CN108484842B - Ester low-sensitivity polycarboxylate superplasticizer and preparation method thereof - Google Patents
Ester low-sensitivity 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
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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 an ester low-sensitivity polycarboxylate superplasticizer and a preparation method thereof, wherein the molecular weight of active ingredients is 10000-150000, and the structural formula of the active ingredients is as follows:
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to an ester low-sensitivity type polycarboxylate 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.
With the wider application range of the polycarboxylic acid water reducing agent, problems also occur in the process of using the polycarboxylic acid water reducing agent due to the difference of raw materials, the difference of regional environments, the recognition limitation of technical personnel, the use habit and the theoretical cognition level in the process of premixing concrete, and the using effect of the polycarboxylic acid water reducing agent is directly influenced. At present, the action mechanism, the self-sensitivity and the like of the polycarboxylic acid water reducing agent in China cannot be completely controlled. Particularly in actual engineering, due to various reasons such as various types of cement, sand and mud content in concrete raw materials and the like, when the polycarboxylic acid water reducer is directly applied to concrete, the problems of poor adaptability to the cement, unexpected working performance of the concrete, large collapse loss and the like often occur, so that the requirements of construction sites cannot be met. Therefore, the development of the polycarboxylate superplasticizer with low sensitivity is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ester low-sensitivity type polycarboxylate superplasticizer.
The invention also aims to provide a preparation method of the ester low-sensitivity polycarboxylate superplasticizer.
The technical scheme of the invention is as follows:
the molecular weight of an active ingredient of the ester low-sensitivity polycarboxylate superplasticizer is 10000-150000, and the structural formula of the active ingredient is as follows:
wherein R is1Is H or CH3，R2Is SO3M、NH2Or CONH2，R3Is H or COOM, R4Is H or CH3，R5Is H or COOM, R6Is H or CH3，R7Is empty or C1-4 alkyl, and M is H, Na, K or NH4。
The preparation method of the ester low-sensitivity polycarboxylate superplasticizer comprises the following steps:
(1) esterification reaction: heating dicarboxylic acid and methoxypolyethylene glycol with molecular weight of 200-1000 to 60-100 ℃ under the protection of nitrogen, adding a first catalyst, performing heat preservation reaction for 0.4-2.5 h, adding polyethylene glycol with molecular weight of 200-1000 and a second catalyst, performing heat preservation reaction for 0.4-3.0 h, adding unsaturated carboxylic acid or unsaturated carboxylic anhydride, a polymerization inhibitor and a third catalyst, performing heat preservation reaction for 0.4-3.5 h, removing water by vacuumizing or introducing nitrogen to carry out water, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride; the dicarboxylic acid is at least one of oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid, the unsaturated carboxylic acid or unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid, fumaric acid, itaconic acid and maleic anhydride, the first catalyst is at least one of periodic acid, dinitrobenzoic acid and ethylene diamine tetraacetic acid, the second catalyst is at least one of periodic acid, dinitrobenzoic acid and ethylene diamine tetraacetic acid, and the third catalyst is at least one of concentrated sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid and ethylsulfonic acid;
(2) monomer blending: mixing the first mixture prepared in the step (1) with a small comonomer in a mass ratio of 200: 1-5 to obtain a comonomer mixture solution, wherein the small comonomer is at least one of sodium methallylsulfonate, acrylamide and acrylamide;
(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 10-63 ℃, 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;
(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 ester low-sensitivity polycarboxylate superplasticizer.
In a preferred embodiment of the present invention, the step (1) is: heating dicarboxylic acid and methoxypolyethylene glycol with molecular weight of 200-1000 to 60-90 ℃ under the protection of nitrogen, adding a first catalyst, performing heat preservation reaction for 0.5-2.5 h, adding polyethylene glycol with molecular weight of 200-1000 and a second catalyst, performing heat preservation reaction for 0.5-3.0 h, adding unsaturated carboxylic acid or unsaturated carboxylic anhydride, a polymerization inhibitor and a third catalyst, performing heat preservation reaction for 0.5-3.5 h, removing water by vacuumizing or introducing nitrogen and carrying water, cooling to room temperature after the reaction is finished, obtaining a first mixture containing an esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride, wherein the molar ratio of the dicarboxylic acid, the methoxypolyethylene glycol, the polyethylene glycol and the unsaturated carboxylic acid or unsaturated carboxylic anhydride is 1: 2-10, and the dosage of the first catalyst is 0.2-4.2% of the total mass of the dicarboxylic acid and the methoxypolyethylene glycol, the dosage of the second catalyst is 0.2-4.2% of the mass of the polyethylene glycol, the dosage of the third catalyst is 0.2-4.2% of the mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride, and the dosage of the polymerization inhibitor is 0.2-6.0% of the mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride.
