CN110642993A - Preparation method of retarding ether polycarboxylate superplasticizer - Google Patents
Preparation method of retarding ether polycarboxylate superplasticizer Download PDFInfo
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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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
- C04B2103/302—Water reducers
Abstract
The invention discloses a preparation method of a retarding ether polycarboxylic acid water reducing agent, which comprises the following steps: (1) preparing an esterified monomer; (2) carrying out copolymerization reaction; (3) and (4) neutralizing. The preparation method of the invention prepares the esterified monomer by esterifying the carbohydrate and the crotonic acid, and has the advantages of low cost and simple and convenient operation, and the prepared carbohydrate esterified product participates in the next copolymerization reaction, so that the main chain of the polycarboxylic acid water reducing agent is provided with a polyhydroxy structure, the prepared polycarboxylic acid water reducing agent has better retardation effect, the initial setting time and the final setting time of cement are effectively prolonged, and the negative effect brought by using the retarder can be reduced. And the carbohydrate polyhydroxy structure enables the polycarboxylate superplasticizer to have better slump retaining performance, thereby being beneficial to the pumping construction of concrete in summer.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a preparation method of a retarding ether polycarboxylic acid water reducer.
Background
Along with the construction of national large-scale infrastructure nuclear power, water conservancy, bridges and various large-scale projects, the requirements on the performance of concrete in all aspects are continuously improved, and the requirements on the performance of concrete admixtures are certainly improved.
Although the excellent water reducing performance of the polycarboxylic acid water reducing agent is widely accepted by the industry at present, the polycarboxylic acid water reducing agent has the problems of too fast slump loss, poor workability and the like in practical application due to factors such as the change of cement, the mud content of sand and stone materials and the like. The setting time of concrete transported for long distance in summer and constructed in hot weather is usually prolonged by adopting a method of compounding the retarder, but the polycarboxylate water reducer compounded with more retarders has longer standing time, so that the retarder components contained in the upper and lower water reducers are different easily, and the problem of short or long setting time can be caused in the practical application process to influence the engineering construction, so that the development of the retarding type ester polycarboxylate water reducer has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a retarding ether polycarboxylic acid water reducing agent.
The technical scheme of the invention is as follows:
a preparation method of a retarding ether polycarboxylate superplasticizer comprises the following steps:
(1) preparing an esterified monomer: adding a saccharide compound, crotonic acid, a first catalyst and a polymerization inhibitor into a first reaction device provided with a condensing device, reacting at a constant temperature of 90-120 ℃ for 4-6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer containing a mixture of a saccharide esterified product and crotonic acid; the saccharide compound is glucose or sucrose, and the first catalyst is a supported solid acid catalyst SO4 2-/SiO2-TiO2The polymerization inhibitor is 4-tert-butyl catechol, hydroquinone, 2, 5-di-tert-butyl hydroquinone, methyl hydroquinone or p-benzoquinone;
(2) and (3) copolymerization reaction: adding unsaturated polyoxyethylene ether, azo initiator, second catalyst and water into a second reaction device; uniformly mixing the esterified monomer prepared in the step (1), unsaturated phosphate, acrylic acid and water in a first dripping device; uniformly mixing an oxidant and water in a second dripping device; uniformly mixing a reducing agent, a chain transfer agent and water in a third dripping device; at normal temperature, materials in the second dripping device, the third dripping device and the first dripping device are dripped into the second reaction device in sequence, the materials in the first dripping device, the third dripping device and the second dripping device are dripped in 1-1.5 hours respectively, and the constant temperature reaction is carried out for 0.4-0.6 hour; the unsaturated polyoxyethylene ether is 4-hydroxybutyl vinyl ether polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene polyoxypropylene ether or allyl alcohol polyoxyethylene ether with the molecular weight of 3000-5000, the azo initiator is azobisisobutyramidine hydrochloride, azobisisobutyronitrile or N, N' -dihydroxyethyl azobisisobutyramidine hydrochloride, the second catalyst is one or two of manganese sulfate, zirconium chloride and zinc chloride, the unsaturated phosphate is methacrylic acid-beta-hydroxyethyl phosphate or acrylic acid-beta-hydroxyethyl phosphate, and the chain transfer agent is sodium hypophosphite;
(3) and (3) neutralization reaction: and (3) adding a proper amount of aqueous solution of a neutralizing agent into the material obtained in the step (2) to obtain the retarding ether polycarboxylic acid water reducing agent.
