CN108623745B - Phosphorus-containing polycarboxylate superplasticizer and preparation method thereof - Google Patents
Phosphorus-containing polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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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
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- C04B24/246—Phosphorus-containing polymers containing polyether side chains
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
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Abstract
The invention discloses a phosphorus-containing polycarboxylate superplasticizer and a preparation method thereof, wherein the molecular weight of the phosphorus-containing polycarboxylate superplasticizer is 10000-150000, and the structural formula of the phosphorus-containing polycarboxylate superplasticizer is as follows:
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a phosphorus-containing polycarboxylic acid water reducer and a preparation method thereof.
Background
The polycarboxylate superplasticizer serving as a novel high-performance water reducing agent has a series of outstanding performances of low mixing amount, high water reducing rate, good slump retentivity, small shrinkage, relatively good adaptability to cement and admixtures, obvious reinforcing effect and the like. Meanwhile, the production process is environment-friendly, and the method is widely applied to various engineering fields at present. However, due to the rapid development of real estate market and infrastructure construction in China, a large amount of cement and gravel are consumed by a large amount of engineering construction, the shortage of gravel resource supply is aggravated, natural sand and stone resources in many areas in China are increasingly deficient, the supply of gravel materials is insufficient, so that the gravel materials are extremely unstable, the mud content of the gravel is high and unstable, and the polycarboxylic acid water reducer is applied to concrete, so that the problems of insufficient water reducing rate, poor slump loss resistance and increasingly prominent sensitivity are caused. Therefore, the water reducer which has high water reduction and slump retaining performance and is insensitive to the mud content of the material is significant.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a phosphorus-containing polycarboxylic acid water reducing agent.
The invention also aims to provide a preparation method of the phosphorus-containing polycarboxylate superplasticizer.
The technical scheme of the invention is as follows:
a phosphorus-containing polycarboxylic acid water reducing agent has a molecular weight of 10000-150000 and has a structural formula as follows:
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 with an alkyl phosphate 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 phosphorus-containing polycarboxylate superplasticizer 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:
(2) second esterification reaction: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, hydroxynaphthalene phosphoric 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 above-mentioned hydroxynaphthalene phosphoric acid is 1-hydroxynaphthalene-4 phosphoric acid, 1-hydroxynaphthalene-5 phosphoric acid, 1-hydroxynaphthalene-6 phosphoric acid, 1-hydroxynaphthalene-7 phosphoric acid, 2-hydroxynaphthalene-4 phosphoric acid, 2-hydroxynaphthalene-5 phosphoric acid, 2-hydroxynaphthalene-6 phosphoric acid, 2-hydroxynaphthalene-7 phosphoric acid, 1-hydroxymethylnaphthalene-4 phosphoric acid, 1-hydroxymethylnaphthalene-5 phosphoric acid, 1-hydroxymethylnaphthalene-6 phosphoric acid, 1-hydroxymethylnaphthalene-7 phosphoric acid, 2-hydroxymethylnaphthalene-4 phosphoric acid, 2-hydroxymethylnaphthalene-5 phosphoric acid, 2-hydroxymethylnaphthalene-6 phosphoric acid, 2-hydroxymethylnaphthalene-7 phosphoric acid, 1-hydroxynaphthalene-4 methylphosphoric acid, 1-hydroxynaphthalene-5 methylphosphoric acid, At least one of 1-hydroxynaphthalene-6 methylphosphoric acid, 1-hydroxynaphthalene-7 methylphosphoric acid, 2-hydroxynaphthalene-4 methylphosphoric acid, 2-hydroxynaphthalene-5 methylphosphoric acid, 2-hydroxynaphthalene-6 methylphosphoric acid, 2-hydroxynaphthalene-7 methylphosphoric acid, 1-hydroxymethylnaphthalene-4 methylphosphoric acid, 1-hydroxymethylnaphthalene-5 methylphosphoric acid, 1-hydroxymethylnaphthalene-6 methylphosphoric acid, 1-hydroxymethylnaphthalene-7 methylphosphoric acid, 2-hydroxymethylnaphthalene-4 methylphosphoric acid, 2-hydroxymethylnaphthalene-5 methylphosphoric acid, 2-hydroxymethylnaphthalene-6 methylphosphoric acid, 2-hydroxymethylnaphthalene-7 methylphosphoric 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 phosphorus-containing polycarboxylic acid water reducer.
