CN107987235B - Preparation method of low-hydration-heat anti-cracking polycarboxylate superplasticizer - Google Patents
Preparation method of low-hydration-heat anti-cracking polycarboxylate superplasticizer Download PDFInfo
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- CN107987235B CN107987235B CN201711290313.5A CN201711290313A CN107987235B CN 107987235 B CN107987235 B CN 107987235B CN 201711290313 A CN201711290313 A CN 201711290313A CN 107987235 B CN107987235 B CN 107987235B
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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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
Abstract
The invention discloses a preparation method of a low hydration heat anti-cracking type polycarboxylate superplasticizer, which comprises the following steps: (1) acylation and esterification reaction; (2) blending monomers; (3) carrying out copolymerization reaction; (4) and (4) neutralizing. The water reducing agent prepared by the preparation method disclosed by the invention contains ester groups, phenyl groups and phosphate groups in molecules, and is applied to concrete, the ester groups are hydrolyzed under the alkaline condition of the concrete to gradually release carboxyl groups with a water reducing function and hydroxyphenyl phosphate groups with a hydration heat reducing function, so that the hydration heat of the concrete can be effectively reduced, the heat dissipation time is prolonged, the problem of concrete cracking can be effectively prevented to a certain extent, and the durability of the concrete can be improved. Meanwhile, as the polyether side chain is connected with the main chain through an ester bond, a layer of water film can be formed on the surface of the concrete, the excessive water loss of the surface of the concrete is reduced, the shrinkage of the concrete is effectively reduced, and the cracking of the concrete is favorably reduced.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a preparation method of a low-hydration-heat anti-cracking type polycarboxylate superplasticizer.
Background
Since the 20 th century since the advent of portland cement, concrete materials became indispensable materials for civil engineering with its practical utility and low cost, and were widely used in structures such as bridges, dams, highways, industrial and civil buildings, and the like. 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, and is widely applied to various engineering fields at present.
With the acceleration of concrete engineering project construction, the durability and the appearance requirements of China on concrete are gradually improved, and main influencing factors causing concrete cracks include freeze thawing, corrosion of aggressive chemical substances, corrosion of reinforcing steel bars, temperature stress cracks and alkali-aggregate reaction. In order to solve the problem of concrete durability, China also expends huge financial and material resources, researches and develops a polycarboxylate superplasticizer with double properties of cracking resistance and hydration heat reduction, and is very significant and valuable for improving the concrete durability.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a low hydration heat anti-cracking type polycarboxylate superplasticizer.
The technical scheme of the invention is as follows:
a preparation method of a low hydration heat anti-cracking polycarboxylate superplasticizer comprises the following steps:
(1) acylation and esterification reactions: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether with the molecular weight of 400-5000, a compound A and a polymerization inhibitor, heating to 63-86 ℃ under the protection of nitrogen, adding a catalyst, carrying out heat preservation reaction for 0.5-3.5 h, removing water by vacuumizing or introducing nitrogen during the reaction, cooling to room temperature after the reaction is finished to obtain a first mixture of an acylation esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride, wherein the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, the alcohol amine, the polyethylene glycol monomethyl ether and the compound A is 5-20: 0.2-1.2: 0.5-2, the dosage of the catalyst is 0.2-4.3% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, the alcohol amine, the polyethylene glycol monomethyl ether and the compound A, and the dosage of the polymerization inhibitor is 0.2-4.3% of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, the alcohol, 0.1-3.2% of the total mass of the compound A; the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is at least one of maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, and itaconic acid, the alkanolamine is at least one of monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine, the compound A is at least one of (2-hydroxyphenyl) phosphoric acid, (3-hydroxyphenyl) phosphoric acid, (4-hydroxyphenyl) phosphoric acid, (2-hydroxymethylphenyl) phosphoric acid, (3-hydroxymethylphenyl) phosphoric acid, (4-hydroxymethylphenyl) phosphoric acid, (2-hydroxybenzyl) phosphoric acid, (3-hydroxybenzyl) phosphoric acid, (4-hydroxybenzyl) phosphoric acid, (2-hydroxymethylbenzyl) phosphoric acid, (3-hydroxymethylbenzyl) phosphoric acid, and (4-hydroxymethylbenzyl) phosphoric acid, the catalyst is at least one of periodic acid, dinitrobenzoic acid and ethylene diamine tetraacetic acid;
