-hydroxymethylnaphthalene-5 methanesulfonic acid, 1-hydroxymethylnaphthalene-6 methanesulfonic acid, 1-hydroxymethylnaphthalene-7 methanesulfonic acid, 2-hydroxymethylnaphthalene-4 methanesulfonic acid, 2-hydroxymethylnaphthalene-5 methanesulfonic acid, 2-hydroxymethylnaphthalene-6 methanesulfonic acid, and 2-hydroxymethylnaphthalene-7 methanesulfonic acid;
(3) monomer blending: mixing the first mixture prepared in the step (1) and the second mixture prepared in the step (2) in a mass ratio of 100: 6-18, and adding water to dissolve the mixture to obtain a comonomer mixture solution;
(4) and (3) copolymerization reaction: dripping the comonomer mixture solution, the initiator aqueous solution and the molecular weight regulator aqueous solution into water for reaction at the reaction temperature of 10-60 ℃ for 0.2-6.0 h, and preserving heat for 0-3.0 h after dripping to obtain a copolymerization product;
(5) and (3) neutralization reaction: and (4) adjusting the pH of the copolymerization product prepared in the step (3) to 5-7 by using alkali to obtain the sulfonic acid modified polycarboxylic acid water reducing agent.
In the step (1), the molar ratio of the unsaturated polyether to the first compound is 1-1.5: 1, and the amount of the catalyst is 0.05-0.3% of the total mass of the unsaturated polyether and the first compound. In the step (2), the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride to the hydroxynaphthalene carboxylic acid is 2-7: 1, and the dosage of the catalyst is 0.03-0.3% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalene carboxylic acid; the dosage of the polymerization inhibitor is 0.2-3.0% of the total mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride and the hydroxynaphthalene carboxylic acid. The total amount of water used in the step (3) and the step (4) enables the mass concentration of the copolymerization product to be 20-70%, the amount of the initiator is 0.5-3.0% of the total mass of the solute in the comonomer mixture solution, and the amount of the molecular weight regulator is 0.2-2.0% of the total mass of the solute in the comonomer mixture solution.
The catalyst is at least one of mellitic acid, nitrogen-sulfur squaric acid and trinitrobenzene sulfonic acid. The polymerization inhibitor is at least one of hydroquinone, phenothiazine and diphenylamine. The initiator is a water-soluble redox initiation system or a water-soluble azo initiator. The molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, sodium formate, sodium acetate and dodecanethiol.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (8)

1. A sulfonic acid modified polycarboxylic acid water reducing agent is characterized in that: the molecular weight of the compound is 10000-150000;
the preparation method comprises the following steps:
(1) a first esterification reaction: mixing unsaturated polyether and a first compound, heating to 70-90 ℃ under the protection of nitrogen, adding a catalyst, carrying out heat preservation reaction for 0.5-3.0 h, removing water by using a vacuumizing or nitrogen-introducing and water-carrying method, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an esterification product and unreacted unsaturated polyether; the unsaturated polyether is at least one of allyl polyethylene glycol, 3-methyl-3-butylene-1-polyethylene glycol and 2-methylallyl polyethylene glycol with the molecular weight of 600-5000; the structural formula of the first compound is as follows:
Figure DEST_PATH_IMAGE002
；
(2) second esterification reaction: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, hydroxynaphthalene sulfonic acid and a polymerization inhibitor, heating to 90-120 ℃ under the protection of nitrogen, adding a catalyst, carrying out heat preservation reaction for 0.5-3.0 h, removing water by vacuumizing or introducing nitrogen during the reaction, and cooling to room temperature after the reaction is finished to obtain a second mixture containing an esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride; the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is at least one of acrylic acid, methacrylic acid, maleic acid and maleic anhydride; the hydroxynaphthalene sulfonic acid is 1-hydroxynaphthalene-4 sulfonic acid, 1-hydroxynaphthalene-5 sulfonic acid, 1-hydroxynaphthalene-6 sulfonic acid, 1-hydroxynaphthalene-7 