CN104861127A - Preparation method for anti-mud-type polycarboxylic-acid water-reducing agent and application thereof - Google Patents
Preparation method for anti-mud-type polycarboxylic-acid water-reducing agent and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method for an anti-mud-type polycarboxylic-acid water-reducing agent and application thereof. The method is used to improve production efficiency of the anti-mud-type polycarboxylic-acid water-reducing agent, save energy and reinforce anti-mud performance and gradual plasticity-maintaining property of the anti-mud-type polycarboxylic-acid water-reducing agent. The preparation method for the anti-mud-type polycarboxylic-acid water-reducing agent provided by the invention comprises the following steps: under the normal temperature condition of 5 to 35 DEG C, mixing isobutylene alcohol polyoxyethylene ether and maleic anhydride-beta-cyclodextrin and then dissolving the mixture in water; adding a mixed solution of acrylic acid and p-styryl formate; adding hydrogen peroxide; under the protection of nitrogen, adding a mixed solution of mercaptopropionic acid and ascorbic acid, a mixed solution of acylic acid and p-styryl formate, and sodium dithionite; and adding an aqueous sodium hydroxide solution and adjusting the pH value to 6 to 7 so as to obtain the anti-mud-type polycarboxylic-acid water-reducing agent. The anti-mud-type polycarboxylic-acid water-reducing agent provided by the invention has a cup-shaped structure.
Description
Technical field
The present invention relates to material of construction cement water reducing agent field, particularly relate to a kind of preparation method and application thereof of anti-chamotte mould polycarboxylate water-reducer.
Background technology
Anti-chamotte mould polycarboxylate water-reducer is the class that proposes the eighties in the last century water reducer of new generation by the unsaturated monomer containing carboxyl and other monomer polymerization, there is due to it advantages such as volume is low, water-reducing rate is high, function is adjustable, environmental protection, oneself is widely used in middle low grade ready mixed concrete industry, but anti-chamotte mould polycarboxylate water-reducer is especially responsive to the clay mineral component of aggregate in low-grade concrete application process.Along with the explosive growth of concrete construction amount in recent years, quality sand and stone aggregate resources falls sharply, and aggregate silt content improves constantly, and along with the increase of clay content, mixes anti-chamotte mould polycarboxylate water-reducer concrete initial fluidity, slump retention performance constantly reduces.Although can be eased by improving water reducer volume, easily causing the problem such as concrete coagulating time overlength and compressive strength rate reduction, and greatly increasing cost.
Disclose in patent CN 101798197A and a kind of suppress to gather materials silt content slow release polycarboxylate water reducing agent, it is primarily of anti-chamotte mould polycarboxylate water-reducer, retardant and natural zeolite powder is composite forms.Because clay mineral can be preferentially adsorbed on natural zeolite powder particle surface, so anti-chamotte mould polycarboxylate water-reducer molecule is liberated, be more easily adsorbed in cement particle surface, thus alleviate the clay problem excessive to poly carboxylic acid molecular adsorption.But because zeolite vesicular structure also can adsorb too much poly carboxylic acid molecule, therefore ready mixed concrete will reach identical degree of mobilization, still can add large dosage.
In patent CN 102617811A, disclose the anti-mud agent of a kind of amphoteric ethylene polymkeric substance, traditional poly carboxylic acid molecular structure introduces vinyl-based cationic monomer.This anti-mud agent mainly utilizes the adsorption to earth and quaternary amine positive and negative charge, and shielding clay is to the absorption of water reducer.But this product is as a class sacrifice agent, and not only production cost is high, but also need other water reducer of compound jointly to use, its cost performance is not as small molecules quaternary ammonium salt compound.
Anti-chamotte mould polycarboxylate water-reducer of a kind of anti-chamotte mould and preparation method thereof is disclosed in patent CN103897116A, adopt vinyl Soxylat A 25-7, Sodium styrene sulfonate, vinylformic acid and acrylamides to be monomer, be polymerized under redox initiation system.This invention uses active higher vinyl Soxylat A 25-7 to be polymeric monomer, and reaction conversion ratio is higher, and product water-reducing rate is large.But its molecule is pectination, side chain easily enters clay skeleton construction, causes water reducer volume excessive.