More preferably, the molar ratio of the dicarboxylic acid, the methoxypolyethylene glycol, the polyethylene glycol and the unsaturated carboxylic acid or unsaturated carboxylic anhydride is 1: 3-8, the dosage of the first catalyst is 0.3-4.0% of the total mass of the dicarboxylic acid and the methoxypolyethylene glycol, the dosage of the second catalyst is 0.3-4.0% of the mass of the polyethylene glycol, the dosage of the third catalyst is 0.3-4.0% of the mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, and the dosage of the polymerization inhibitor is 0.5-5.0% of the mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride.
In a preferred embodiment of the present invention, the step (2) is: and (2) mixing the first mixture prepared in the step (1) with a small comonomer in a mass ratio of 200: 1-4 to obtain a comonomer mixture solution.
In a preferred embodiment of the present invention, the step (3) is: 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; 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 0.5-3.2% 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.
Further preferably, the total amount of water used in the step (3) and the step (2) is such that the mass concentration of the copolymerization product is 20-70%, the amount of the initiator is 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 0.2-2.0% of the total mass of the solutes in the comonomer mixture solution.
In a preferred embodiment of the present invention, the polymerization inhibitor is at least one of hydroquinone, phenothiazine and diphenylamine.
In a preferred embodiment of the invention, the initiator is a water-soluble redox initiator system or a water-soluble azo initiator.
In a preferred embodiment of the present invention, 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: according to the ester low-sensitivity polycarboxylate superplasticizer prepared by the preparation method, the branched chain is of a two-end two-stage polyether structure connected by ester groups, so that the sensitivity of the product can be remarkably reduced, the concrete performance of the product is not influenced when the concrete production factors such as environment temperature, single-formula water consumption, aggregate mud content and the mixing amount of the superplasticizer are changed, the concrete production is easy to control, and the stability of the concrete performance is improved. And because the branched chain and the main chain are connected in the form of ester group, the product has better workability when being used for concrete compared with the product in which the branched chain and the main chain are connected in the form of ether bond.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
The molecular weight of the effective component of the ester low-sensitive polycarboxylate superplasticizer prepared in the following embodiment is 10000-150000, and the structural formula of the effective component is as follows:
wherein R is1Is H or CH3，R2Is SO3M、NH2Or CONH2，R3Is H or COOM, R4Is H or CH3，R5Is H or COOM, R6Is H or CH3，R7Is empty or C1-4 alkyl, and M is H, Na, K or NH4。
Example 1
(1) Esterification reaction: heating 100.00g of oxalic acid and 222.10g of methoxy polyethylene glycol with molecular weight of 200 to 65 ℃ under the protection of nitrogen, adding 2.50g of first catalyst, carrying out heat preservation reaction for 2.0h, adding 222.10g of polyethylene glycol with molecular weight of 200 and 2.20g of second catalyst, carrying out heat preservation reaction for 1.0h, adding 80.00g of acrylic acid, 1.00g of polymerization inhibitor and 1.60g of third catalyst, carrying out heat preservation reaction for 1.0h, 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 esterification product and unreacted acrylic acid;
(2) monomer blending: mixing the first mixture prepared in the step (1) at 200.00 g, sodium methallyl sulfonate and water at 80.00g to obtain a comonomer mixture solution;
(3) and (3) copolymerization reaction: dripping the comonomer mixture solution, a hydrogen peroxide aqueous solution (wherein 1.80g of hydrogen peroxide and 20.00g of water), an ascorbic acid aqueous solution (wherein 0.60g of water and 20.00g of water) and a thioglycolic acid aqueous solution (wherein 1.00g of thioglycolic acid and 20.00g of water) into 60.00g of water for reaction at the reaction temperature of 40 ℃ 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 ester low-sensitivity polycarboxylate superplasticizer PCE-1.