(2) monomer blending: mixing the first mixture prepared in the step (1) and unsaturated sulfonate according to a mass ratio of 180-220: 1-7, and adding water to dissolve the mixture to obtain a comonomer mixture solution, wherein the unsaturated sulfonate is at least one of sodium allyl sulfonate, sodium styrene sulfonate, sodium vinyl sulfonate, sodium methallyl sulfonate and 2-acrylamido-2-methylpropanesulfonic acid;
(3) and (3) copolymerization reaction: dripping the comonomer mixture solution, the initiator aqueous solution and the molecular weight regulator aqueous solution into water for reaction, wherein the reaction temperature is 10-62 ℃, the dripping time is 0.2-6.5 h, and the temperature is kept for 0-3.5 h after the dripping is finished to obtain a copolymerization product; the total amount of water used in the step (2) and the step (2) enables the mass concentration of the copolymerization product to be 20-80%, the dosage of the initiator is 0.5-3.5% of the total mass of the solute in the comonomer mixture solution, and the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of the solute in the comonomer mixture solution;
(4) 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 low hydration heat anti-cracking polycarboxylate superplasticizer.
In a preferred embodiment of the present invention, the step (1) is: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether, compound A and polymerization inhibitor, under the protection of nitrogen, heating to 65-85 ℃, adding a catalyst, carrying out heat preservation reaction for 0.5-3 h, removing water by using a vacuumizing or nitrogen-introducing water-carrying method during the reaction, cooling to room temperature after the reaction is finished, and obtaining a first mixture of an acylation esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride, wherein the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether and a compound A is 5-20: 1: 0.5-2, the dosage of the catalyst is 0.3-4.0% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether and the compound A, and the dosage of the polymerization inhibitor is 0.1-3.0% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether and the compound A;
in a preferred embodiment of the present invention, the step (2) is: mixing the first mixture prepared in the step (1) and unsaturated sulfonate according to the mass ratio of 200: 1-5, and adding water to dissolve the mixture to obtain a comonomer mixture solution.
In a preferred embodiment of the present invention, the step (3) is: dripping the comonomer mixture solution, an initiator aqueous solution and a 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; the total amount of water used in the step (2) and the step (2) enables the mass concentration of the copolymerization product to be 20-70%, the dosage of the initiator is 0.5-3.0% of the total mass of the solute in the comonomer mixture solution, and the dosage of the molecular weight regulator is 0.2-2.0% of the total mass of the solute in the comonomer mixture solution.
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. the preparation method comprises the steps of preparing an unsaturated small monomer with an amide group, an unsaturated small monomer with an amino group, an unsaturated large monomer with a polyether side chain and an unsaturated small monomer with a benzene ring and a phosphate group by acylation and esterification of unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether and a compound A, copolymerizing with excessive unsaturated carboxylic acid or unsaturated carboxylic anhydride and unsaturated sulfonate during acylation and esterification, and introducing an amide group, an amino group, a phosphate group, a carboxylic acid group, a sulfonic acid group, an amide group, a polyether side chain and a benzene ring into a molecular structure, so that the product has high initial water reduction rate.
2. The water reducing agent prepared by the preparation method disclosed by the invention contains ester groups, phenyl groups and phosphate groups in molecules, and is applied to concrete, the ester groups are hydrolyzed under the alkaline condition of the concrete to gradually release carboxyl groups with a water reducing function and hydroxyphenyl phosphate groups with a hydration heat reducing function, so that the hydration heat of the concrete can be effectively reduced, the heat dissipation time is prolonged, the problem of concrete cracking can be effectively prevented to a certain extent, and the durability of the concrete can be improved. Meanwhile, as the polyether side chain is connected with the main chain through an ester bond, a layer of water film can be formed on the surface of the concrete, the excessive water loss of the surface of the concrete is reduced, the shrinkage of the concrete is effectively reduced, and the cracking of the concrete is favorably reduced.