But prior art prepares anti-chamotte mould polycarboxylate water-reducer, have requirement in various degree for temperature, generated time is long, needs heating, expends the energy, the prepared anti-mud of anti-chamotte mould polycarboxylate water-reducer and through time protect plasticity poor.
Summary of the invention
Embodiments provide a kind of preparation method and application thereof of anti-chamotte mould polycarboxylate water-reducer, prepare anti-chamotte mould polycarboxylate water-reducer consuming time short, efficiency is high, do not need heating, save the energy, prepared anti-chamotte mould polycarboxylate water-reducer agent anti-mud performance and through time protect plasticity can be superior.
The preparation method of the anti-chamotte mould polycarboxylate water-reducer of the present invention, at the active slightly high vinylformic acid of the initial front introducing portion of polyreaction-to styrylformic acid ester mix monomer, active lower maleic anhydride-beta-cyclodextrin monomer conversion can be improved, and then shorten anti-chamotte mould polycarboxylate water-reducer generated time, enhance productivity; Simultaneously, the present invention introduces ternary redox-catalyst system, can maleic anhydride-beta-cyclodextrin, isobutene alcohol Soxylat A 25-7 and acrylic acid polyreaction that under normal temperature condition, catalytic activity is lower efficiently, production process is without the need to heating, low-carbon (LC), efficient, environmental protection, be applicable to commercial scale production.
Further, the anti-chamotte mould polycarboxylate water-reducer of anti-chamotte mould prepared by the present invention introduces cup-shaped and rigid structure unit in poly carboxylic acid molecular structure, poly carboxylic acid molecule space steric hindrance can be increased, weaken itself and clay mineral to intert and act on, while guarantee is compared with high water reducing rate, effectively improve the anti-mud function of anti-chamotte mould polycarboxylate water-reducer.
In view of this, the invention provides a kind of preparation method and application thereof of anti-chamotte mould polycarboxylate water-reducer, can comprise:
(1) under 5 ~ 35 DEG C of normal temperature conditions, isobutene alcohol Soxylat A 25-7, maleic anhydride-beta-cyclodextrin are mixed soluble in water, obtains monomer solution;
(2) by vinylformic acid be mixed to get vinylformic acid to styrylformic acid ester and to styrylformic acid ester mixed solution;
(3) in described monomer solution, the described vinylformic acid of part is added and to styrylformic acid ester mixed solution;
(4) hydrogen peroxide is added;
(5) thiohydracrylic acid and xitix mixed solution, residual acrylic acid and to styrylformic acid ester mixed solution, V-Brite B is added under nitrogen protection;
(6) adding aqueous sodium hydroxide solution regulates pH to be 6-7, obtains anti-chamotte mould polycarboxylate water-reducer.
Preferably, described butenol Soxylat A 25-7, vinylformic acid, be 100-130:15-25:1-5:5-15:0.1-10.0:0.3-1.2:0.1-1.0:0.5-5.0 to styrylformic acid ester, maleic anhydride-beta-cyclodextrin, thiohydracrylic acid, xitix, V-Brite B, hydrogen peroxide quality proportioning.
Preferably, in mass, step (2) described part acrylic acid and be described vinylformic acid and (5-15) % to styrylformic acid ester to styrylformic acid ester mixed solution.
Preferably, step (5) was added complete in 2.0-3.5 hour.
Preferably, described V-Brite B starts to add after reaction carries out 0.5-1.5 hour.
Preferably, described vinylformic acid is the aqueous solution to styrylformic acid ester mixed solution, and mass concentration is (80-95) %.
Preferably, in mass, the concentration of described monomer solution is (50-70) %, described hydrogen peroxide is (27-50) % aqueous solution, described thiohydracrylic acid and xitix mixed solution are (1-15) % aqueous solution, and described V-Brite B adopts (20-40) % aqueous solution.
The present invention also provides a kind of anti-chamotte mould polycarboxylate water-reducer, and described anti-chamotte mould polycarboxylate water-reducer adopts the preparation method of aforementioned anti-chamotte mould polycarboxylate water-reducer to obtain.
Preferably, described anti-chamotte mould polycarboxylate water-reducer is cup-like structure.
The present invention also provides the application of anti-chamotte mould polycarboxylate water-reducer in concrete.
