CN109517114B - Early-strength slump-retaining polycarboxylic acid water reducer and preparation method thereof - Google Patents
Early-strength slump-retaining polycarboxylic acid water reducer and preparation method thereof Download PDFInfo
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers 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
An early strength slump retaining polycarboxylic acid type water reducing agent and a preparation method thereof, wherein the early strength slump retaining polycarboxylic acid type water reducing agent comprises the following components in parts by weight: methallyl polyoxyethylene ether: 0.8-1.2 parts; n-methylolacrylamide: 3-5 parts; functional monomer: 2-4 parts; acrylic acid: 5-9 parts of a solvent; ammonium persulfate: 0.02-0.04 parts of sodium bisulfite: 0.01-0.02 parts of chain transfer agent: 0.005-0.01 portion. Based on the molecular structure design principle, the novel polycarboxylic acid water reducing agent with the functions of early strength and slump loss resistance is synthesized by taking methyl allyl polyoxyethylene ether as a raw material, adding a self-made functional monomer containing more carboxyl and ester groups with plasticity retention property and introducing amide and other groups with the function of early strength, and the technical bias in the field is broken through.
Description
The technical field is as follows:
the invention relates to an early-strength slump-retaining polycarboxylic acid water reducer and a preparation method thereof.
Background art:
the polycarboxylic acid water reducing agent has the most significant advantages, and the yield of the polycarboxylic acid water reducing agent (20 percent mother liquor) reaches 6219 ten thousand tons accounting for 80 percent of the market yield of the high-efficiency water reducing agent in 2015. However, the polycarboxylic acid water reducing agent has the main problems that the adopted macromonomer is seriously homogenized and has poor adaptability with sandstone with high mud content; the early strength and slump loss of the prepared concrete are often contradictory. In order to solve the problems, a concrete mixing plant usually adopts a method of compounding a retarder, a slump retaining agent, an early strength agent and the like, but the compounded components are difficult to control, the compatibility is poor, and the mixing plant is also very troubled.
The technical personnel introduce a beta-dextrin esterified intermediate as a comonomer, so that the copolymer contains a large amount of retarding groups, and the synthesized super-retarding comb-shaped copolymer water reducing agent has obvious retarding effect, small flow loss of cement paste in a long time and no influence on the strength of the middle and later periods. The polycarboxylic acid water reducer with the early strength function is prepared by using acrylic acid, isobutylene alcohol polyoxyethylene ether (HPEG), sodium methallyl sulfonate and the like as monomers, partially substituting acrylic acid by using a monomer containing an amide group through an aqueous solution polymerization method. And the Liu Xiao and the like are synthesized into a novel amide water reducing agent by taking amino-terminated methoxy polyethylene glycol (NPEG) as a side chain and connecting the side chain with main chain polyacrylic acid through amido bond. Compared with the common water reducing agent, the concrete doped with the amide water reducing agent has better air content, slump retention capacity and frost resistance. However, in the above studies, early strength contradicts slump retention (i.e., slump retention may be reduced while early strength is improved, and slump retention may be reduced while slump retention is improved). The prior art does not have a good solution to this problem.
The invention content is as follows:
aiming at the defects in the prior art, the invention provides the early-strength slump-retaining polycarboxylic acid water reducer and the preparation method thereof, the components and the preparation method are reasonable, the problem of contradiction between early strength and slump-retaining performance is effectively solved, and the problems in the prior art are solved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the structural formula of the early strength slump retaining type polycarboxylic acid water reducing agent is shown as the formula (I):
wherein n, x, y, z are positive integers.
Preferably, the early-strength slump-retaining polycarboxylic acid water reducer comprises the following components in parts by weight: methallyl polyoxyethylene ether: 0.8-1.2 parts; n-methylolacrylamide: 3-5 parts; functional monomer: 2-4 parts; acrylic acid: 5-9 parts of a solvent; ammonium persulfate: 0.02-0.04 parts of sodium bisulfite: 0.01-0.02 parts of chain transfer agent: 0.005-0.01 portion; the structural formula of the functional monomer is shown as the formula (II):
preferably, the functional monomer is synthesized according to the following steps: adding maleic acid and tartaric acid with equal amount of substances into a reactor, heating to 60-80 deg.C, stirring under reflux condensation for 20-50min, dripping triethanolamine with equal amount of substances into the reactor with a constant pressure dropping funnel, heating to 95-105 deg.C, sealing for 5-6h, and naturally cooling to obtain the functional monomer.