In a preferred embodiment of the present invention, in the step (1), the mass ratio of the saccharide compound, the crotonic acid, the first catalyst and the polymerization inhibitor is 100: 30 to 220: 0.5 to 1.5: 0.5 to 2.
In a preferred embodiment of the present invention, in the second reaction device in the step (2), the mass ratio of the unsaturated polyoxyethylene ether, the azo initiator, the second catalyst and the water is 200: 1 to 4: 0.05 to 0.8: 265 to 290.
In a preferred embodiment of the invention, in the first dripping device in the step (2), the mass ratio of the esterified monomer prepared in the step (1), the unsaturated phosphate, the acrylic acid and the water is 3-10: 3-7: 10-18: 20.
In a preferred embodiment of the present invention, in the second dripping device in the step (2), the mass ratio of the oxidant to the water is 1-4: 20.
In a preferred embodiment of the present invention, in the third dripping device in the step (2), the mass ratio of the reducing agent, the chain transfer agent and the water is 2-4: 1.5-4: 20.
In a preferred embodiment of the present invention, the oxidizing agent is hydrogen peroxide, sodium persulfate or ammonium persulfate.
In a preferred embodiment of the invention, the reducing agent is ascorbic acid, erythorbic acid, ferrous sulfate, sodium bisulfite, ferrous pyrophosphate or ferrous chloride.
In a preferred embodiment of the invention, the neutralizing agent is sodium hydroxide, sodium tert-butoxide or sodium methoxide.
The invention has the beneficial effects that:
1. the preparation method of the invention prepares the esterified monomer by esterifying the carbohydrate and the crotonic acid, and has the advantages of low cost and simple and convenient operation, and the prepared carbohydrate esterified product participates in the next copolymerization reaction, so that the main chain of the polycarboxylic acid water reducing agent is provided with a polyhydroxy structure, the prepared polycarboxylic acid water reducing agent has better retardation effect, the initial setting time and the final setting time of cement are effectively prolonged, and the negative effect brought by using the retarder can be reduced. And the carbohydrate polyhydroxy structure enables the polycarboxylate superplasticizer to have better slump retaining performance, thereby being beneficial to the pumping construction of concrete in summer.
2. According to the preparation method, unsaturated phosphate ester monomer copolymerization is introduced, so that phosphate radicals with two negative charges in the water reducing agent are adsorbed on the surfaces of cement particles, and the early-stage dispersing capacity of the cement particles is improved due to the action of electrostatic repulsion;
3. the catalyst is introduced into the copolymerization process, so that the reaction efficiency can be effectively improved, the reaction time is shortened, and the production cost is saved.
4. In the copolymerization process, a low-temperature initiation system and a medium-high temperature azo initiator are used for composite initiation, so that the polymerization reaction can be carried out under the initial low-temperature condition, the heat generated by the polymerization reaction is utilized to promote the medium-high temperature azo initiator to continue to initiate the polymerization of residual monomers in the solution, the conversion rate of the monomers is effectively improved, the reaction is more complete, the reaction monomer residue is reduced, the improvement of the performance of the water reducing agent is facilitated, the waste of raw materials is effectively avoided, and the high-conversion-rate block polymer with better dispersibility and dispersibility maintaining capability is facilitated to be obtained.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
(1) Preparing an esterified monomer: according to the weightBased on the parts by weight, 100 parts of sucrose, 32 parts of crotonic acid and 0.5 part of supported solid acid catalyst SO4 2-/SiO2-TiO2Adding 1.5 parts of p-benzoquinone into a first reaction device provided with a condensing device, reacting for 4 hours at the constant temperature of 95 ℃ under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer containing a mixture of a sugar esterified product and crotonic acid;
(2) and (3) copolymerization reaction: firstly, 200 parts by weight of allyl polyoxyethylene polyoxypropylene ether with the molecular weight of 3000, 2.5 parts by weight of azobisisobutyronitrile, 0.08 part by weight of zirconium chloride and 275 parts by weight of water are added into a second reaction device; 8 parts of the esterified monomer prepared in the step (1), 5 parts of methacrylic acid-beta-hydroxyethyl phosphate, 12 parts of acrylic acid and 20 parts of water are uniformly mixed in a first dripping device; uniformly mixing 1 part of ammonium persulfate and 20 parts of water in a second dripping device; 3 parts of ferrous sulfate, 2.5 parts of sodium hypophosphite and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, materials in the second dripping device, the third dripping device and the first dripping device are dripped into the second reaction device in sequence, the materials in the first dripping device, the third dripping device and the second dripping device are dripped in 1.5 hours respectively, and the constant temperature reaction is carried out for 0.5 hour;
(3) and (3) neutralization reaction: and adding 20 parts by weight of sodium hydroxide with the mass concentration of 30% to obtain the retarding ether polycarboxylic acid water reducer with the concentration of 40%.