Example 2
(1) Esterification reaction: heating 100.00g of malonic acid and 384.40g of methoxy polyethylene glycol with the molecular weight of 400 to 70 ℃ under the protection of nitrogen, adding 3.00g of a first catalyst, carrying out heat preservation reaction for 1.5h, adding 288.30g of polyethylene glycol with the molecular weight of 300 and 3.00g of a second catalyst, carrying out heat preservation reaction for 1.0h, adding 82.60g of methacrylic acid, 1.10g of a polymerization inhibitor and 2.00g of a third catalyst, carrying out heat preservation reaction for 1.5h, removing water by vacuumizing or introducing nitrogen, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an esterification product and unreacted methacrylic acid;
(2) monomer blending: mixing the first mixture obtained in the step (1) at 200.00 g, acrylamide at 3.00g and water at 80.00g to obtain 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 3.00g, the weight of the water is 40.00g) and an aqueous solution of sodium hypophosphite (wherein the weight of the sodium hypophosphite is 2.20g, the weight of the water is 20.00g) into 60.00g of water for reaction, wherein the reaction temperature is 50 ℃, the dropping time is 2.5 hours, and after the dropping is finished, preserving the heat for 1.0 hour 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 ester low-sensitivity polycarboxylate superplasticizer PCE-2.
Example 3
(1) Esterification reaction: heating 100.00g of succinic acid and 508.00g of methoxypolyethylene glycol with the molecular weight of 600 to 65 ℃ under the protection of nitrogen, adding 3.20g of a first catalyst, carrying out heat preservation reaction for 2.0h, adding 338.70g of polyethylene glycol with the molecular weight of 400 and 3.50g of a second catalyst, carrying out heat preservation reaction for 2.0h, adding 98.20g of fumaric acid, 1.20g of a polymerization inhibitor and 1.00g of a third catalyst, carrying out heat preservation reaction for 2.0h, 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 esterification product and unreacted fumaric acid;
(2) monomer blending: mixing the first mixture prepared in the step (1) of 200.00, 2.50g of allylamine and 80.00g of water to obtain a comonomer mixture solution;
(3) and (3) copolymerization reaction: dripping the comonomer mixture solution, an azodicyano valeric acid aqueous solution (wherein 3.20g of azodicyano valeric acid and 40.00g of water) and a trisodium phosphate aqueous solution (wherein 3.50g of trisodium phosphate and 20.00g of water) into 60.00g of water for reaction at the reaction temperature of 60 ℃ for 2.0h, and preserving heat for 0.5h 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 ester low-sensitivity polycarboxylate superplasticizer PCE-3.
Example 4
(1) Esterification reaction: heating 100.00g of glutaric acid and 605.50g of methoxy polyethylene glycol with molecular weight of 800 to 75 ℃ under the protection of nitrogen, adding 5.20g of first catalyst, carrying out heat preservation reaction for 1.5h, adding 378.50g of polyethylene glycol with molecular weight of 500 and 3.80g of second catalyst, carrying out heat preservation reaction for 1.0h, adding 98.40g of itaconic acid, 1.80g of polymerization inhibitor and 1.50g of third catalyst, carrying out heat preservation reaction for 2.0h, removing water by vacuumizing or introducing nitrogen, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an esterification product and unreacted itaconic acid;
(2) monomer blending: mixing the first mixture prepared in the step (1) at 200.00 g, sodium methallyl sulfonate and water at 80.00g to obtain a comonomer mixture solution;
(3) and (3) copolymerization reaction: dripping the comonomer mixture solution, a hydrogen peroxide aqueous solution (wherein, 1.30g 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, 0.50 g of ascorbic acid and 20.00g of water) into 60.00g of water for reaction at the reaction temperature of 30 ℃ for 4.0h, and preserving heat for 2.0h after finishing 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 ester low-sensitivity polycarboxylate superplasticizer PCE-4.