3. The molecular structure of the water reducing agent prepared by the preparation method contains amide groups, and the water reducing agent is applied to concrete, can improve the early strength of the concrete, and does not influence the 28-day strength.
4. The preparation method of the invention introduces the high-efficiency catalyst for catalysis, so that the acylation esterification temperature is lower, the production energy consumption is reduced, the production cost is saved, the double bond retention rate is higher, the conversion rate of the product is further improved, and the comprehensive performance of the product can be improved.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
(1) Acylation and esterification reactions: 147.00g of maleic anhydride, 2.20g of monoethanolamine, 29.00g of (4-hydroxyphenyl) phosphoric acid, 100.00g of polyethylene glycol monomethyl ether with the molecular weight of 600, 2.00g of hydroquinone and 2.00g of phenothiazine are mixed, the temperature is increased to 65 ℃ under the protection of nitrogen, 2.00g of periodic acid and 5.00g of dinitrobenzoic acid are added, the temperature is kept for reaction for 2.0h, water is removed by vacuumizing or introducing nitrogen to carry water, and the temperature is reduced to the room temperature after the reaction is finished to obtain a first mixture containing the acylation esterification product and unreacted maleic anhydride;
(2) monomer blending: mixing 200.00g of the first mixture prepared in the step (1) and 4.00g of sodium styrene sulfonate, and adding 70.00g of water to dissolve the mixture to obtain a comonomer mixture solution;
(3) and (3) copolymerization reaction: dripping the comonomer mixture solution, a hydrogen peroxide aqueous solution (wherein the weight of hydrogen peroxide is 1.60g, and the weight of water is 20.00g), an ascorbic acid aqueous solution (wherein the weight of water is 0.40g, and the weight of water is 20.00g) and trisodium phosphate (wherein the weight of trisodium phosphate is 2.00g, and the weight of water is 20.00g) into 60.00g of water for reaction, wherein the reaction temperature is 30 ℃, the dripping time is 4.0h, and after the dripping is finished, preserving heat for 3.0h to obtain a copolymerization product;
(4) 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 low hydration heat anti-cracking polycarboxylate superplasticizer PCE-1.
Example 2
(1) Acylation and esterification reactions: mixing 36.00g of acrylic acid, 4300g of methacrylic acid, 4.00g of diethanolamine, 24.00g of (3-hydroxymethyl phenyl) phosphoric acid, 100.00g of polyethylene glycol monomethyl ether with the molecular weight of 800, 1.00g of hydroquinone and 2.00g of diphenylamine, heating to 70 ℃ under the protection of nitrogen, adding 3.00g of dinitrobenzoic acid and 3.00g of ethylenediamine tetraacetic acid, carrying out heat preservation reaction for 3 hours, removing water by vacuumizing or introducing nitrogen and carrying water, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an acylated esterification product and unreacted acrylic acid and methacrylic acid;
(2) monomer blending: mixing 200.00g of the first mixture prepared in the step (1), 1.00g of sodium allylsulfonate and 4.00g of sodium vinylsulfonate, and adding 70.00g of water to dissolve them, thereby obtaining a comonomer mixture solution;
(3) and (3) copolymerization reaction: dropping the comonomer mixture solution, an aqueous solution of azobisisobutylamidine hydrochloride (wherein the weight of the azobisisobutylamidine hydrochloride is 2.00g, the weight of the water is 40.00g) and an aqueous solution of sodium hypophosphite (wherein the weight of the sodium hypophosphite is 3.00g, the weight of the water is 20.00g) into 60.00g of water for reaction, wherein the reaction temperature is 40 ℃, the dropping time is 4.0h, and after the dropping is finished, preserving the heat for 2.0h to obtain a copolymerization product;
(4) 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 low hydration heat anti-cracking polycarboxylate superplasticizer PCE-2.