Example 2
(1) Preparing an esterified monomer: based on the parts by weight, 100 parts of sucrose, 40 parts of crotonic acid and 1.2 parts of supported solid acid catalyst SO4 2-/SiO2-TiO2Adding 1 part of 4-tert-butyl catechol into a first reaction device provided with a condensing device, reacting for 5 hours at a constant temperature of 115 ℃ under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer containing a mixture of a sugar esterified product and crotonic acid;
(2) and (3) copolymerization reaction: adding 200 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether with the molecular weight of 5000, 3 parts by weight of azobisisobutyramidine hydrochloride, 0.1 part by weight of zinc chloride and 270 parts by weight of water into a second reaction device; 5 parts of the esterified monomer prepared in the step (1), 3 parts of methacrylic acid-beta-hydroxyethyl phosphate, 15 parts of acrylic acid and 20 parts of water are uniformly mixed in a first dripping device; 2 parts of hydrogen peroxide and 20 parts of water are uniformly mixed in a second dripping device; 2 parts of ascorbic acid, 1.8 parts of sodium hypophosphite and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, materials in the second dripping device, the third dripping device and the first dripping device are dripped into the second reaction device in sequence, the materials in the first dripping device, the third dripping device and the second dripping device are dripped in 1.5 hours respectively, and the constant temperature reaction is carried out for 0.5 hour;
(3) and (3) neutralization reaction: and adding 20 parts by weight of sodium hydroxide with the mass concentration of 30% to obtain the retarding ether polycarboxylic acid water reducer with the concentration of 40%.
Example 3
(1) Preparing an esterified monomer: based on the parts by weight, 100 parts of glucose, 214 parts of crotonic acid and 0.8 part of supported solid acid catalyst SO4 2-/SiO2-TiO2Adding 0.8 part of 2, 5-di-tert-butylhydroquinone into a first reaction device provided with a condensing device, reacting at a constant temperature of 105 ℃ for 5 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer containing a mixture of a saccharide esterified product and crotonic acid;
(2) and (3) copolymerization reaction: firstly, 200 parts by weight of methallyl alcohol polyoxyethylene ether with the molecular weight of 2400, 1 part by weight of azobisisobutyramidine hydrochloride, 0.5 part by weight of manganese sulfate and 282 parts by weight of water are added into a second reaction device; uniformly mixing 10 parts of the esterified monomer prepared in the step (1), 7 parts of acrylic acid-beta-hydroxyethyl phosphate, 10 parts of acrylic acid and 20 parts of water in a first dripping device; 3 parts of sodium persulfate and 20 parts of water are uniformly mixed in a second dripping device; 4 parts of isoascorbic acid, 4 parts of sodium hypophosphite and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, materials in the second dripping device, the third dripping device and the first dripping device are dripped into the second reaction device in sequence, the materials in the first dripping device, the third dripping device and the second dripping device are respectively dripped in 1h, and the constant temperature reaction is carried out for 0.5 h;
(3) and (3) neutralization reaction: and adding 20 parts by weight of sodium hydroxide with the mass concentration of 30% to obtain the retarding ether polycarboxylic acid water reducer with the concentration of 40%.
Example 4
(1) Preparing an esterified monomer: 100 portions of glucose, 193 portions of crotonic acid and 1.8 portions of supported solid acid catalyst SO are added according to the weight portion4 2-/SiO2-TiO2Adding 1.2 parts of methyl hydroquinone into a first reaction device provided with a condensing device, reacting for 4 hours at a constant temperature of 100 ℃ under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer containing a mixture of a sugar esterified product and crotonic acid;
(2) and (3) copolymerization reaction: adding 200 parts by weight of methallyl polyoxyethylene polyoxypropylene ether with the molecular weight of 5000, 1.8 parts by weight of N, N' -dihydroxyethyl azo diisobutylamine hydrochloride, 0.2 part by weight of zinc chloride and 274 parts by weight of water into a second reaction device; 3 parts of the esterified monomer prepared in the step (1), 8 parts of acrylic acid-beta-hydroxyethyl phosphate, 13 parts of acrylic acid and 20 parts of water are uniformly mixed in a first dripping device; 4 parts of ammonium persulfate and 20 parts of water are uniformly mixed in the second dripping device; 2 parts of ferrous pyrophosphate, 3 parts of sodium hypophosphite and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, materials in the second dripping device, the third dripping device and the first dripping device are dripped into the second reaction device in sequence, the materials in the first dripping device, the third dripping device and the second dripping device are respectively dripped in 1h, and the constant temperature reaction is carried out for 0.5 h;
(3) and (3) neutralization reaction: and adding 20 parts by weight of sodium hydroxide with the mass concentration of 30% to obtain the retarding ether polycarboxylic acid water reducer with the concentration of 40%.