Example 5
(1) Esterification reaction: heating 100.00g of adipic acid and 684.30g of methoxy polyethylene glycol with molecular weight of 1000 to 80 ℃ under the protection of nitrogen, adding 4.50g of a first catalyst, carrying out heat preservation reaction for 1.0h, adding 410.60g of polyethylene glycol with molecular weight of 600 and 4.20g of a second catalyst, carrying out heat preservation reaction for 1.0h, adding 67.00g of maleic anhydride, 1.40g of a polymerization inhibitor and 1.50g of a third catalyst, carrying out heat preservation reaction for 1.5h, removing water by vacuumizing or introducing nitrogen, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an esterification product and unreacted maleic anhydride;
(2) monomer blending: mixing the first mixture prepared in the step (1) with 200.00 g of acrylamide and 80.00g of water 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 35 ℃, the dropping time is 4.0h, and after the dropping is finished, keeping the temperature for 0.5h 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-ester low-sensitivity polycarboxylate superplasticizer PCE-5.
Adopting Huarun P.O 42.5.5 ordinary portland cement, the concrete mix proportion is: 300kg/m3 of cement, 80kg/m3 of fly ash, 80kg/m3 of mineral powder, 735kg/m3 of sand, 1040kg/m3 of pebbles and 165kg/m3 of water, and the performance tests of the ether low-sensitivity polycarboxylate water reducer prepared in the embodiments 1 to 5 and the commercially available polycarboxylate water reducer (PCE) are respectively carried out on different environmental temperatures, single-component water consumption, aggregate mud content and water reducer mixing amount under the same conditions, and the test results are shown in tables 1, 2, 3 and 4.
TABLE 1 ambient temperature sensitivity
TABLE 2 sensitivity to Water consumption by Individual formula
TABLE 3 sensitivity of aggregate content to mud
TABLE 4 sensitivity of water reducing agent incorporation
As can be seen from tables 1-4, compared with the commercially available polycarboxylate superplasticizer (PCE), the synthesized examples of the present invention have higher water reducing rate, better concrete slump retention capacity and lower sensitivity to ambient temperature, single-formula water consumption, aggregate mud content and water reducer doping amount.
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:
the molecular weight of an active ingredient of the ester low-sensitivity polycarboxylate superplasticizer is 10000-150000, and the structural formula of the active ingredient is as follows:
wherein R is1Is H or CH3，R2Is SO3M、NH2Or CONH2，R3Is H or COOM, R4Is H or CH3，R5Is H or COOM, R6Is H or CH3，R7Is empty or C1-4 alkyl, and M is H, Na, K or NH4。
The preparation method of the ester low-sensitivity polycarboxylate superplasticizer comprises the following steps:
(1) esterification reaction: heating dicarboxylic acid and methoxypolyethylene glycol with molecular weight of 200-1000 to 60-100 ℃ under the protection of nitrogen, adding a first catalyst, performing heat preservation reaction for 0.4-2.5 h, adding polyethylene glycol with molecular weight of 200-1000 and a second catalyst, performing heat preservation reaction for 0.4-3.0 h, adding unsaturated carboxylic acid or unsaturated carboxylic anhydride, a polymerization inhibitor and a third catalyst, performing heat preservation reaction for 0.4-3.5 h, removing water by vacuumizing or introducing nitrogen to carry out water, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride; the dicarboxylic acid is at least one of oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid, the unsaturated carboxylic acid or unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid, fumaric acid, itaconic acid and maleic anhydride, the first catalyst is at least one of periodic acid, dinitrobenzoic acid and ethylene diamine tetraacetic acid, the second catalyst is at least one of periodic acid, dinitrobenzoic acid and ethylene diamine tetraacetic acid, and the third catalyst is at least one of concentrated sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid and ethylsulfonic acid;
(2) monomer blending: mixing the first mixture prepared in the step (1) with a small comonomer in a mass ratio of 200: 1-5 to obtain a comonomer mixture solution, wherein the small comonomer is at least one of sodium methallylsulfonate, acrylamide and acrylamide;
(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 10-63 ℃, 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;
(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 ester low-sensitivity polycarboxylate superplasticizer.