Example 3
(1) Acylation and esterification reactions: mixing 58.00g of acrylic acid, 23.00g of fumaric acid, 3.00g of diethanolamine, 14.00g of (3-hydroxyphenyl) phosphoric acid, 4.00g of (4-hydroxybenzyl) phosphoric acid, 100.00g of polyethylene glycol monomethyl ether with the molecular weight of 1000, 3.00g of hydroquinone and 1.00g of phenothiazine, heating to 75 ℃ under the protection of nitrogen, adding 2.00g of periodic acid and 2.00g of ethylenediamine tetraacetic acid, carrying out heat preservation reaction for 2.0h, removing water by vacuumizing or introducing nitrogen during the heat preservation reaction, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an acylated esterification product, unreacted acrylic acid and fumaric acid;
(2) monomer blending: mixing 200.00g of the first mixture prepared in the step (1), 2.00g of sodium styrene sulfonate and 1.00g of sodium methallyl sulfonate, and adding 70.00g of water to dissolve the mixture to obtain a comonomer mixture solution;
(3) and (3) copolymerization reaction: dripping the comonomer mixture solution, an azodicyano valeric acid aqueous solution (wherein 3.00g of azodicyano valeric acid and 40.00g of water) and a trisodium phosphate aqueous solution (wherein 1.00g of trisodium phosphate and 20.00g of water) into 60.00g of water for reaction at the reaction temperature of 45 ℃ for 3.0h, and preserving heat for 1.0h after dripping to obtain a copolymerization product;
(4) 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 low hydration heat anti-cracking polycarboxylate superplasticizer PCE-3.
Example 4
(1) Acylation and esterification reactions: mixing 98.00g of maleic anhydride, 43.00g of itaconic acid, 4.50g of triethanolamine, 15.00g of (3-hydroxyphenyl) phosphoric acid, 100.00g of polyethylene glycol monomethyl ether with the molecular weight of 1200, 2.00g of hydroquinone and 3.00g of phenothiazine, heating to 80 ℃ under the protection of nitrogen, adding 1.00g of periodic acid and 2.00g of dinitrobenzoic acid, carrying out heat preservation reaction for 1.0h, removing water by vacuumizing or introducing nitrogen during the reaction, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an acylated esterification product, unreacted maleic anhydride and itaconic acid;
(2) monomer blending: dissolving 200.00g of the first mixture prepared in the step (1), 1.00g of sodium allylsulfonate and 1.00g of sodium styrene sulfonate by adding 70.00g of water to obtain a comonomer mixture solution;
(3) and (3) copolymerization reaction: dripping the comonomer mixture solution, a hydrogen peroxide aqueous solution (wherein, 2.20g of hydrogen peroxide and 20.00g of water), a trisodium phosphate aqueous solution (wherein, 1.80g of trisodium phosphate and 20.00g of water) and an ascorbic acid aqueous solution (wherein, 0.80 g of ascorbic acid and 20.00g of water) into 60.00g of water for reaction at the reaction temperature of 50 ℃ for 5.0h, and preserving heat for 5.0h after dripping to obtain a copolymerization product;
(4) 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 low hydration heat anti-cracking polycarboxylate superplasticizer PCE-4.
Example 5
(1) Acylation and esterification reactions: mixing 14.00g of acrylic acid, 35.00g of methacrylic acid, 1.20g of diethanolamine, 9.00g of (4-hydroxybenzyl) phosphoric acid, 100.00g of polyethylene glycol monomethyl ether with the molecular weight of 2000, 3.00g of hydroquinone and 3.00g of diphenylamine, heating to 85 ℃ under the protection of nitrogen, adding 2.00g of periodic acid and 3.00g of dinitrobenzoic acid, carrying out heat preservation reaction for 1.5h, removing water by vacuumizing or introducing nitrogen during the heat preservation reaction, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an acylated esterification product and unreacted acrylic acid and methacrylic acid;
(2) monomer blending: mixing 200.00g of the first mixture prepared in the step (1), 2.00g of sodium allylsulfonate and 2.00g of sodium styrene sulfonate, and adding 70.0 g of water to dissolve them, to obtain a comonomer mixture solution;
(3) and (3) copolymerization reaction: dripping the comonomer mixture solution and an azodicyano valeric acid aqueous solution (wherein, 2.00g of azodicyano valeric acid and 40.00g of water) and a sodium hypophosphite aqueous solution (wherein, 3.00g of sodium hypophosphite and 20.00g of water) into 60.00g of water for reaction, wherein the reaction temperature is 60 ℃, the dripping time is 1.5h, and preserving heat for 2.0h after dripping is finished to obtain a copolymerization product;
(4) 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 low hydration heat anti-cracking polycarboxylate superplasticizer PCE-5.