Preferably, the chain transfer agent is mercaptopropionic acid or mercaptoacetic acid or isopropanol or sodium methallylsulfonate or alkyl mercaptan or alkyl dithioxanthate.
A preparation method of an early-strength slump-retaining polycarboxylic acid water reducer comprises the following steps:
s1, adding methyl allyl polyoxyethylene ether, N-hydroxymethyl acrylamide, a functional monomer and water into a reactor, and heating to dissolve;
s2, adding sodium bisulfite when the temperature is raised to 50-70 ℃, and then stirring for not less than 10 min;
s3, dropwise adding the prepared chain transfer agent solution, acrylic acid solution and ammonium persulfate solution into the reactor by using a constant-pressure dropping funnel respectively at the dropping speed of 0.15-0.30ml/min, and then keeping the temperature to continue reacting for 1.0-1.5 h;
and S4, after the reaction is finished, cooling to 20-30 ℃, and adjusting the pH value to 6.5-7.5 by using a sodium hydroxide solution to obtain a final product.
Preferably, in S3, the delay is at least 30min after the last addition of the ammonium persulfate solution.
Preferably, in S4, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 30% to 50%.
Preferably, the chain transfer agent is mercaptopropionic acid or mercaptoacetic acid or isopropanol or sodium methallylsulfonate or alkyl mercaptan or alkyl dithioxanthate.
Preferably, in S3, the concentration of the chain transfer agent solution is 0.20-0.30 mol/L.
Preferably, in S3, the concentration of the acrylic acid solution is 0.03 to 0.06 mol/L; the concentration of the ammonium persulfate solution is 0.03-0.06mol/L, the mass of the used ammonium persulfate is 2-4% of that of the vinyl monomer, and the molar ratio of the used sodium bisulfite to the ammonium persulfate is 1: 1.5-2.5.
Compared with the prior art, the invention has the advantages that: based on the molecular structure design principle, the novel polycarboxylic acid water reducing agent with the functions of early strength and slump loss resistance is synthesized by taking methyl allyl polyoxyethylene ether as a raw material, adding a self-made functional monomer containing more carboxyl and ester groups with plasticity retention property and introducing amide and other groups with the function of early strength, and the technical bias in the field is broken through.
Description of the drawings:
FIG. 1 is an infrared spectrum of a functional monomer.
FIG. 2 is an infrared spectrum of the water reducing agent.
FIG. 3 is a water reducing agent Gel Permeation Chromatogram (GPC).
FIG. 4 is an XRD (X-ray diffraction) spectrum of a blank sample in the 1d age and a cement sample doped with a water reducing agent.
The specific implementation mode is as follows:
in order to clearly illustrate the technical features of the present invention, the present invention will be explained in detail by the following embodiments and the accompanying drawings.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the structural formula of the early strength slump retaining type polycarboxylic acid water reducing agent is shown as the formula (I):
wherein n, x, y, z are positive integers.
The early-strength slump-retaining polycarboxylic acid water reducer comprises the following components in parts by weight: methallyl polyoxyethylene ether: 0.8-1.2 parts; n-methylolacrylamide: 3-5 parts; functional monomer: 2-4 parts; acrylic acid: 5-9 parts of a solvent; ammonium persulfate: 0.02-0.04 parts of sodium bisulfite: 0.01-0.02 parts of chain transfer agent: 0.005-0.01 portion; the structural formula of the functional monomer is shown as the formula (II):
the novel polycarboxylic acid water reducing agent with the functions of early strength and slump loss resistance is finally synthesized by self-preparing functional monomers containing more carboxyl and ester groups with plasticity retention property and simultaneously introducing amide and other groups with the early strength function into the water reducing agent.