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 to the hydroxynaphthalene phosphoric 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 phosphoric 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 phosphoric 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, the esterification product of the unsaturated polyether monomer and the first compound is used for synthesis of the polycarboxylate water reducer, a benzene ring and a phosphate 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 phosphate 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. According to the invention, the esterification product of unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalene phosphoric acid is used for synthesis of the polycarboxylate water reducer, and the naphthalene phosphoric acid side group is introduced into the main chain of the polycarboxylate water reducer molecule, so that the adsorption effect of the 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 phosphorus-containing polycarboxylate superplasticizer prepared in the following embodiment is 10000-150000, and the structural formula is as follows:
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 with an alkyl phosphate 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: 600.00g of allyl polyethylene glycol with molecular weight of 1000 and 100.00g of o-carboxyphenylphosphoric acid are mixed, the temperature is raised to 75 ℃ under the protection of nitrogen, 0.38g 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 removal in the reaction period, and the temperature is lowered to 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 75.00g of acrylic acid, 100.00g of 1-hydroxynaphthalene-4 phosphoric acid and 1.80g of hydroquinone, heating to 105 ℃ under the protection of nitrogen, adding 0.15g of mellitic acid, carrying out heat preservation reaction for 2.0h, 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 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), an ascorbic acid aqueous solution (wherein 0.20g of water and 10.00g of water) and a thioglycolic acid aqueous solution (wherein 0.70g of thioglycolic acid and 10.00g of water) into 40.00g of water for reaction at the reaction temperature of 40 ℃ for 3.0h, and preserving heat for 1.5h 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 phosphorus-containing polycarboxylic acid water reducer PCE-1.
Example 2
(1) A first esterification reaction: 1050.00g of 3-methyl-3-butene-1-polyethylene glycol with molecular weight of 2000 and 100.00g of m-carboxymethyl phenylphosphonic acid are mixed, the temperature is raised to 75 ℃ under the protection of nitrogen, 1.50g of nitrogen-sulfur squaric acid is added, the mixture is kept for reaction for 1.5h, 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: 88.00g of methacrylic acid, 100.00g of 1-hydroxynaphthalene-5 phosphoric acid and 1.60g of phenothiazine are mixed, the temperature is raised to 100 ℃ under the protection of nitrogen, 0.30g of nitrogen-sulfur squaric acid is added, the reaction is kept for 2.0h, water is removed by a method of vacuumizing or introducing nitrogen to carry water in the reaction period, and the temperature is reduced 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 13.00g 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 1.20g and the weight of the water is 10.00g) and sodium hypophosphite aqueous solution (wherein the weight of the sodium hypophosphite is 0.90g and the weight of the water is 10.00g) into 40.00g of water for reaction, wherein the reaction temperature is 45 ℃, 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 phosphorus-containing polycarboxylic acid water reducer PCE-2.
Example 3
(1) A first esterification reaction: 1140.00g of 2-methylallyl polyethylene glycol with the molecular weight of 2400 and 100.00g of p-carboxyethyl benzene phosphoric acid are mixed, the temperature is raised to 85 ℃ under the protection of nitrogen, 2.80g 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: 165.00g of maleic acid, 100.00g of 1-hydroxynaphthalene-6 phosphoric acid and 1.80g of diphenylamine are mixed, the temperature is raised to 110 ℃ under the protection of nitrogen, 0.60g of trinitrobenzenesulfonic acid is added, the mixture is subjected to heat preservation reaction for 2.5 hours, water is removed by vacuumizing or introducing nitrogen to carry water in the reaction period, and the temperature is reduced 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 15.00g 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 2.20g of azodicyano valeric acid and 10.00g of water) and a trisodium phosphate aqueous solution (wherein 1.60g of trisodium phosphate and 10.00g of water) into 40.00g of water for reaction at the reaction temperature of 50 ℃ for 2.0h, 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 phosphorus-containing polycarboxylic acid water reducer PCE-3.