Example 6
(1) Acylation and esterification reactions: mixing 20.00g of maleic anhydride, 36.00g of itaconic acid, 1.30g of triethanolamine, 3.00g of (4-hydroxyphenyl) phosphoric acid, 5.00g of (4-hydroxymethylbenzyl) phosphoric acid, 100.00g of polyethylene glycol monomethyl ether with the molecular weight of 2400, 1.00g of phenothiazine and 1.00g of diphenylamine, heating to 80 ℃ under the protection of nitrogen, adding 2.00g of ethylenediamine tetraacetic acid and 1.00g of dinitrobenzoic acid, carrying out heat preservation reaction for 2.0h, removing water by vacuumizing or introducing nitrogen during the reaction, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an acylated esterification product, unreacted maleic anhydride and itaconic acid;
(2) monomer blending: mixing 200.00g of the first mixture obtained in the step (1), 1.00g of sodium allylsulfonate and 2.00g of sodium vinylsulfonate, and adding 70.00g of water to dissolve them, to obtain a comonomer mixture solution;
(3) and (3) copolymerization reaction: dropping the comonomer mixture solution and an aqueous solution of azodiisobutyl amidine hydrochloride (wherein the weight of the azodiisobutyl amidine hydrochloride is 4.00g, the weight of the water is 40.00g) and an aqueous solution of sodium acetate (wherein the weight of the sodium acetate is 2.00g, and the weight of the water is 20.00g) into 60.00g of water for reaction, wherein the reaction temperature is 20 ℃, the dropping time is 6.0h, and after the dropping is finished, preserving the heat for 1.0h to obtain a copolymerization product;
(4) 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 low hydration heat anti-cracking polycarboxylate superplasticizer PCE-6.
According to GB/T8076-2008, the low hydration heat crack resistance type polycarboxylate water reducing agents prepared in the embodiments 1 to 6 are tested, and when the bonding and mixing amount is 0.12 wt% (relative to the cement amount, the water reducing rate is higher than 25%, the 1d compressive strength ratio is larger than 180%, the 28d compressive strength ratio is larger than 140%, the 28d shrinkage ratio is smaller than 90%, and the 28d shrinkage ratio of the concrete is smaller, the volume stability of the concrete is effectively improved, the cracking of the concrete is reduced, and the crack resistance effect of the product is better.
The Huarun P.O42.5 ordinary portland cement is adopted, and the concrete mixing proportion is as follows: the concrete fluidity stabilizer prepared in the examples 1 to 6 and the commercial polycarboxylate water reducer (PCE) were respectively subjected to performance tests according to the bending and mixing amount of 0.12%, and the hydration heat test results of different additives are shown in Table 1, wherein the performances of the concrete fluidity stabilizer and the commercial polycarboxylate water reducer (PCE) are respectively tested according to the bending and mixing amount of 300kg/m3, the fly ash 80kg/m3, the mineral powder 80kg/m3, the sand 735kg/m3, the stone 1040kg/m3 and the water 165kg/m 3.
TABLE 1 hydration heat test results for different additives
| Test number | Kind of additive | TL0(mm) | TL2(mm) | tmax/h | Tmax/℃ |
| 1 | PCE | 200 | 150 | 16 | 73 |
| 2 | PCE-1 | 210 | 210 | 28 | 61 |
| 3 | PCE-2 | 210 | 205 | 27 | 60 |
| 4 | PCE-3 | 210 | 200 | 29 | 59 |
| 5 | PCE-4 | 205 | 200 | 28 | 61 |
| 6 | PCE-5 | 210 | 205 | 27 | 61 |
| 7 | PCE-6 | 215 | 215 | 30 | 58 |
tmax: the corresponding time when the hydration heat release of the cement paste reaches the highest temperature;
tmax: the corresponding temperature when the hydration heat release of the cement paste reaches the highest temperature;
as can be seen from Table 1, the examples synthesized by this patent compare with the commercial polycarboxylate water reducer (PCE, concrete slump retention ability is better, hydration heat release speed is slower, and hydration heat is significantly lower.