The object of the invention is to for the anti-chamotte mould polycarboxylate water-reducer problem larger to sandstone silt content susceptibility, under normal temperature condition, use three-element catalytic system to synthesize the anti-chamotte mould polycarboxylate water-reducer of the anti-chamotte mould of a class cup-like structure.Sterically hinderedly weaken the interspersed adsorption of molecule to clay mineral by increasing, solve silt content higher time, the phenomenon that anti-chamotte mould polycarboxylate water-reducer volume is large, concrete gradual loss is too fast.
The present invention relates to process characteristic to be: 1. improve poly carboxylic acid molecule by introducing cyclodextrin cup-like structure and styrenic rigid radical and prop up chain size, weaken and intert between clay seam acting on, improve the anti-mud performance of product; 2. amount of activated monomer and inert monomer premix are merged and introduce three-element catalytic system, by reducing activation energy, improving normal temperature, high efficiency that initial reaction speed realizes poly carboxylic acid production technique.This invention relates to product and not only has higher water-reducing rate, also has good anti-mud and protects effect of collapsing, and effectively can improve the ready mixed concrete production status that sandstone aggregate anxiety, silt content are too high.
Embodiment
Embodiments provide a kind of preparation method and application thereof of anti-chamotte mould polycarboxylate water-reducer, prepare anti-chamotte mould polycarboxylate water-reducer consuming time short, efficiency is high, do not need heating, save the energy, prepared anti-chamotte mould polycarboxylate water-reducer agent anti-mud performance and through time protect plasticity can be superior.
The invention provides a kind of preparation method of anti-chamotte mould polycarboxylate water-reducer, comprising:
Material prepares, and butenol Soxylat A 25-7, vinylformic acid, is 100-130:15-25:1-5:5-15:0.1-10.0:0.3-1.2:0.1-1.0:0.5-5.0 to styrylformic acid ester, maleic anhydride-beta-cyclodextrin, thiohydracrylic acid, xitix, V-Brite B, hydrogen peroxide quality proportioning;
Under 5 ~ 35 DEG C of normal temperature conditions, mix soluble in water by isobutene alcohol Soxylat A 25-7, maleic anhydride-beta-cyclodextrin, obtain monomer solution, mass concentration is (50-70) %;
By vinylformic acid with to the mixing of styrylformic acid ester, be configured to mass concentration for the aqueous solution of (80-95) %, obtain vinylformic acid and to styrylformic acid ester mixed solution;
Vinylformic acid described in (5-15) % is added and to styrylformic acid ester mixed solution in described monomer solution;
Add (27-50) % aqueous hydrogen peroxide solution;
Add mass concentration to be under nitrogen protection the thiohydracrylic acid of (1-15) % and xitix mixed aqueous solution, to remain described vinylformic acid and be the V-Brite B of (20-40) % to styrylformic acid ester mixed solution, mass concentration, added complete in 2.0-3.5 hour, wherein V-Brite B starts to add after reaction carries out 0.5-1.5 hour;
Adding aqueous sodium hydroxide solution regulates pH to be 6-7, obtains anti-chamotte mould polycarboxylate water-reducer.
Anti-chamotte mould polycarboxylate water-reducer prepared by the present invention is cup-like structure, is mainly used in concrete field.
The preparation method of the anti-chamotte mould polycarboxylate water-reducer of the present invention, at the active slightly high vinylformic acid of the initial front introducing portion of polyreaction-to styrylformic acid ester mix monomer, active lower maleic anhydride-beta-cyclodextrin monomer conversion can be improved, and then shorten anti-chamotte mould polycarboxylate water-reducer generated time, enhance productivity; Simultaneously, the present invention introduces ternary redox-catalyst system, can maleic anhydride-beta-cyclodextrin, isobutene alcohol Soxylat A 25-7 and acrylic acid polyreaction that under normal temperature condition, catalytic activity is lower efficiently, production process is without the need to heating, low-carbon (LC), efficient, environmental protection, be applicable to commercial scale production.
Further, anti-chamotte mould polycarboxylate water-reducer prepared by the present invention introduces cup-shaped and rigid structure unit in poly carboxylic acid molecular structure, poly carboxylic acid molecule space steric hindrance can be increased, weaken itself and clay mineral to intert and act on, while guarantee is compared with high water reducing rate, effectively improve the anti-mud function of anti-chamotte mould polycarboxylate water-reducer.