Preferably, the step (1) is: heating dicarboxylic acid and methoxypolyethylene glycol with molecular weight of 200-1000 to 60-90 ℃ under the protection of nitrogen, adding a first catalyst, performing heat preservation reaction for 0.5-2.5 h, adding polyethylene glycol with molecular weight of 200-1000 and a second catalyst, performing heat preservation reaction for 0.5-3.0 h, adding unsaturated carboxylic acid or unsaturated carboxylic anhydride, a polymerization inhibitor and a third catalyst, performing heat preservation reaction for 0.5-3.5 h, removing water by vacuumizing or introducing nitrogen and carrying water, cooling to room temperature after the reaction is finished, obtaining a first mixture containing an esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride, wherein the molar ratio of the dicarboxylic acid, the methoxypolyethylene glycol, the polyethylene glycol and the unsaturated carboxylic acid or unsaturated carboxylic anhydride is 1: 2-10, and the dosage of the first catalyst is 0.2-4.2% of the total mass of the dicarboxylic acid and the methoxypolyethylene glycol, the dosage of the second catalyst is 0.2-4.2% of the mass of the polyethylene glycol, the dosage of the third catalyst is 0.2-4.2% of the mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride, and the dosage of the polymerization inhibitor is 0.2-6.0% of the mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride. More preferably, the molar ratio of the dicarboxylic acid, the methoxypolyethylene glycol, the polyethylene glycol and the unsaturated carboxylic acid or unsaturated carboxylic anhydride is 1: 3-8, the dosage of the first catalyst is 0.3-4.0% of the total mass of the dicarboxylic acid and the methoxypolyethylene glycol, the dosage of the second catalyst is 0.3-4.0% of the mass of the polyethylene glycol, the dosage of the third catalyst is 0.3-4.0% of the mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride, and the dosage of the polymerization inhibitor is 0.5-5.0% of the mass of the unsaturated carboxylic acid or unsaturated carboxylic anhydride.
Preferably, the step (2) is: and (2) mixing the first mixture prepared in the step (1) with a small comonomer in a mass ratio of 200: 1-4 to obtain a comonomer mixture solution.
Preferably, the step (3) is: 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; 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 0.5-3.2% 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. Further preferably, the total amount of water used in the step (3) and the step (2) is such that the mass concentration of the copolymerization product is 20-70%, the amount of the initiator is 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 0.2-2.0% of the total mass of the solutes in the comonomer mixture solution.
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 (9)
1. An ester low-sensitivity polycarboxylate superplasticizer is characterized in that: the molecular weight of the effective component is 10000-150000, and the structural formula of the effective component is as follows:
wherein R is1Is H or CH3，R2Is SO3M、NH2Or CONH2，R3Is H or COOM, R4Is H or CH3，R5Is H or COOM, R6Is H or CH3，R7Is empty or C1-4 alkyl, and M is H, Na, K or NH4；
The preparation method comprises the following steps:
(1) esterification reaction: heating dicarboxylic acid and methoxypolyethylene glycol with molecular weight of 200-1000 to 60-100 ℃ under the protection of nitrogen, adding a first catalyst, performing heat preservation reaction for 0.4-2.5 h, adding polyethylene glycol with molecular weight of 200-1000 and a second catalyst, performing heat preservation reaction for 0.4-3.0 h, adding unsaturated carboxylic acid or unsaturated carboxylic anhydride, a polymerization inhibitor and a third catalyst, performing heat preservation reaction for 0.4-3.5 h, removing water by vacuumizing or introducing nitrogen to carry out water, and cooling to room temperature after the reaction is finished to obtain a first mixture containing an esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride; the dicarboxylic acid is at least one of oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid, the unsaturated carboxylic acid or unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid, fumaric acid, itaconic acid and maleic anhydride, the first catalyst is at least one of periodic acid, dinitrobenzoic acid and ethylene diamine tetraacetic acid, the second catalyst is at least one of periodic acid, dinitrobenzoic acid and ethylene diamine tetraacetic acid, and the third catalyst is at least one of concentrated sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid and ethylsulfonic acid;
(2) monomer blending: mixing the first mixture prepared in the step (1) with a small comonomer in a mass ratio of 200: 1-5 to obtain a comonomer mixture solution, wherein the small comonomer is at least one of sodium methallylsulfonate, acrylamide and acrylamide;
(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 10-63 ℃, 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;
(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 ester low-sensitivity polycarboxylate superplasticizer.