The functional monomer is synthesized according to the following steps: adding maleic acid and tartaric acid with equal amount of substances into a reactor, heating to 60-80 deg.C, stirring under reflux condensation for 20-50min, dripping triethanolamine with equal amount of substances into the reactor with a constant pressure dropping funnel, heating to 95-105 deg.C, sealing for 5-6h, and naturally cooling to obtain the functional monomer. The method has the advantages of simple synthesis method and high yield.
The chain transfer agent is mercaptopropionic acid, mercaptoacetic acid, isopropanol, sodium methyl propylene sulfonate, alkyl mercaptan or alkyl dithioxanthate.
A preparation method of an early-strength slump-retaining polycarboxylic acid water reducer comprises the following steps:
s1, adding methyl allyl polyoxyethylene ether, N-hydroxymethyl acrylamide, a functional monomer and water into a reactor, and heating to dissolve;
s2, adding sodium bisulfite when the temperature is raised to 50-70 ℃, and then stirring for not less than 10 min;
s3, dropwise adding the prepared chain transfer agent solution, acrylic acid solution and ammonium persulfate solution into the reactor by using a constant-pressure dropping funnel respectively at the dropping speed of 0.15-0.30ml/min, and then keeping the temperature to continue reacting for 1.0-1.5 h;
and S4, after the reaction is finished, cooling to 20-30 ℃, and adjusting the pH value to 6.5-7.5 by using a sodium hydroxide solution to obtain a final product.
In S3, the last addition of the ammonium persulfate solution is completed, and the delay is at least 30 min. Ensuring the reaction to be carried out completely.
In S4, the sodium hydroxide solution has a sodium hydroxide mass fraction of 30% to 50%. Controlling the water content of the material.
The chain transfer agent is mercaptopropionic acid, mercaptoacetic acid, isopropanol, sodium methyl propylene sulfonate, alkyl mercaptan or alkyl dithioxanthate.
In S3, the concentration of the chain transfer agent solution is 0.20-0.30 mol/L.
In S3, the concentration of the acrylic acid solution is 0.03-0.06 mol/L; the concentration of the ammonium persulfate solution is 0.03-0.06mol/L, the mass of the used ammonium persulfate is 2-4% of that of the vinyl monomer, and the molar ratio of the used sodium bisulfite to the ammonium persulfate is 1: 1.5-2.5. Through experimental research, the finally obtained water reducing agent has excellent performance by adopting the substances with the concentrations and the qualities.
Orthogonal tests were designed with a fixed molar amount of methallyl polyoxyethylene ether as the base number, and the molar ratio of other raw materials to it and the reaction temperature as factors, and are shown in table 1:
TABLE 1 orthogonal factor horizon
And then carrying out performance test on the obtained water reducing agent according to the following method: the fluidity of the cement paste and the water reducing rate of the cement mortar are tested according to GB/T8077-2012 'homogeneity test method for concrete admixture'. W/C is 0.29, and the mixing amount of the synthetic water reducing agent is 0.08% (in bending solid). The application performance of the water reducer in concrete is tested according to the standard of a high-performance water reducer specified in GB 8076 plus 2008 'concrete admixture', and the concrete slump loss and the compressive strength ratios of different ages are tested. The concrete test block is formed according to the mixing proportion of C40, wherein W/C is 0.40, Sp is 36%, and the mixing amount of the water reducing agent is 0.15% (in bending and fixing).
The molecular structure and molecular weight analysis of the water reducing agent is carried out according to the following modes: and (3) taking a small amount of the synthesized macromonomer and water reducer samples to be detected, completely drying the samples at 60 ℃ in a vacuum drying oven, and determining the FT-IR spectrum of the samples by a tabletting method to represent the molecular structure of the samples. Adopts a domestic PE Paragon-1000 infrared spectrometer with a scanning frequency range of 500-4000 cm-1. A gel chromatograph Breeze 2HPLC of Waters company in America is adopted to characterize the molecular weight and the molecular weight distribution condition of the water reducing agent, the flow rate is 2.0ml/min, the sample injection volume is 50.00 mu l, the running time is 35min, and the mobile phase is tetrahydrofuran.