The slump constant, the strength of each stage of concrete and the initial setting time of concrete were measured by using the retarding ether polycarboxylic acid water reducing agent synthesized in examples 1 to 4 and a reference sample (commercial retarding polycarboxylic acid water reducing agent) with standard cement in an amount of 0.2% by mass of cement (converted into solid) according to GB 8076 + 2008 concrete admixture. The concrete mixing proportion is as follows: the initial slump of cement 360kg/m3, sand 803kg/m3 and stones 982kg/m3 was controlled at 100. + -.10 mm, and the results are shown in Table 1.
Table 1 comparison of the properties of the examples
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 preparation method of a retarding ether polycarboxylate superplasticizer comprises the following steps:
(1) preparing an esterified monomer: adding a saccharide compound, crotonic acid, a first catalyst and a polymerization inhibitor into a first reaction device provided with a condensing device, reacting at a constant temperature of 90-120 ℃ for 4-6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer containing a mixture of a saccharide esterified product and crotonic acid; the saccharide compound is glucose or sucrose, and the first catalyst is a supported solid acid catalyst SO4 2-/SiO2-TiO2The polymerization inhibitor is 4-tert-butyl catechol, hydroquinone, 2, 5-di-tert-butyl hydroquinone, methyl hydroquinone or p-benzoquinone;
(2) and (3) copolymerization reaction: adding unsaturated polyoxyethylene ether, azo initiator, second catalyst and water into a second reaction device; uniformly mixing the esterified monomer prepared in the step (1), unsaturated phosphate, acrylic acid and water in a first dripping device; uniformly mixing an oxidant and water in a second dripping device; uniformly mixing a reducing agent, a chain transfer agent and water in a third dripping device; at normal temperature, materials in the second dripping device, the third dripping device and the first dripping device are dripped into the second reaction device in sequence, the materials in the first dripping device, the third dripping device and the second dripping device are dripped in 1-1.5 hours respectively, and the constant temperature reaction is carried out for 0.4-0.6 hour; the unsaturated polyoxyethylene ether is 4-hydroxybutyl vinyl ether polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene polyoxypropylene ether or allyl alcohol polyoxyethylene ether with the molecular weight of 3000-5000, the azo initiator is azobisisobutyramidine hydrochloride, azobisisobutyronitrile or N, N' -dihydroxyethyl azobisisobutyramidine hydrochloride, the second catalyst is one or two of manganese sulfate, zirconium chloride and zinc chloride, the unsaturated phosphate is methacrylic acid-beta-hydroxyethyl phosphate or acrylic acid-beta-hydroxyethyl phosphate, and the chain transfer agent is sodium hypophosphite;
(3) and (3) neutralization reaction: and (3) adding a proper amount of aqueous solution of a neutralizing agent into the material obtained in the step (2) to obtain the retarding ether polycarboxylic acid water reducing agent.
In the step (1), the mass ratio of the carbohydrate, the crotonic acid, the first catalyst and the polymerization inhibitor is 100: 30-220: 0.5-1.5: 0.5-2. In the second reaction device in the step (2), the mass ratio of unsaturated polyoxyethylene ether, azo initiator, second catalyst and water is 200: 1-4: 0.05-0.8: 265-290, in the first dripping device, the mass ratio of esterified monomer, unsaturated phosphate, acrylic acid and water prepared in the step (1) is 3-10: 3-7: 10-18: 20, in the second dripping device, the mass ratio of oxidant and water is 1-4: 20, and in the third dripping device, the mass ratio of reducing agent, chain transfer agent and water is 2-4: 1.5-4: 20.