Example 4
(1) A first esterification reaction: 1450.00g of allyl polyethylene glycol with the molecular weight of 3000 and 100.00g of o-carboxyphenylmethyl phosphoric acid are mixed, the temperature is raised to 90 ℃ under the protection of nitrogen, 4.40g of mellitic acid is added, the temperature is kept for reaction for 3.0h, water is removed by vacuumizing or introducing nitrogen to carry out water-carrying reaction in the period, and the temperature is lowered to 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: 170.00g of maleic anhydride, 100.00g of 1-hydroxynaphthalene-7 phosphoric acid and 2.00g of hydroquinone are mixed, the temperature is raised to 100 ℃ under the protection of nitrogen, 0.70g of trinitrobenzenesulfonic acid is added, the mixture is subjected to heat preservation reaction for 1.5h, water is removed by a vacuum pumping or nitrogen introducing water carrying method during the reaction, and the temperature is reduced 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 16.00g 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, 1.20g of hydrogen peroxide and 10.00g of water), a trisodium phosphate aqueous solution (wherein, 1.00g of trisodium phosphate and 10.00g of water) and an ascorbic acid aqueous solution (wherein, 0.20g of ascorbic acid and 10.00g of water) into 40.00g of water for reaction at the reaction temperature of 35 ℃ for 2.5h, 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 phosphorus-containing polycarboxylic acid water reducer PCE-4.
Example 5
(1) A first esterification reaction: 1990.00g of 3-methyl-3-butene-1-polyethylene glycol with the molecular weight of 4000 and 100.00g of p-carboxymethylbenzylethyl phosphoric acid are mixed, the temperature is raised to 80 ℃ under the protection of nitrogen, 6.00g of trinitrobenzene sulfonic acid is added, the mixture is subjected to heat preservation reaction for 3.0h, 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 unreacted 3-methyl-3-butene-1-polyethylene glycol is obtained.
(2) Second esterification reaction: mixing 99.00g of acrylic acid, 100.00g of 2-hydroxynaphthalene-4 phosphoric acid and 3.60g of phenothiazine, heating to 115 ℃ 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 13.00g 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 1.80g, the water is 10.00g) and a sodium hypophosphite aqueous solution (wherein, the sodium hypophosphite is 1.40g, the water is 20.00g) into 40.00g of water for reaction, wherein the reaction temperature is 40 ℃, the dripping time is 2.0h, 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 phosphorus-containing polycarboxylic acid water reducer PCE-5.
According to GB/T8076-2008, when the phosphorus-containing polycarboxylic acid water reducing agent prepared in the embodiments 1 to 5 is tested, when the folding and solid content is 0.2% (relative to the cement content), the water reducing rate is higher than 45%, 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 water3And 3.5% of bentonite (relative to the amount of cement) was added, and a performance test was conducted on the phosphorus-containing polycarboxylic acid water reducing agent obtained in examples 1 to 5 and a commercially available polycarboxylic acid water reducing agent (PCE) in accordance with the anchoring 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
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 retaining performance compared with the commercially available polycarboxylate superplasticizer (PCE), so that the polycarboxylate superplasticizer prepared by the patent has lower sensitivity to the material with high mud content and has the mud resistance effect.