The effect of the water reducing agent on the early hydration products of the cement is carried out as follows: and (3) observing the composition of hydration products of the water-reducing agent-doped blank sample in the 1d age by adopting a TD-3700 type X-ray diffractometer, wherein the testing angle range is 10-80 degrees.
The orthogonal test was performed under the conditions of table 1, and the test results obtained are shown in table 2:
TABLE 2 results of orthogonal experiments
According to the optimized level combination of each index factor in the table 2, it can be seen that each index performance at 60 ℃ is optimal, the temperature has a large influence on the latter three test indexes, and the reaction temperature has a large influence on the polymerization degree and the reaction activity because the reaction adopts a redox system of sodium bisulfite-ammonium persulfate. The influence of the amount of acrylic acid on the water reducing rate and the initial slump is the largest, the optimal performance is realized for four indexes when the molar ratio of the acrylic acid to the methallyl polyoxyethylene ether is 1:7, and the optimal performance is realized for 2h slump only when the molar ratio of the acrylic acid to the methallyl polyoxyethylene ether is 1: 4. It can be seen that the acid ether ratio has a greater influence on the performance of the water reducing agent, and as the molar ratio of the acid ether increases, the water reducing rate of the water reducing agent increases, but the slump retention capacity decreases. The content of the functional monomer is a secondary factor, but the optimized combination of all indexes is irregular, and according to the range difference result, when the molar ratio of the functional monomer to the methyl allyl polyoxyethylene ether is 1:3, the water-reducing rate index is only 2% higher than 1:2, and the initial slump is 50mm higher; but the slump after 2 hours is reduced by 40mm, and the molar ratio of the functional monomer to the methallyl polyoxyethylene ether is 1:3 by combining other two strength ratio indexes; similarly, the molar ratio of N-methylolacrylamide to methallyl polyoxyethylene ether can be determined by a factor of 1: 4. The optimal combination is that the molar ratio of acrylic acid to the methyl allyl polyoxyethylene ether is 1:7, the molar ratio of N-hydroxymethyl acrylamide to the methyl allyl polyoxyethylene ether is 1:4, the molar ratio of the functional monomer to the methyl allyl polyoxyethylene ether is 1:3, the optimal temperature is 60 ℃, and the water reducing agent is not in orthogonal 9 groups of tests, so that the water reducing agent is synthesized again according to the optimal combination, and the performances of all aspects are tested: the water reducing rate is 32 percent, and the initial slump is 220 mm; the slump is 160mm after 2 hours; the compressive strength ratio of the 1d mortar test block is 185%; the 3d compressive strength ratio is 177 percent, and the 28d compressive strength ratio is 145 percent, which all meet the performance index requirements of the high-performance early-strength water reducing agent in the concrete admixture standard. Comprehensively considering all performance indexes, the optimal synthesis process condition is determined as n (methyl allyl polyoxyethylene ether): n (acrylic acid): n (N-methylolacrylamide): n (functional monomer) ═ 1:7:4:3, the reaction temperature is 60 ℃, and the reaction time is 4-5 h.
And then carrying out structural analysis on the final product water reducing agent:
the infrared spectrum of the functional monomer is shown in figure 1, and can be seen from figure 1, at 3467cm-1A wide and strong-OH absorption peak appears at the position, which is intramolecular association-OH, and shows that-OH at the tail end of a macromonomer branch chain forms a large number of intramolecular hydrogen bonds. At 3031, 2973cm-1Is a C-H bond stretching vibration peak, and the characteristic absorption peak of the ester group is the stretching vibration peak of C ═ O and C-O-C, 1743cm-1The strong absorption peak is the stretching vibration peak of carbonyl in ester group, 1168cm-1Is an asymmetric C-O-C stretching vibration peak, and proves the existence of the carboxylic ester. In addition, C ═ C double bonds and CH are present2The stretching vibration peak of (1). It is demonstrated that the number of ester groups formed in the synthesis of functional macromonomer is large and the reaction proceeds sufficiently.