It will be understood by those skilled in the art that the raw materials and parameters used in the present invention can still obtain the same or similar technical effects as the above examples when they are changed within the following ranges, and still fall into the protection scope of the present invention:
a preparation method of a low hydration heat anti-cracking polycarboxylate superplasticizer comprises the following steps:
(1) acylation and esterification reactions: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether with the molecular weight of 400-5000, a compound A and a polymerization inhibitor, heating to 63-86 ℃ (preferably 65-85 ℃) under the protection of nitrogen, adding a catalyst, performing heat preservation reaction for 0.5-3.5 h (preferably 0.5-3 h), removing water by using a vacuum pumping method or a nitrogen-introducing water-carrying method during the heat preservation reaction, cooling to room temperature after the reaction is finished, and obtaining a first mixture of an acylation esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride, wherein the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, the alcohol amine, the polyethylene glycol monomethyl ether and the compound A is 5-20: 0.2-1.2: 0.5-2 (preferably 5-20: 1: 0.5-0.5), and the dosage of the catalyst is 0.2-4.3% (preferably 0.3-4.0%) of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, the alcohol amine, the polyethylene glycol monomethyl ether and the compound, the dosage of the polymerization inhibitor is 0.1-3.2% (preferably 0.1-3.0%) of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether and the compound A; the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is at least one of maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, and itaconic acid, the alkanolamine is at least one of monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine, the compound A is at least one of (2-hydroxyphenyl) phosphoric acid, (3-hydroxyphenyl) phosphoric acid, (4-hydroxyphenyl) phosphoric acid, (2-hydroxymethylphenyl) phosphoric acid, (3-hydroxymethylphenyl) phosphoric acid, (4-hydroxymethylphenyl) phosphoric acid, (2-hydroxybenzyl) phosphoric acid, (3-hydroxybenzyl) phosphoric acid, (4-hydroxybenzyl) phosphoric acid, (2-hydroxymethylbenzyl) phosphoric acid, (3-hydroxymethylbenzyl) phosphoric acid, and (4-hydroxymethylbenzyl) phosphoric acid, the catalyst is at least one of periodic acid, dinitrobenzoic acid and ethylene diamine tetraacetic acid;
(2) monomer blending: mixing the first mixture prepared in the step (1) and unsaturated sulfonate according to a mass ratio of 180-220: 1-7 (preferably 200: 1-5), and adding water to dissolve the mixture to obtain a comonomer mixture solution, wherein the unsaturated sulfonate is at least one of sodium allyl sulfonate, sodium styrene sulfonate, sodium vinyl sulfonate, sodium methallyl sulfonate and 2-acrylamido-2-methylpropanesulfonic acid;
(3) 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 temperature of 10-62 ℃ (preferably 10-60 ℃), wherein the dripping time is 0.2-6.5 h (preferably 0.2-6.0 h), and preserving heat for 0-3.5 h (preferably 0-3.0 h) after the dripping is finished to obtain a copolymerization product; the total amount of water used in the step (2) and the step (3) is such that the mass concentration of the copolymerization product is 20-80% (preferably 20-70%), the amount of the initiator is 0.5-3.5% (preferably 0.5-3.0%) of the total mass of the solutes in the comonomer mixture solution, and the amount of the molecular weight regulator is 0.2-3.0% (preferably 0.2-2.0%) of the total mass of the solutes in the comonomer mixture solution;
(4) 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 low hydration heat anti-cracking polycarboxylate superplasticizer.