Anti-chamotte mould polycarboxylate water-reducer prepared by the present invention consuming time short, efficiency is high, do not need heating, save the energy, prepared anti-chamotte mould polycarboxylate water-reducer agent anti-mud performance and through time protect plasticity can be superior.
In order to make those skilled in the art understand technical scheme of the present invention better, below by specific embodiment, the present invention is described in further detail.
Embodiment 1
18.0g vinylformic acid is mixed styrylformic acid ester with 4.0g, and adds deionized water, be mixed with the solution A of 80% concentration.
0.7g xitix is mixed with 1.0g thiohydracrylic acid, and adds deionized water, be mixed with the solution B of 5% concentration.
3.0g V-Brite B is mixed with 7.0g deionized water, is mixed with the solution C of 30% concentration.
At normal temperature 20 DEG C, by 120.0g molecular weight be 2400 isobutene alcohol Soxylat A 25-7 and 7.0g maleic anhydride-beta-cyclodextrin join in reactor, adding 98.0g deionized water again, to be mixed with monomer mass concentration be 56% large monomer solution, then add 3.0g solution A, to be mixed evenly after add 3.0g 27.5% superoxol.Said mixture starts after stirring 10 minutes to drip solution B, remaining solution A and solution C under nitrogen protection, drips and controls respectively to complete in 2.0,2.5,1.5 hours, and wherein solution C drips after 0.5 hour in reaction beginning.Dropwise and need not be incubated, until temperature be naturally down to after room temperature with 30% aqueous sodium hydroxide solution adjustment pH be 6-7, obtain the anti-chamotte mould polycarboxylate water-reducer of anti-chamotte mould.
Embodiment 2
21.0g vinylformic acid is mixed styrylformic acid ester with 2.5g, and adds deionized water, be mixed with the solution A of 85% concentration.
0.5g xitix is mixed with 0.5g thiohydracrylic acid, and adds deionized water, be mixed with the solution B of 2.5% concentration.
1.5g V-Brite B is mixed with deionized water, is mixed with the solution C of 35% concentration.
At normal temperature 5 DEG C, by 130.0g molecular weight be 2400 isobutene alcohol Soxylat A 25-7 and 5.5g maleic anhydride-beta-cyclodextrin join in reactor, adding 60.0g deionized water again, to be mixed with monomer mass concentration be 69% large monomer solution, then add 2.0g solution A, to be mixed evenly after add 1.5g 27.5% superoxol.Said mixture starts after stirring 10 minutes to drip solution B, remaining solution A and solution C under nitrogen protection, drips and controls respectively to complete in 2.0,2.0,1.0 hours, and wherein solution C starts to drip in reaction for latter 0.5 hour.Dropwise and need not be incubated, until temperature be naturally down to after room temperature with 30% aqueous sodium hydroxide solution adjustment pH be 6-7, obtain the anti-chamotte mould polycarboxylate water-reducer of anti-chamotte mould.
Embodiment 3
15.0g vinylformic acid is mixed with 4.0 pairs of styrylformic acid esters, and adds deionized water, be mixed with the solution A of 90% concentration.
1.0g xitix is mixed with 0.6g thiohydracrylic acid, and adds deionized water, be mixed with the solution B of 15% concentration.
2.0g V-Brite B is mixed with deionized water, is mixed with the solution C of 20% concentration.
At normal temperature 35 DEG C, by 100.0g molecular weight be 2400 isobutene alcohol Soxylat A 25-7 and 15.0g maleic anhydride-beta-cyclodextrin join in reactor, adding 30.0g deionized water again, to be mixed with monomer mass concentration be 79% large monomer solution, then add 1.0g solution A, to be mixed evenly after add 5.0g 27.5% superoxol.Said mixture starts after stirring 10 minutes to drip solution B, remaining solution A and solution C under nitrogen protection, drips and controls respectively to complete in 2.0,2.5,1.5 hours, and wherein solution C starts to drip in reaction for latter 1.5 hours.Dropwise and need not be incubated, until temperature be naturally down to after room temperature with 30% aqueous sodium hydroxide solution adjustment pH be 6-7, obtain the anti-chamotte mould polycarboxylate water-reducer of anti-chamotte mould.