Optimally synthesized water-reducing agentThe infrared spectrum of the agent is shown in figure 2, 3500cm-1-3000cm-1Shows an-OH absorption peak at 2879cm-1Is positioned at 1720cm of C-H bond stretching vibration peak-1Is the stretching vibration peak of carbonyl in ester group, 1650cm-1Is a stretching vibration peak of-C ═ O-in the amide group, 1571cm-1Characteristic absorption peak of bending vibration having a series of hydroxyl groups and C-H bonds of alkane, 1095cm-1Is an asymmetric stretching vibration peak of ether bond. 1680cm-1The compound has a stretching vibration peak of C, and no absorption peak is nearby, so that residual double bonds are few, and the polymerization reaction is relatively completely carried out; the molecular structure of the water reducer is proved to have carboxyl, amido, ester and ether groups, which shows that the structure of the synthesized water reducer is consistent with that of the formula (I).
The water reducing agent synthesized under the optimum conditions is subjected to gel permeation chromatography to obtain molecular weight results shown in Table 3, and GPC chromatogram is shown in FIG. 3, wherein M isnIs the number average molecular weight, MwIs the weight average molecular weight, MzIs the Z average molecular weight, Mw/MnThe dispersibility index. General Mw/MnA dispersity index of less than 2 indicates a narrow molecular weight distribution. Mz，Mw，MnThe molecular weight is large, which indicates that the proportion of molecules with large molecular weight in the molecules is higher; mw/Mn1.75, the molecular weight distribution of the synthesized water reducing agent is relatively uniform. According to the molecular weight measurement result, if x, y and z in the molecular structural formula of the water reducing agent are 1, calculating according to the weight average molecular weight, and the theoretical degree of polymerization of the synthesized water reducing agent molecules is 12-15; the theoretical degree of polymerization is 8-10, calculated as the number average molecular weight.
TABLE 3 molecular weight results for water reducing Agents
In order to further research the influence of the synthesis of the early-strength slump-retaining water reducer on the formation of early hydration products of cement, a 1d hydration-stage cement paste test block is characterized and tested by XRD (X-ray diffraction), FIG. 4 is an XRD (X-ray diffraction) spectrum of a 1d hydration-stage blank sample and a water reducer-doped cement sample, and it can be seen from the XRD spectrum that calcium in the hydration products of the water reducer-doped cement sample is compared with that of the blank sampleThe diffraction peak intensity of the alumite AFt is higher, the diffraction peak of the AFm is more obvious, and simultaneously, the unhydrated clinker mineral C3S and C2Higher diffraction peak intensity of S, Ca (OH)2The diffraction peak intensity is lower. The hydration process of silicate minerals is delayed to a certain extent by doping the water reducing agent, but the generation of AFt is promoted, the AFt is converted into AFm quickly, gypsum is basically consumed completely, the hydration rate is accelerated, and a certain early strength effect is achieved. From the molecular structure analysis of the synthesized polycarboxylate superplasticizer, the amide group with early strength function can be in lone electron pair with Ca in cement slurry2+And the reaction is carried out to form soluble calcium salt complex, so that the reaction induction period is ended in advance, and the generation of ettringite is promoted, thereby accelerating the hydration process of cement. The ester group with slump retention property is hydrolyzed under alkaline condition to generate carboxyl, and the carboxyl can also react with Ca2+React to form soluble calcium salt, and reduce Ca in cement slurry2+Thereby delaying Ca (OH)2And the generation of calcium silicate hydrate gel products, and meanwhile, the carboxyl has strong adsorption effect on cement particles and strong dispersion retention performance. This is in substantial agreement with the results of the XRD analysis.
The above-described embodiments should not be construed as limiting the scope of the invention, and any alternative modifications or alterations to the embodiments of the present invention will be apparent to those skilled in the art.
The present invention is not described in detail, but is known to those skilled in the art.