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 (7)
1. A preparation method of a low hydration heat anti-cracking polycarboxylate superplasticizer is characterized by comprising the following steps: the method comprises the following steps:
(1) acylation and esterification reactions: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether with the molecular weight of 400-5000, a compound A and a polymerization inhibitor, heating to 63-86 ℃ under the protection of nitrogen, adding a catalyst, carrying out heat preservation reaction for 0.5-3.5 h, removing water by vacuumizing or introducing nitrogen during the reaction, cooling to room temperature after the reaction is finished to obtain a first mixture of an acylation esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride, wherein the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, the alcohol amine, the polyethylene glycol monomethyl ether and the compound A is 5-20: 0.2-1.2: 0.5-2, the dosage of the catalyst is 0.2-4.3% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, the alcohol amine, the polyethylene glycol monomethyl ether and the compound A, and the dosage of the polymerization inhibitor is 0.2-4.3% of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, the alcohol, 0.1-3.2% of the total mass of the compound A; the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is at least one of maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, and itaconic acid, the alkanolamine is at least one of monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine, the compound A is at least one of (2-hydroxyphenyl) phosphoric acid, (3-hydroxyphenyl) phosphoric acid, (4-hydroxyphenyl) phosphoric acid, (2-hydroxymethylphenyl) phosphoric acid, (3-hydroxymethylphenyl) phosphoric acid, (4-hydroxymethylphenyl) phosphoric acid, (2-hydroxybenzyl) phosphoric acid, (3-hydroxybenzyl) phosphoric acid, (4-hydroxybenzyl) phosphoric acid, (2-hydroxymethylbenzyl) phosphoric acid, (3-hydroxymethylbenzyl) phosphoric acid, and (4-hydroxymethylbenzyl) phosphoric acid, the catalyst is at least one of periodic acid, dinitrobenzoic acid and ethylene diamine tetraacetic acid;
(2) monomer blending: mixing the first mixture prepared in the step (1) and unsaturated sulfonate according to a mass ratio of 180-220: 1-7, and adding water to dissolve the mixture to obtain a comonomer mixture solution, wherein the unsaturated sulfonate is at least one of sodium allyl sulfonate, sodium styrene sulfonate, sodium vinyl sulfonate, sodium methallyl sulfonate and 2-acrylamido-2-methylpropanesulfonic acid;
(3) and (3) copolymerization reaction: dripping the comonomer mixture solution, the initiator aqueous solution and the molecular weight regulator aqueous solution into water for reaction, wherein the reaction temperature is 10-62 ℃, the dripping time is 0.2-6.5 h, and the temperature is kept for 0-3.5 h after the dripping is finished to obtain a copolymerization product; the total amount of water used in the step (2) and the step (2) enables the mass concentration of the copolymerization product to be 20-80%, the dosage of the initiator is 0.5-3.5% of the total mass of the solute in the comonomer mixture solution, and the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of the solute in the comonomer mixture solution;
(4) 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 low hydration heat anti-cracking polycarboxylate superplasticizer.
2. The method of claim 1, wherein: the step (1) is as follows: mixing unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether, compound A and polymerization inhibitor, under the protection of nitrogen, heating to 65-85 ℃, adding a catalyst, carrying out heat preservation reaction for 0.5-3 h, removing water by a vacuumizing or nitrogen-introducing water-carrying method during the reaction, cooling to room temperature after the reaction is finished, and obtaining a first mixture of an acylation esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride, wherein the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether and a compound A is 5-20: 1: 0.5-2, the dosage of the catalyst is 0.3-4.0% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether and the compound A, and the dosage of the polymerization inhibitor is 0.1-3.0% of the total mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, alcohol amine, polyethylene glycol monomethyl ether and the compound A.
3. The method of claim 1, wherein: the step (2) is as follows: mixing the first mixture prepared in the step (1) and unsaturated sulfonate according to the mass ratio of 200: 1-5, and adding water to dissolve the mixture to obtain a comonomer mixture solution.
4. The method of claim 1, wherein: the step (3) is as follows: dripping the comonomer mixture solution, an initiator aqueous solution and a 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; the total amount of water used in the step (2) and the step (2) enables the mass concentration of the copolymerization product to be 20-70%, the dosage of the initiator is 0.5-3.0% of the total mass of the solute in the comonomer mixture solution, and the dosage of the molecular weight regulator is 0.2-2.0% of the total mass of the solute in the comonomer mixture solution.
5. The production method according to any one of claims 1 to 4, characterized in that: the polymerization inhibitor is at least one of hydroquinone, phenothiazine and diphenylamine.
6. The production method according to 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.
7. The production method according to 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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