The oxidant is hydrogen peroxide, sodium persulfate or ammonium persulfate. The reducing agent is ascorbic acid, isoascorbic acid, ferrous sulfate, sodium bisulfite, ferrous pyrophosphate or ferrous chloride. The neutralizer is sodium hydroxide, sodium tert-butoxide or sodium methoxide.
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. A preparation method of a retarding ether polycarboxylate superplasticizer is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing an esterified monomer: mixing saccharide compound, crotonic acid, and catalystAdding a catalyst and a polymerization inhibitor into a first reaction device provided with a condensing device, reacting at a constant temperature of 90-120 ℃ for 4-6 h under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer containing a mixture of a saccharide esterified product and crotonic acid; the saccharide compound is glucose or sucrose, and the first catalyst is a supported solid acid catalyst SO4 2-/SiO2-TiO2The polymerization inhibitor is 4-tert-butyl catechol, hydroquinone, 2, 5-di-tert-butyl hydroquinone, methyl hydroquinone or p-benzoquinone;
(2) and (3) copolymerization reaction: adding unsaturated polyoxyethylene ether, azo initiator, second catalyst and water into a second reaction device; uniformly mixing the esterified monomer prepared in the step (1), unsaturated phosphate, acrylic acid and water in a first dripping device; uniformly mixing an oxidant and water in a second dripping device; uniformly mixing a reducing agent, a chain transfer agent and water in a third dripping device; at normal temperature, materials in the second dripping device, the third dripping device and the first dripping device are dripped into the second reaction device in sequence, the materials in the first dripping device, the third dripping device and the second dripping device are dripped in 1-1.5 hours respectively, and the constant temperature reaction is carried out for 0.4-0.6 hour; the unsaturated polyoxyethylene ether is 4-hydroxybutyl vinyl ether polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene polyoxypropylene ether or allyl alcohol polyoxyethylene ether with the molecular weight of 3000-5000, the azo initiator is azobisisobutyramidine hydrochloride, azobisisobutyronitrile or N, N' -dihydroxyethyl azobisisobutyramidine hydrochloride, the second catalyst is one or two of manganese sulfate, zirconium chloride and zinc chloride, the unsaturated phosphate is methacrylic acid-beta-hydroxyethyl phosphate or acrylic acid-beta-hydroxyethyl phosphate, and the chain transfer agent is sodium hypophosphite;
(3) and (3) neutralization reaction: and (3) adding a proper amount of aqueous solution of a neutralizing agent into the material obtained in the step (2) to obtain the retarding ether polycarboxylic acid water reducing agent.
2. The method of claim 1, wherein: in the step (1), the mass ratio of the carbohydrate, the crotonic acid, the first catalyst and the polymerization inhibitor is 100: 30-220: 0.5-1.5: 0.5-2.
3. The method of claim 1, wherein: in the second reaction device in the step (2), the mass ratio of the unsaturated polyoxyethylene ether, the azo initiator, the second catalyst and the water is 200: 1-4: 0.05-0.8: 265-290.
4. The method of claim 1, wherein: in the first dripping device in the step (2), the mass ratio of the esterified monomer prepared in the step (1), the unsaturated phosphate, the acrylic acid and the water is 3-10: 3-7: 10-18: 20.
5. The method of claim 1, wherein: in the second dripping device in the step (2), the mass ratio of the oxidant to the water is 1-4: 20.
6. The method of claim 1, wherein: in the third dripping device in the step (2), the mass ratio of the reducing agent, the chain transfer agent and the water is 2-4: 1.5-4: 20.
7. The method of claim 1, wherein: the oxidant is hydrogen peroxide, sodium persulfate or ammonium persulfate.
8. The method of claim 1, wherein: the reducing agent is ascorbic acid, isoascorbic acid, ferrous sulfate, sodium bisulfite, ferrous pyrophosphate or ferrous chloride.
9. The method of claim 1, wherein: the neutralizer is sodium hydroxide, sodium tert-butoxide or sodium methoxide.
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| CN113861353A (en) * | 2021-10-20 | 2021-12-31 | 陕西科之杰新材料有限公司 | Antibacterial slump retaining agent and preparation method thereof |
| CN113956406A (en) * | 2021-10-09 | 2022-01-21 | 科之杰新材料集团有限公司 | Slump-retaining type polycarboxylate superplasticizer and preparation method thereof |
| CN114014990A (en) * | 2021-10-09 | 2022-02-08 | 科之杰新材料集团有限公司 | High-workability slow-release polycarboxylate superplasticizer and preparation method thereof |
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