2. The ester low-sensitivity polycarboxylate superplasticizer according to claim 1, characterized in that: the step (1) is as follows: heating dicarboxylic acid and methoxypolyethylene glycol with molecular weight of 200-1000 to 60-90 ℃ under the protection of nitrogen, adding a first catalyst, performing heat preservation reaction for 0.5-2.5 h, adding polyethylene glycol with molecular weight of 200-1000 and a second catalyst, performing heat preservation reaction for 0.5-3.0 h, adding unsaturated carboxylic acid or unsaturated carboxylic anhydride, a polymerization inhibitor and a third catalyst, performing heat preservation reaction for 0.5-3.5 h, removing water by vacuumizing or introducing nitrogen and carrying water, cooling to room temperature after the reaction is finished, obtaining a first mixture containing an esterification product and unreacted unsaturated carboxylic acid or unsaturated carboxylic anhydride, wherein the molar ratio of the dicarboxylic acid, the methoxypolyethylene glycol, the polyethylene glycol and the unsaturated carboxylic acid or unsaturated carboxylic anhydride is 1: 2-10, and the dosage of the first catalyst is 0.2-4.2% of the total mass of the dicarboxylic acid and the methoxypolyethylene glycol, the dosage of the second catalyst is 0.2-4.2% of the mass of the polyethylene glycol, the dosage of the third catalyst is 0.2-4.2% of the mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride, and the dosage of the polymerization inhibitor is 0.2-6.0% of the mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride.
3. The ester low-sensitivity polycarboxylate superplasticizer according to claim 2, wherein: the molar ratio of the dicarboxylic acid to the methoxypolyethylene glycol to the polyethylene glycol to the unsaturated carboxylic acid or the unsaturated carboxylic anhydride is 1: 3-8, the dosage of the first catalyst is 0.3-4.0% of the total mass of the dicarboxylic acid and the methoxypolyethylene glycol, the dosage of the second catalyst is 0.3-4.0% of the mass of the polyethylene glycol, the dosage of the third catalyst is 0.3-4.0% of the mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride, and the dosage of the polymerization inhibitor is 0.5-5.0% of the mass of the unsaturated carboxylic acid or the unsaturated carboxylic anhydride.
4. The ester low-sensitivity polycarboxylate superplasticizer according to claim 1, characterized in that: the step (2) is as follows: and (2) mixing the first mixture prepared in the step (1) with a small comonomer in a mass ratio of 200: 1-4 to obtain a comonomer mixture solution.
5. The ester low-sensitivity polycarboxylate superplasticizer according to claim 1, characterized in that: the step (3) is as follows: 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; 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 0.5-3.2% 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.
6. The ester low-sensitivity polycarboxylate superplasticizer according to claim 5, wherein: the total amount of water used in the step (3) 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.
7. The ester type low-sensitivity polycarboxylate superplasticizer according to any one of claims 1 to 6, wherein: the polymerization inhibitor is at least one of hydroquinone, phenothiazine and diphenylamine.
8. The ester type low-sensitivity polycarboxylate superplasticizer according to any one of claims 1 to 6, wherein: the initiator is a water-soluble redox initiation system or a water-soluble azo initiator.
9. The ester type low-sensitivity polycarboxylate superplasticizer according to any one of claims 1 to 6, wherein: 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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| CN107602781A (en) * | 2017-09-20 | 2018-01-19 | 科之杰新材料集团有限公司 | A kind of esters promote the preparation method of solidifying Early-strength polycarboxylate superplasticizer |
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| CN107602781A (en) * | 2017-09-20 | 2018-01-19 | 科之杰新材料集团有限公司 | A kind of esters promote the preparation method of solidifying Early-strength polycarboxylate superplasticizer |
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