Embodiment 4
The present invention, by introducing maleic anhydride-beta-cyclodextrin class large space steric hindrance monomer, weakens poly carboxylic acid molecule (PCE) and acts on the interlayer of clay composition is interspersed, thus obtain anti-mud performance, the better product of function of slump protection.
According to the preparation method of the anti-chamotte mould polycarboxylate water-reducer of the present invention, when other conditions are identical, prepare two kinds of anti-chamotte mould polycarboxylate water-reducers respectively, A group is for being non-maleic anhydride-beta-cyclodextrin of mixing, B group mixes 6% maleic anhydride-beta-cyclodextrin, contrast the adsorption of itself and clay, result is as shown in the table:
The anti-chamotte mould polycarboxylate water-reducer of two kinds, table 1 compares with polynite effect
From table 1 result, under condition not argillaceous, two kinds of PCE all show good initial dispersion with through time protect plasticity energy, meet product construction requirement completely.After substituting 2% cement with clay, common PCE concrete flowability diminishes and gradual loss is serious, and within 1 hour, slump-loss reaches 50mm.The PCE initial flow degree mixing 6% maleic anhydride-beta-cyclodextrin monomer on the contrary still reaches 180mm, without obvious gradual loss, maintains good serviceability.When the clay amount of substituting is more than 4%, common PCE mixing concrete slump only has 80mm, without any mobility after 1 hour, but with under condition, the PCE mixing maleic anhydride-beta-cyclodextrin monomer then show good initial dispersion effect and through time protect and mould ability, within 1 hour, slump-loss is no more than 20mm.These results suggest that the introducing of maleic anhydride-beta-cyclodextrin monomer can increase poly carboxylic acid molecule space steric hindrance, weaken itself and clay mineral to intert and act on, while guarantee is compared with high water reducing rate, effectively improve the anti-mud function of anti-chamotte mould polycarboxylate water-reducer, demonstrate its large cup-shaped space structure and effectively limit the adsorption of poly carboxylic acid molecule to clay.
Embodiment 5
As embodiment 1, add solution A in two steps, be labeled as feed postition 2; Other conditions are identical, change the addition manner of solution A, change into and slowly drip solution A continuously, be labeled as feed postition 1; Other conditions are identical, change the addition manner of solution A, change a property time into and add solution A, be labeled as feed postition 3.Anti-chamotte mould polycarboxylate water-reducer performance test data prepared by the addition means of three kinds of solution A is as shown in table 2.
Table 2 B expects concrete performance test result under different dropping mode
From table 2 result, feed postition 2 concrete initial slump is obviously greater than feed postition 1, the feed postition 2 concrete slump almost free of losses after 1 hour simultaneously, feed postition 1 concrete slump then have lost 10mm, although feed postition 3 initial dispersion effect is excellent, but slump-loss is exceedingly fast, less than 10 minutes completely without mobility.Reason is: the polymerization activity of isobutene alcohol Soxylat A 25-7 is relatively low, when minor comonomer employing drips continuously, initial reaction stage reactive monomer concentration is lower, can not effectively be polymerized between isobutene alcohol polyoxyethylene ether monomer, reacts in initial 1 hour and generates without obvious diminishing molecular structure.Contrary minor comonomer adopts and disposablely adds fashionable completely, and initial reaction stage reactive monomer concentration is higher, and form macromolecule polyacrylic polymer fast each other, TPEG transformation efficiency is relatively low, and product initial stage dispersion effect is better, but gradual loss is fast.The active minor comonomer feed postition of this result verification can have material impact to the water-reducing property of product and protect plasticity.
The present invention adds (5-15) % vinylformic acid early stage and to styrylformic acid ester mixed solution, the later stage adds remainder under nitrogen protection, and obtained anti-chamotte mould polycarboxylate water-reducer water-reducing property and protect plasticity significantly improve.