Claims (9)
1. The utility model provides an early strong slump retaining type polycarboxylate water reducing agent which characterized in that: the structural formula of the early-strength slump-retaining polycarboxylic acid water reducer is shown as the formula (I):
wherein n, x, y, z are positive integers; the early-strength slump-retaining polycarboxylic acid water reducer comprises the following components in parts by weight: methallyl polyoxyethylene ether: 0.8-1.2 parts; n-methylolacrylamide: 3-5 parts; functional monomer: 2-4 parts; acrylic acid: 5-9 parts of a solvent; ammonium persulfate: 0.02-0.04 parts of sodium bisulfite: 0.01-0.02 parts of chain transfer agent: 0.005-0.01 portion; the structural formula of the functional monomer is shown as the formula (II):
2. the early strength slump retaining type polycarboxylic acid water reducer according to claim 1, characterized in that: the functional monomer is synthesized according to the following steps: adding maleic acid and tartaric acid with equal amount of substances into a reactor, heating to 60-80 deg.C, stirring under reflux condensation for 20-50min, dripping triethanolamine with equal amount of substances into the reactor with a constant pressure dropping funnel, heating to 95-105 deg.C, sealing for 5-6h, and naturally cooling to obtain the functional monomer.
3. The early strength slump retaining type polycarboxylic acid water reducer according to claim 1, characterized in that: the chain transfer agent is mercaptopropionic acid, mercaptoacetic acid, isopropanol, sodium methyl propylene sulfonate, alkyl mercaptan or alkyl dithioxanthate.
4. The preparation method of the early strength slump retaining polycarboxylic acid water reducer as claimed in claim 1, characterized in that: the method comprises the following steps:
s1, adding methyl allyl polyoxyethylene ether, N-hydroxymethyl acrylamide, a functional monomer and water into a reactor, and heating to dissolve;
s2, adding sodium bisulfite when the temperature is raised to 50-70 ℃, and then stirring for not less than 10 min;
s3, dropwise adding the prepared chain transfer agent solution, acrylic acid solution and ammonium persulfate solution into the reactor by using a constant-pressure dropping funnel respectively at the dropping speed of 0.15-0.30ml/min, and then keeping the temperature to continue reacting for 1.0-1.5 h;
and S4, after the reaction is finished, cooling to 20-30 ℃, and adjusting the pH value to 6.5-7.5 by using a sodium hydroxide solution to obtain a final product.
5. The preparation method of the early strength slump retaining type polycarboxylic acid water reducer as claimed in claim 4, characterized in that: in S3, the last addition of the ammonium persulfate solution is completed, and the delay is at least 30 min.
6. The preparation method of the early strength slump retaining type polycarboxylic acid water reducer as claimed in claim 4, characterized in that: in S4, the sodium hydroxide solution has a sodium hydroxide mass fraction of 30% to 50%.
7. The preparation method of the early strength slump retaining type polycarboxylic acid water reducer as claimed in claim 4, characterized in that: the chain transfer agent is mercaptopropionic acid, mercaptoacetic acid, isopropanol, sodium methyl propylene sulfonate, alkyl mercaptan or alkyl dithioxanthate.
8. The preparation method of the early strength slump retaining type polycarboxylic acid water reducer as claimed in claim 4, characterized in that: in S3, the concentration of the chain transfer agent solution is 0.20-0.30 mol/L.
9. The preparation method of the early strength slump retaining type polycarboxylic acid water reducer as claimed in claim 4, characterized in that: in S3, the concentration of the acrylic acid solution is 0.03-0.06 mol/L; the concentration of the ammonium persulfate solution is 0.03-0.06mol/L, the mass of the used ammonium persulfate is 2-4% of that of the vinyl monomer, and the molar ratio of the used sodium bisulfite to the ammonium persulfate is 1: 1.5-2.5.
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| CN112011015A (en) * | 2020-09-10 | 2020-12-01 | 贵州铁建恒发新材料科技股份有限公司 | Method for preparing slump-retaining type polycarboxylate superplasticizer by modifying maleic anhydride with tartaric acid |
| CN112646090A (en) * | 2020-12-23 | 2021-04-13 | 惠州市华力得建材有限公司 | Super early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN113185179B (en) * | 2021-05-17 | 2022-06-24 | 无锡南方混凝土有限公司 | Super slump retaining concrete additive, preparation method thereof and super slump retaining concrete |
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| CN106397681A (en) * | 2016-08-24 | 2017-02-15 | 安徽鑫固环保股份有限公司 | Early-strength-type polycarboxylic high-performance water reducing agent and preparation method thereof |
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