sulfonic acid, 2-hydroxynaphthalene-4 sulfonic acid, 2-hydroxynaphthalene-5 sulfonic acid, 2-hydroxynaphthalene-6 sulfonic acid, 2-hydroxynaphthalene-7 sulfonic acid, 1-hydroxymethylnaphthalene-4 sulfonic acid, 1-hydroxymethylnaphthalene-5 sulfonic acid, 1-hydroxymethylnaphthalene-6 sulfonic acid, 1-hydroxymethylnaphthalene-7 sulfonic acid, 2-hydroxymethylnaphthalene-4 sulfonic acid, 2-hydroxymethylnaphthalene-5 sulfonic acid, 2-hydroxymethylnaphthalene-6 sulfonic acid, 2-hydroxymethylnaphthalene-7 sulfonic acid, 1-hydroxynaphthalene-4 methanesulfonic acid, 1-hydroxynaphthalene-5 methanesulfonic acid, At least one of 1-hydroxynaphthalene-6 methanesulfonic acid, 1-hydroxynaphthalene-7 methanesulfonic acid, 2-hydroxynaphthalene-4 methanesulfonic acid, 2-hydroxynaphthalene-5 methanesulfonic acid, 2-hydroxynaphthalene-6 methanesulfonic acid, 2-hydroxynaphthalene-7 methanesulfonic acid, 1-hydroxymethylnaphthalene-4 methanesulfonic acid, 1-hydroxymethylnaphthalene-5 methanesulfonic acid, 1-hydroxymethylnaphthalene-6 methanesulfonic acid, 1-hydroxymethylnaphthalene-7 methanesulfonic acid, 2-hydroxymethylnaphthalene-4 methanesulfonic acid, 2-hydroxymethylnaphthalene-5 methanesulfonic acid, 2-hydroxymethylnaphthalene-6 methanesulfonic acid, and 2-hydroxymethylnaphthalene-7 methanesulfonic acid;
(3) monomer blending: mixing the first mixture prepared in the step (1) and the second mixture prepared in the step (2) in a mass ratio of 100: 6-18, and adding water to dissolve the mixture to obtain a comonomer mixture solution;
(4) and (3) copolymerization reaction: dripping the comonomer mixture solution, the initiator aqueous solution and the molecular weight regulator aqueous solution into water for reaction at the reaction temperature of 10-60 ℃ for 0.2-6.0 h, and preserving heat for 0-3.0 h after dripping to obtain a copolymerization product;
(5) and (3) neutralization reaction: and (4) adjusting the pH of the copolymerization product prepared in the step (4) to 5-7 by using alkali to obtain the sulfonic acid modified polycarboxylic acid water reducing agent.
2. The sulfonic acid modified polycarboxylic acid water reducing agent of claim 1, characterized in that: in the step (1), the molar ratio of the unsaturated polyether to the first compound is 1-1.5: 1, and the amount of the catalyst is 0.05-0.3% of the total mass of the unsaturated polyether and the first compound.
3. The sulfonic acid modified polycarboxylic acid water reducing agent of claim 1, characterized in that: in the step (2), the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride to the hydroxynaphthalene sulfonic acid is 2-7: 1, and the dosage of the catalyst is 0.03-0.3% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalene sulfonic acid; the dosage of the polymerization inhibitor is 0.2-3.0% of the total mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride and the hydroxynaphthalene sulfonic acid.
4. The sulfonic acid modified polycarboxylic acid water reducing agent of claim 1, characterized in that: the total amount of water used in the step (3) and the step (4) enables the mass concentration of the copolymerization product to be 20-70%, the amount of the initiator is 0.5-3.0% of the total mass of the solute in the comonomer mixture solution, and the amount of the molecular weight regulator is 0.2-2.0% of the total mass of the solute in the comonomer mixture solution.
5. The sulfonic acid-modified polycarboxylic acid water reducing agent of any one of claims 1 to 4, characterized in that: the catalyst is at least one of mellitic acid, nitrothiofanic acid and trinitrobenzene sulfonic acid.
6. The sulfonic acid-modified polycarboxylic acid water reducing agent of any one of claims 1 to 4, characterized in that: the polymerization inhibitor is at least one of hydroquinone, phenothiazine and diphenylamine.
7. The sulfonic acid-modified polycarboxylic acid water reducing agent of any one of claims 1 to 4, characterized in that: the initiator is a water-soluble redox initiation system or a water-soluble azo initiator.
8. The sulfonic acid-modified polycarboxylic acid water reducing agent of any one of claims 1 to 4, characterized in that: the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, sodium formate, sodium acetate and dodecanethiol.
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