In addition, than the generated time of usual way 4-6 hour, 3 hours consuming time of the preparation method of the present invention's anti-chamotte mould polycarboxylate water-reducer, greatly save preparation time, efficiency is high, is conducive to suitability for industrialized production.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for anti-chamotte mould polycarboxylate water-reducer, is characterized in that, comprising:
(1) under 5 ~ 35 DEG C of normal temperature conditions, isobutene alcohol Soxylat A 25-7, maleic anhydride-beta-cyclodextrin are mixed soluble in water, obtains monomer solution;
(2) by vinylformic acid be mixed to get vinylformic acid to styrylformic acid ester and to styrylformic acid ester mixed solution;
(3) in described monomer solution, the described vinylformic acid of part is added and to styrylformic acid ester mixed solution;
(4) hydrogen peroxide is added;
(5) thiohydracrylic acid and xitix mixed solution, residual acrylic acid and to styrylformic acid ester mixed solution, V-Brite B is added under nitrogen protection;
(6) adding aqueous sodium hydroxide solution regulates pH to be 6-7, obtains anti-chamotte mould polycarboxylate water-reducer.
2. according to the preparation method of the anti-chamotte mould polycarboxylate water-reducer described in claim 1, it is characterized in that, described isobutene alcohol Soxylat A 25-7, vinylformic acid, be 100-130:15-25:1-5:5-15:0.1-10.0:0.3-1.2:0.1-1.0:0.5-5.0 to styrylformic acid ester, maleic anhydride-beta-cyclodextrin, thiohydracrylic acid, xitix, V-Brite B, hydrogen peroxide quality proportioning.
3. according to the preparation method of the anti-chamotte mould polycarboxylate water-reducer described in claim 2, it is characterized in that, in mass, step (3) described part acrylic acid and be described vinylformic acid and (5-15) % to styrylformic acid ester to styrylformic acid ester mixed solution.
4. according to the preparation method of the anti-chamotte mould polycarboxylate water-reducer described in claim 1, it is characterized in that, step (5) was added complete in 2.0-3.5 hour.
5. according to the preparation method of the anti-chamotte mould polycarboxylate water-reducer described in claim 4, it is characterized in that, described V-Brite B starts to add after reaction carries out 0.5-1.5 hour.
6. according to the preparation method of the anti-chamotte mould polycarboxylate water-reducer described in claim 1, it is characterized in that, described vinylformic acid and be the aqueous solution to styrylformic acid ester mixed solution, mass concentration is (80-95) %.
7. according to the preparation method of the anti-chamotte mould polycarboxylate water-reducer described in claim 1, it is characterized in that, in mass, the concentration of described monomer solution is (50-70) %, described hydrogen peroxide is (27-50) % aqueous solution, described thiohydracrylic acid and xitix mixed solution are (1-15) % aqueous solution, and described V-Brite B adopts (20-40) % aqueous solution.
8. an anti-chamotte mould polycarboxylate water-reducer, is characterized in that, described anti-chamotte mould polycarboxylate water-reducer adopts right to ask the preparation method of the anti-chamotte mould polycarboxylate water-reducer described in 1-7 to obtain.
9. according to Claim 8 described in anti-chamotte mould polycarboxylate water-reducer, it is characterized in that, described anti-chamotte mould polycarboxylate water-reducer is cup-like structure.
10. the application of anti-chamotte mould polycarboxylate water-reducer according to claim 8 in concrete.
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| CN105778012A (en) * | 2016-03-21 | 2016-07-20 | 中国科学院兰州化学物理研究所 | Method for preparing anti-mud polycarboxylic acid water reducing agents |
| CN106397686A (en) * | 2016-09-29 | 2017-02-15 | 湖北工业大学 | Modified polycarboxylate superplasticizer master batch and preparation method thereof |
| CN106749901A (en) * | 2015-11-20 | 2017-05-31 | 衡阳市银利实业有限公司 | A kind of method for preparing anti-chamotte mould cement water reducing agent |
| CN107501479A (en) * | 2017-08-16 | 2017-12-22 | 科之杰新材料集团有限公司 | A kind of preparation method of viscosity reduction type polycarboxylate water-reducer |
| CN108948294A (en) * | 2018-07-04 | 2018-12-07 | 武汉源锦建材科技有限公司 | A kind of anti-mud slow-release slump retaining agent and preparation method thereof containing cyclodextrin side group |
| CN109534715A (en) * | 2018-12-14 | 2019-03-29 | 南京福盛建材有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer and preparation method thereof |
| CN111592272A (en) * | 2019-09-11 | 2020-08-28 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Polycarboxylate superplasticizer for machine-made sand concrete prestressed component and preparation method thereof |
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