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 phosphorus-containing polycarboxylic acid water reducing agent has a molecular weight of 10000-150000 and has a structural formula as follows:
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 with an alkyl phosphate 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 phosphorus-containing polycarboxylate superplasticizer 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:
(2) second esterification reaction: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, hydroxynaphthalene phosphoric 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 above-mentioned hydroxynaphthalene phosphoric acid is 1-hydroxynaphthalene-4 phosphoric acid, 1-hydroxynaphthalene-5 phosphoric acid, 1-hydroxynaphthalene-6 phosphoric acid, 1-hydroxynaphthalene-7 phosphoric acid, 2-hydroxynaphthalene-4 phosphoric acid, 2-hydroxynaphthalene-5 phosphoric acid, 2-hydroxynaphthalene-6 phosphoric acid, 2-hydroxynaphthalene-7 phosphoric acid, 1-hydroxymethylnaphthalene-4 phosphoric acid, 1-hydroxymethylnaphthalene-5 phosphoric acid, 1-hydroxymethylnaphthalene-6 phosphoric acid, 1-hydroxymethylnaphthalene-7 phosphoric acid, 2-hydroxymethylnaphthalene-4 phosphoric acid, 2-hydroxymethylnaphthalene-5 phosphoric acid, 2-hydroxymethylnaphthalene-6 phosphoric acid, 2-hydroxymethylnaphthalene-7 phosphoric acid, 1-hydroxynaphthalene-4 methylphosphoric acid, 1-hydroxynaphthalene-5 methylphosphoric acid, At least one of 1-hydroxynaphthalene-6 methylphosphoric acid, 1-hydroxynaphthalene-7 methylphosphoric acid, 2-hydroxynaphthalene-4 methylphosphoric acid, 2-hydroxynaphthalene-5 methylphosphoric acid, 2-hydroxynaphthalene-6 methylphosphoric acid, 2-hydroxynaphthalene-7 methylphosphoric acid, 1-hydroxymethylnaphthalene-4 methylphosphoric acid, 1-hydroxymethylnaphthalene-5 methylphosphoric acid, 1-hydroxymethylnaphthalene-6 methylphosphoric acid, 1-hydroxymethylnaphthalene-7 methylphosphoric acid, 2-hydroxymethylnaphthalene-4 methylphosphoric acid, 2-hydroxymethylnaphthalene-5 methylphosphoric acid, 2-hydroxymethylnaphthalene-6 methylphosphoric acid, and 2-hydroxymethylnaphthalene-7 methylphosphoric 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 phosphorus-containing polycarboxylic acid water reducer.
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 phosphoric 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 the hydroxynaphthalene phosphoric 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 phosphoric 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 phosphorus-containing polycarboxylic acid water reducing agent is characterized in that: the molecular weight of the compound is 10000-150000, and the structural formula is as follows:
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 with an alkyl phosphate substituent, M is H, Na, K or NH4；R3And R4The relation of the relative benzene ring is ortho-position, meta-position or para-position;
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:
(2) second esterification reaction: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, hydroxynaphthalene phosphoric 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 above-mentioned hydroxynaphthalene phosphoric acid is 1-hydroxynaphthalene-4 phosphoric acid, 1-hydroxynaphthalene-5 phosphoric acid, 1-hydroxynaphthalene-6 phosphoric acid, 1-hydroxynaphthalene-7 phosphoric acid, 2-hydroxynaphthalene-4 phosphoric acid, 2-hydroxynaphthalene-5 phosphoric acid, 2-hydroxynaphthalene-6 phosphoric acid, 2-hydroxynaphthalene-7 phosphoric acid, 1-hydroxymethylnaphthalene-4 phosphoric acid, 1-hydroxymethylnaphthalene-5 phosphoric acid, 1-hydroxymethylnaphthalene-6 phosphoric acid, 1-hydroxymethylnaphthalene-7 phosphoric acid, 2-hydroxymethylnaphthalene-4 phosphoric acid, 2-hydroxymethylnaphthalene-5 phosphoric acid, 2-hydroxymethylnaphthalene-6 phosphoric acid, 2-hydroxymethylnaphthalene-7 phosphoric acid, 1-hydroxynaphthalene-4 methylphosphoric acid, 1-hydroxynaphthalene-5 methylphosphoric acid, At least one of 1-hydroxynaphthalene-6 methylphosphoric acid, 1-hydroxynaphthalene-7 methylphosphoric acid, 2-hydroxynaphthalene-4 methylphosphoric acid, 2-hydroxynaphthalene-5 methylphosphoric acid, 2-hydroxynaphthalene-6 methylphosphoric acid, 2-hydroxynaphthalene-7 methylphosphoric acid, 1-hydroxymethylnaphthalene-4 methylphosphoric acid, 1-hydroxymethylnaphthalene-5 methylphosphoric acid, 1-hydroxymethylnaphthalene-6 methylphosphoric acid, 1-hydroxymethylnaphthalene-7 methylphosphoric acid, 2-hydroxymethylnaphthalene-4 methylphosphoric acid, 2-hydroxymethylnaphthalene-5 methylphosphoric acid, 2-hydroxymethylnaphthalene-6 methylphosphoric acid, and 2-hydroxymethylnaphthalene-7 methylphosphoric 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 phosphorus-containing polycarboxylic acid water reducer.
2. The phosphorus-containing polycarboxylate water reducer 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 dosage of the catalyst is 0.05-0.3% of the total mass of the unsaturated polyether and the first compound.
3. The phosphorus-containing polycarboxylate water reducer 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 phosphoric 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 the hydroxynaphthalene phosphoric 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 phosphoric acid.
4. The phosphorus-containing polycarboxylic acid water reducing agent of claim 2, 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 phosphorus-containing polycarboxylic acid water reducer 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 phosphorus-containing polycarboxylic acid water reducer 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 phosphorus-containing polycarboxylic acid water reducer 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 phosphorus-containing polycarboxylic acid water reducer 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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| PCT/CN2018/122569 WO2019233085A1 (en) | 2018-06-08 | 2018-12-21 | Phosphorus-containing polycarboxylate superplasticizer and preparation method therefor |
| MYPI2018002722A MY197439A (en) | 2018-06-08 | 2018-12-21 | Phosphorus?containing polycarboxylate superplasticizer and method for making same |
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| CN110255958B (en) * | 2019-05-29 | 2020-07-31 | 科之杰新材料集团有限公司 | Wet-mixed mortar plasticity stabilizer and preparation method thereof |
| CN110358021B (en) * | 2019-05-29 | 2022-04-22 | 科之杰新材料集团有限公司 | Cross-linking type wet-mixed mortar plasticity-maintaining agent and preparation method thereof |
| CN110228962B (en) * | 2019-05-29 | 2021-10-29 | 科之杰新材料集团有限公司 | Water-retention type wet-mixed mortar plasticizer and preparation method thereof |
| CN110330600B (en) * | 2019-05-29 | 2022-04-22 | 科之杰新材料集团有限公司 | Low-sensitivity wet-mixed mortar plasticizer and preparation method thereof |
| CN113185185B (en) * | 2021-05-31 | 2022-08-02 | 扬州工业职业技术学院 | Multifunctional auxiliary agent for building material and preparation method thereof |
| CN115838458A (en) * | 2022-11-14 | 2023-03-24 | 科之杰新材料集团有限公司 | Novel polycarboxylate superplasticizer and preparation method thereof |
| CN115894889B (en) * | 2022-12-29 | 2024-08-13 | 科之杰新材料集团有限公司 | Viscosity-reducing slow-release polycarboxylate superplasticizer and preparation method thereof |
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| CN104261719B (en) * | 2014-08-06 | 2016-09-14 | 中交二航武汉港湾新材料有限公司 | A kind of high-performance polycarboxylic acids water reducing agent and preparation method thereof |
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| CN106186781B (en) * | 2016-06-29 | 2018-10-23 | 南京瑞迪高新技术有限公司 | A kind of preparation method of modified naphthalene series water-reducing agent |
| CN107325234B (en) * | 2017-07-07 | 2020-04-24 | 江苏奥莱特新材料股份有限公司 | Anti-mud phosphate modified polycarboxylate superplasticizer and preparation method thereof |
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